# Patent

## Title
Inkjet recording method and inkjet recording apparatus

## Abstract

An inkjet recording method and apparatus including: forming a color image with color inks and an invisible ink by while scanning a first recording head multiple times on a same recording area, forming a thinned-out image, and jetting an invisible ink from a second recording head in accordance with an adhering amount of the color inks per, wherein a nozzle pitch of the first recording head is from 10 to 50 μm, the color inks comprise C, M, Y and BK inks and at least one special color ink, the color inks contain pigments, at least one organic solvent with high boiling point and water, a dot formed color inks has a size of 10 to 50 μm, and the recording medium has a transferred amount at 0.04 seconds of absorption time of 10 ml/m2 or more, a micro-porous layer containing inorganic fine particles and a hydrophilic binder.

## Background
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a novel inkjet recording method and inkjet recording apparatus.
2. Description of Related Art
An inkjet recording mode is one for recording images and texts by flying minute droplets of ink to adhere onto a recording medium by various operation principles, and has advantages such as relatively high speed, low noise and easiness of multiple coloration. In the above inkjet recording mode, various improvements have been performed in various fields such as an ink, inkjet recording medium and inkjet recording apparatus, and at present, the mode has become rapidly popular for various fields such as various printers, facsimiles and computer terminals. In particular, recently high-quality picture technology in the printer has been improved, and its level has come at a picture quality of photograph.
As the inkjet recording apparatus used in the inkjet recording mode, for enhancing a printing speed, those where multiple ink jet openings (nozzle sections) and ink liquid paths are integrated as a recording head where multiple recording elements are integrated/arrayed (hereinafter also referred to as a multihead) are used. Additionally, for corresponding to coloration, those where multiple recording heads composed of the above configuration are comprised are frequently used. In that case, it is general that heads which ejaculate inks of respective colors are disposed in parallel with a main scanning direction.
Here, when a color image picture is printed, differently from those where only characters are printed in a black-and-white printer, various factors such as color density, gradation and uniformity are important to obtain high-quality pictures. In particular, with respect to the uniformity, slight dispersion of nozzle units which occurs in difference of multihead fabrication steps influences jetting amounts and jetting directions of inks at respective nozzles, and becomes a cause which finally deteriorates image quality as uneven density of a printed image. Also, speed variation at a main scanning of a carriage where heads are loaded, variation of sub scanning paper feeding amount of the recording medium, and variation of a distance between a recording medium surface and a nozzle face on the recording medium cause deterioration of the image.
For the above problems, a so-called multi-pass recording method has been proposed where image deterioration due to the dispersion of respective nozzles and various variations is reduced by scanning multiple times the recording head having multiple nozzle sections onto the same recording area on the inkjet recording medium and forming an image of a complementary thinning-out pattern. As a mask used in this case, as described in JP-Tokukaisho-60-107975A, the method of using a complementary pattern with a constant thinning-out rate of a certain rule is the commonest.
However, as described below, when using such a regular mask, conversely uneven colors, stripe unevenness and white spots sometimes remarkably appear, and thus, the method of using a mask pattern without regularity has been proposed as an improving countermeasure of this. By forming an image thinned out of this thinning-out pattern without regularity, it is possible to prevent the uneven density and uneven colors produced due to a synergistic effect of regularity of the image and regularity of the mask, and realize high-quality picture and high speed printing to some extent (for example, refer to JP-Tokukaihei-7-52390A, JP-Tokukai-2002-96461A, and JP-Tokukai-2002-144552A.).
Whereas, the present applicant has found that when a certain inks and a recording medium is used, and in particular when high-quality printing such as silver halide photograph is required, sufficient image quality is not obtained only by the proposed thinning-out printing method. This is illustrated below.
The inks used in the inkjet recoding mode are broadly divided into dye inks where color materials are dissolved in solvents and dispersion inks where color materials, mainly pigments are dispersed in solvents. The dye dissolves in the solvents and is in a molecular state or a cluster state, which makes its absorption spectrum sharp, and develops clear color with high purity. Additionally, there is no particle pattern due to particles and no scattered light and reflected light occur, therefore it is possible to obtain an inkjet image with high translucent feeling and clear color phase. The dye has a property excellent in scratch/abrasion resistance because no color material particle is present on the surface of media. The dye, however, has drawbacks of poor light resistance because dye molecules tend to break by photochemical reaction. The reduction in dye molecular number directly reflects upon a color density. It is an actual state that the inkjet recording image using the dye inks is the high image quality but the poor image stability against light, and the technology which is superior to silver halide photographs in the light of stability has not appeared yet.
As the method for solving this problem, pigment inks where the pigments with good light resistance are used as colorants have been used for the intended use where the high light stability is required.
However, when the pigment inks are used, the pigment particles locate at the upper part of the ink accepting layer after the printing. Therefore, it occurs a difference of glossiness, texture and the like between a shadow portion where adhering amount of the ink is large, and a white portion where the surface of a recording medium is exposed or a high-light portion where an adhering amount of the ink is small. As a result, it was impossible to obtain an image of high definition such like a silver halide photograph. An attempt of obtaining an image of high definition which has a quality comparable to an silver halide photograph has been made, in which invisible ink containing polymer latex and the like is jetted onto a non-printed portion of an image in order to dissolve the difference of glossiness between an image portion and a non-image portion and the like, so that glossiness evenness of the surface of a recording medium is improved (for example, see JP-Tokukai-2003-266913A).
In order to prevent uneven image density due to regular pattern of an image, thinned-out image has been used in which the above-described recording head including a plurality of nozzle parts is scanned a plurality times on one recording area of a recording medium and the thinned-out images are formed in each of the scans according to a thinning-out pattern without regularity such as a random pattern.
However, when an inkjet image recording according to the thinning-out pattern without regularity is performed using the pigment inks, a dot position formed at each scanning has no regularity. Therefore, the case where the ink droplets of cyan, magenta, yellow and black are adjacently printed on the inkjet recording medium at the same scanning becomes frequent. As a result, the respective ink droplets are mixed one another, which causes aggregation of pigment particles, and a phenomenon that glossiness of an image portion becomes uneven occurs. Even if the invisible ink is adhered onto a recording medium, it is impossible to obtain an image of high definition and high quality having transparency feeling such as a silver halide photograph.
In particular, in order to form the image at high definition like a silver halide photograph, when a recording medium having a micro-porous layer containing inorganic fine particles with a mean particle size of 100 nm or less is used, an absorption speed of inks is fast and the aggregation of pigment particles present on the recording medium occurs more easily. Besides, it has been found that due to using the mask pattern without regularity, a probability that different color dots are adjacently printed becomes high, and the formation of image at high definition becomes difficult because the pigment particles having different color tone are mixed on the recording medium.
This is because when using the regular thinning-out pattern, the position of each ink formed on the recording medium at one scanning can be finely controlled and mixture of the dots can be effectively inhibited whereas it is difficult to perform such a control in the case without regularity.
SUMMARY OF THE INVENTION
The present invention is made to dissolve the above problems.
According to the first aspect of the invention, an inkjet recording method comprising the step of: forming a color image with color inks and an invisible ink onto a recording medium by while scanning a first recording head multiple times on a same recording area of the recording medium, forming a thinned-out image according to an thinning-out pattern without regularity in each scanning, the first recording head having a plurality of nozzle sections for jetting color inks, and jetting an invisible ink from a second recording head in accordance with an adhering amount of the color inks per unit area on the recording medium, wherein a nozzle pitch of the first recording head is from 10 to 50 μm, the color inks comprise cyan, magenta, yellow and black inks and at least one special color ink, the color inks contain pigments, at least one organic solvent with high boiling point and water, a dot formed by jetting the color inks with the first recording head has a size of 10 to 50 μm on the recording medium, the invisible ink contains water, at least one organic solvent with high boiling point and a resin fine particle, and the recording medium has a transferred amount at 0.04 seconds of absorption time by Bristow method of 10 ml/m2 or more, a micro-porous layer containing inorganic fine particles having a mean particle size of 15 to 100 nm and a hydrophilic binder.
According to the second aspect of the invention, an inkjet recording apparatus for forming a color image on a recording medium by jetting color inks and an invisible ink, comprising: a first recording head having a plurality of nozzle sections to jet the color inks, the nozzle sections being arrayed in a pitch of 10 to 50 μm; a scanning section to make the first recording head scan multiple times on one recording area of the recording medium; a second recording head having a plurality of nozzle sections to jet the invisible ink and a control section to allow the first recording head to jet the color inks from the plurality of nozzle sections so that a thinned-out image according to a thinning-out pattern without regularity in each scanning is formed on the recording medium and the second recording head to jet the invisible ink in accordance with an adhering amount of the color inks per unit area on the recording medium, wherein the color inks comprise at least cyan, magenta, yellow and black inks and at least one special color ink, the color inks contain pigments, at least one organic solvent with high boiling point and water,
a dot formed by jetting the color inks with the first recording head has a size of 10 to 50 μm on the recording medium, the invisible ink contains water, at least one organic solvent with high boiling point and a resin fine particle, and the recording medium has a transferred amount at 0.04 seconds of absorption time by Bristow method is 10 ml/m2 or more, a micro-porous layer containing inorganic fine particles having a mean particle size of 15 to 100 nm and a hydrophilic binder.



BRIEF DESCRIPTION OF THE DRAWINGS
The present invention will become more fully understood from the detailed description given hereinbelow and the appended drawings which given by way of illustration only, and thus are not intended as a definition of the limits of the present invention, and wherein;
FIG. 1 is a perspective view representing a major configuration section of an inkjet printer,
FIG. 2 is a perspective view where a carriage of the inkjet printer is enlarged,
FIG. 3 is a bottom view of recording heads of the inkjet printer,
FIG. 4 is a block diagram representing a control section of the inkjet printer,
FIG. 5 is a block diagram representing a configuration of an image forming apparatus,
FIGS. 6A to 6C are schematic diagrams representing one example of multi-pass printing inkjet recording methods,
FIGS. 7A to 7C are schematic diagrams representing one example of multi-pass printing inkjet recording methods,
FIGS. 8A to 8C are schematic diagrams representing one example of multi-pass printing inkjet recording methods,
FIGS. 9A to 9C are schematic diagrams representing one example of multi-pass printing inkjet recording methods,
FIG. 10 is a schematic diagram representing one example of image alignment patterns arrayed regularly,
FIG. 11 is a schematic diagram representing another example of image alignment patterns arrayed regularly,
FIG. 12 is a schematic diagram showing a printing condition when arrayed image data in an increased duty were input,
FIGS. 13A and 13B are schematic diagrams showing a condition where heads jet ink droplets on a flat face of a recording medium at a constant speed v with moving at a constant speed V in a forth or back direction,
FIG. 14 is a schematic diagram showing a jetted dot condition when an image with 100% duty was bidirectionally printed using staggered thinning-out masks,
FIG. 15 is a schematic diagram showing one example of methods of performing multi-pass recording using masks without regularity,
FIG. 16 is a schematic diagram showing another example of methods of performing multi-pass recording using masks without regularity,
FIG. 17 is a schematic diagram showing one examples of nozzle alignments corresponding to mask patterns,
FIG. 18 is a schematic diagram showing one example of mask patterns with blue noise property,
FIG. 19 is a schematic diagram showing one example of mask patterns,
FIG. 20 is a schematic diagram showing another example of mask patterns,
FIG. 21 is a schematic diagram showing another example of mask patterns,
FIG. 22 is a block diagram showing one example of mask processing circuits,
FIG. 23 is a schematic diagram showing one example of mask patterns used in Comparative Examples,
FIG. 24 is a graph showing one example of a relation between an image data and an amount of used ink,
FIG. 25 is a graph showing one example of a relation between an image data and an amount of used color inks,
FIG. 26 is a view showing one example of an aspect of adhesion of color inks at a high-light portion and
FIG. 27 is a view showing one example of an aspect of adhesion of color inks with invisible ink at a high-light portion.



DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the best modes for carrying out the invention are illustrated in detail, but the invention is not limited thereto.
First, an inkjet printer to which the inkjet recording method of the invention can be applied is illustrated with reference to FIG. 1. FIG. 1 is a perspective view representing a major configuration of the inkjet printer, and the inkjet printer is provided with a first recording head to jet color inks constituting a color ink set and a second recording head to jet invisible ink.
As is shown in the figure, an image forming section 2 to jet the color inks onto a recording material to form an image and to jet the invisible ink onto a non-image portion is installed in the inkjet printer 1. A platen 21 which supports a back face (face opposite to a side of a recorded face) of a recording medium P in a given range by its upper face is nearly horizontally arranged. A guiding member 25 which extends along a scanning direction X over the platen 21, for moving a carriage as scanning member 23 which scans in the scanning direction X is installed in the image forming section 2.
In the carriage 23, recording heads 22 to jet the color inks or invisible ink onto a recording medium and a linear encoder sensor 27 which reads an optical pattern of a linear scale 26 where the optical pattern extends along the scanning direction X and is arranged in its longitudinal direction with 300 dpi cycle to output as clock signals are loaded. Meanwhile, dpi referred to in the invention represents a dot number per 2.54 cm. In the present embodiment, printing operation is performed by dividing this encoder signal, for example, by a printing resolution of 1200 dpi. A moving direction of the carriage 23 is changed by a rotation direction of a driving motor for the carriage, and the carriage 23 is moved back and forth in the scanning direction X by this. At the image formation, the carriage 23 moves forth, back or back and forth when the recording medium stops. A moving speed at that time is, for example, 705 mm/sec at the highest speed.
Next, the recording heads 22 are illustrated in reference to FIG. 2 and FIG. 3. FIG. 2 is a perspective view of the enlarged carriage 23, and FIG. 3 is a bottom view of the recording heads 22.
The recording head 22 may be a piezo mode or a thermal mode, but is preferably the thermal mode in terms of arranging the nozzles at high density, and the recording heads of thermal mode are used in the present embodiment. This recording head 22 is arranged such that a recording face of the recording medium P fed on the platen 21 is faced to a nozzle face 222 at the image recording where the nozzles 221 of the recording heads 22 are formed.
As shown in FIG. 2, total 256 nozzles at a pitch of 42.3 μm (600 dpi) with two rows of each 128 are formed in a feeding direction of the recording medium on the nozzle face 222 of the recording heads. These nozzle rows are arranged with 21.2 μm out of alignment one another. This corresponds to one pixel in 1200 dpi. A distance between two rows is about 500 μm. A thermal inkjet element is installed inside each nozzle 221, and the color inks as a droplet is separately jetted by operation of a jetting member.
The color inks and invisible ink are supplied to each recording head passing through a tube for piping from a cartridge for recording ink which is not shown in the figure. As shown in FIGS. 1 and 2, eight pieces of recording heads 22 are disposed side by side along the scanning direction, and the recording head is composed of the first recording head for color inks, which are used for inks such as light color inks and special color ink as well as 4 color inks of cyan (C), magenta (M), yellow (Y) and black (K) and 3 special color inks, and respectively, and the second recording head for the invisible ink. The above embodiment shows the case where four inks of C, M, Y and K and special color ink are used. However, the same effect of the invention can be obtained in the inkjet printer where pale color ink is used in combination with C, M, Y and K for recording.
Next, An image forming method of the thinned-out image is illustrated, where the first recoding head jetting color inks scans a plural times at a same recording area of a recording medium to form the thinned-out image according to a thinning-out pattern irregular between each of the scanning steps.
First, a control section of the inkjet printer 1 is illustrated in reference to FIG. 4. FIG. 4 is a block diagram representing the control section of the inkjet printer 1.
As shown in FIG. 4, the control section 100 is configured by connecting a feeding motor 101 to feed the recording medium, CPU 103, an interface 104, a driving motor 231 for the carriage, a memory write controller 105, an image memory 106, a memory read controller 107, and a mask processing circuit 108 through a bus 110 as is shown. A detailed configuration of the mask processing circuit 108 is described below. The recording heads 22 of the inkjet printer 1, respective driving sections and the like are also connected to the control section 100.
The control section 100 controls feeding of the recording medium, scanning operation of the carriage 23 and color inks jetting of the recording heads 22, and the like. As is shown in FIG. 4 and FIG. 5, an image forming apparatus 200 such as computer is connected. The image forming apparatus 200 forms an image with multiple colors based on input signals. In this instance, an application program 201 which operates inside the image forming apparatus 200 displays the image on a monitor 300 through a video driver 202 with processing the image. When this application program 201 puts an image formation direction in motion, the printer driver 203 of the image forming apparatus 200 receives image data for the image formation from the application program 201, and the image data are converted into signals capable of forming the image in the inkjet printer 1.
The printer driver 203 comprises a rasterizer 204 which converts the image data dealt in the application program 201 into image gradation data including color information of dot units, a color gradation compensation module 205 which compensates the image gradation data in accordance with color density property and gradation property of the inkjet printer 1, and a halftone module 206 which produces the image data of so-called halftone where a density at a certain area is expressed by the presence or absence of the recording inks at dot units from the image data after the color compensation. A module 207 which performs the thinning-out mask processing can be also incorporated in this printer driver. In that case, a mask setting can be changed depending on a medium type used for the printing, and thus more flexible control is possible than the processing in the printer. When the mask processing circuit 108 is used, the processing at the module 207 is not performed. Conversely, when the mask processing is performed at the module 207, the processing at the mask processing circuit 108 is not performed. Also, it is possible to download a mask pattern every printing from the image processing apparatus 200.
Next, multi-pass inkjet recording method is illustrated. As mentioned above, in the inkjet image recording, particularly when a color image picture is formed, various factors such as color density, gradation and uniformity are required. In particular, with respect to the uniformity, slight unevenness of nozzle units which occurs in difference at multihead fabrication steps influences jetting amounts and jetting directions of color inks at respective nozzles, or strip-shaped unevenness occurs due to mechanical accuracy at movement of the recording medium, and as a result, becomes a cause which finally deteriorates image quality as uneven density of a printed image. Thus, in the present embodiment, to solve such problems, the color image is formed using the multi-pass inkjet recording method where the recording heads 22 are scanned multiple times onto the same recording area of the recording medium.
As the multi-pass ink jet recording method, it is possible to use the method, for example, in JP Tokukaisho 60-107975A. That method is illustrated by FIGS. 6A to 6C and 7A to 7C.
According to this method, to complete a printing area shown in FIGS. 8A to 8C and 9A to 9C, the multihead 1101 is scanned three times, and a half thereof, 4 pixel unit area is completed by 2 passes, that is scanning two times. In this case, 8 nozzles of the multihead are divided into upper 4 nozzles and lower 4 nozzles, and dots printed by scanning one nozzle once are those where defined image data are thinned-out to about a half according to given image data alignment. And at the second scanning, dots are filled in the image data of a remaining half to complete the printing in the 4 pixel unit area.
When using such a recording method, even if using the same one as the multihead shown in FIGS. 9A to 9C, influences intrinsic for each nozzle on a printing image are reduced by half, and therefore, the printed image becomes like FIG. 6B, and black lines and white lines observed in FIG. 9B become indistinctive. Therefore, uneven density as shown in FIG. 6C is considerably alleviated compared to the case of FIG. 9C.
When such recording is performed, the image data are divided to offset one another according to the certain alignment in the first scanning and the second scanning. Typically, as shown in FIG. 7 it is the commonest to use one like staggered grids every vertical and horizontal one pixel as this image data alignment (thinning-out pattern).
Accordingly, in a unit printing area (here 4 pixel unit), the printing is completed by the first scanning where staggered grids are printed and the second scanning where inverse staggered grids are printed.
FIGS. 7A, 7B and 7C illustrate how the record in the given area is completed when these staggered and inverse staggered patterns are used, respectively using the multihead with 8 nozzles as with FIG. 6. First, in the first scanning, the recording of the staggered pattern (shaded circles) is performed using the lower nozzles (FIG. 7A). Next, in the second scanning, paper feeding is performed for 4 pixels (a half of a recording head length) and the recording of the inverse staggered pattern (white circles) is performed (FIG. 7B). Further, in the third scanning, the paper feeding is performed again for 4 pixels (a half of a recording head length) and the recording of the staggered pattern is performed (FIG. 7C).
This way, the recording area of 4 pixel unit every one scanning is completed by alternately performing the paper feeding of 4 pixel unit and the recording of the staggered or inverse staggered pattern in sequence. As illustrated above, it is possible to obtain high-quality image which uneven density is alleviated by completing the printing by the different two types of nozzles in the same area.
However, even when such multi-pass recording is performed, the above uneven density is not sometimes dissolved at all and new uneven density is sometimes affirmed particularly in halftone depending on duties. Such phenomena are illustrated below.
Typically, the image data to be recorded in a certain area, which the printer receives have been already arrayed regularly. In the side of the recording apparatus, a definite amount of those data is stocked in buffer, new mask (image alignment pattern) of the staggered or inverse staggered pattern is given as is already illustrated, and the printing of that pixels is performed only when both the image data and pattern of the mask become an ON state.
FIGS. 10 to 12 illustrate these appearances. In FIG. 10, 1710 represents already arrayed data stocked in the buffer, 1720 represents the staggered pattern mask indicating pixels which allow the printing in the first pass, 1730 represents the inverse staggered pattern mask indicating pixels which allow the printing in the second pass, 1740 and 1750 represent the pixels printed in the first pass and the second pass, respectively.
In FIG. 10, the already arrayed data in the case where 25% printing is performed in a certain area are stocked in the buffer. These data uniformly retain the density in an assigned definite area, and thus, it is common that the printing data are disposed in a scattered state as possible. What image alignment these are is dependent on how area gradation method is performed at image processing before being transferred to the printer body. Those shown in 1710 are one instance of the image alignment for 25% data. When masks of 1720 and 1730 are given to such data and the printing is performed, as shown in 1740 and 1750, the data are allocated and recorded in a state where the data are divided equally in the first pass and the second pass, respectively.
However, as is shown in FIG. 11, when just 50% data come, it can be easily supposed that the data 1810 of image alignment in the most scattered state are completely coincided with either the staggered pattern mask (1820) or the inverse staggered pattern mask (1830).
When such a phenomenon occurs, the printing of all image data is terminated in the first pass (1840) and the recording is not performed in the second pass (1850) at all. Thus, all printing data are printed by the same nozzles. Therefore, the influences of nozzle dispersion are directly reflected upon the uneven density, and original purposes of the above division recording method are not accomplished.
FIG. 12 exhibits a printing state when arrayed image data at a higher duty state than FIGS. 10 and 11 are input. Also in this, it is found that the number of printing dots is considerably different in the first pass and the second pass. This way, there has been an adverse effect that the uneven density which has been improved at high duty of around 100% appears again for the data at low to around 50% duty.
When the thinning-out printing is performed using a specified mask pattern, the printing data and the mask pattern have sometimes the same cycle. An amplitude due to an allocation of the printing pixels and non-printing pixels on the mask pattern and an amplitude of the printing data are overlapped and vibrate sympathetically. Dot alignments of the image formed by this have a pattern with a certain orientation. Typically, this phenomenon is called a moire. This is easily remarkable and easily recognized by users when the images using the same mask pattern are in multiple lines. This moire heavily depends on periodicity of the mask pattern.
In addition to the above problems, the following problems occur when bidirectional printing is performed.
FIG. 13A exhibits a state where as the recording head jets a color ink droplet on a smooth face of the recording medium at a constant speed v with moving in a forth or back direction at a constant speed V. If the face of the recording medium is smooth as in the figure and a distance d between the face of the recording medium and a nozzle face of the recording medium is constantly retained at a constant value, a dot printed in a forth route and a dot printed in a back route are jetted on the same position by primarily adjusting a jet timing in the forth and back routes. However, when the face of the recording medium itself is lifted above an actual position as shown in FIG. 13B for some reason, the distance between the nozzle face and the face of the recording medium is shortened to d′, and a time from jetting by the recording head to arrival of the color ink droplet onto the face of the recording medium is shortened in both forth and back routes. Therefore, printed dots are formed on the positions out of the aimed position as shown in a lower figure. Likewise, when on the same image area, the distance d between the face of the recording medium and the nozzle face at printing in the forth route and the distance d between the face of the recording medium and the nozzle face at printing in the back route are changed due to local lifting of the paper, formed positions are sometimes further separated.
In such a state, when the image at duty of 100% is bidirectionally printed using the staggered thinning-out mask, a jetted dot state becomes one like FIG. 14. Here, the state where each dot is 1⁄4 pixel out of a proper position is shown. Portions where adjacent dots are overlapped more than needs and portions where spaces between adjacent dots are excessively large appear in different allocations depending on the thinning-out mask. In FIG. 14, all dots are printed in an inverse direction of adjacent dots, and thus a space of one dot every one dot occurs and the state where the print density is entirely light occurs.
Such total displacement of jetted positions at the bidirectional printing occurs not only due to partial lows and highs of the face of the recording medium as shown in FIGS. 13A and 13B but also due to various causes such as uneven jetting speed of the recording head 22 and uneven moving speed of the carriage. It is difficult to control the jet timing at the bidirectional printing because values of these factors are not constant for a traveling direction of the carriage. Also, the distance between the recording head 22 and the face of the recording medium in the recording apparatus is sometimes much different depending on individual apparatus, and thus control of jetting positions in the forth and back routes by adjustment of the jet timing has a limitation.
Due to the adverse effects described above, sufficient image quality is not always obtained with respect to the uneven density in the multi-pass printing using the regular thinning-out pattern which has been conventionally performed to compensate the variation of nozzles and the like. These adverse effects for the uneven density has the periodicity where unevenness alternately appears at a certain width of printing area, and thus it facilitates human visual sensation which recognizes as the uneven density.
The present inventors have found that the above issues occur when the regular mask pattern is used. Thus, in the present embodiment, the above problems are solved by performing the multi-pass recording using a thinning-out pattern without regularity, which defines an array of non-record pixel locations and record pixel locations, instead of using the regular mask pattern. As the thinning-out pattern without regularity, for example, it is possible to use a random pattern of a given size prepared using random numbers. Specifically, for example, as described in U.S. Pat. No. 3,176,182B, multiple random mask patterns with a given size where non-recording pixels and recording pixels are randomly arrayed are produced, the produced random mask patterns can be used as masks for thinning out recording data as thinning-out patterns for each recording area.
By forming the printed image in accordance with such random mask patterns, to have pattern cycles on the thinning-out alignment can be inhibited, that is, the adverse effect of uneven density in the formed image which occurs in the conventional multi-pass recording method using the regular masks can be overcome by eliminating the periodicity of uneven density.
Also, in place of the random mask using such random numbers, a dot allocation pattern with so-called blue noise property may be used as the thinning-out pattern without regularity. This pattern has been developed for quantization processing of halftone. When a dither processing is performed using this pattern, there are characteristics that less low frequency component is contained in the produced dots and the image where a particle feel is reduced is obtained.
In order to perform the image formation according to the thinning-out pattern without regularity, the method is not limited to the method using the random mask using random numbers or the dot allocation pattern with the blue noise property, and the other similar patterns for forming the thinned-out image according to the thinning-out pattern without regularity can be used.
Next, with respect to the method of performing the multi-pass recording using the masks without regularity as the above, the case where 4 pass printing is performed using the dot allocation pattern with the blue noise property as the mask is illustrated below in reference to FIGS. 15 and 16.
In an actual figuration of the nozzles of the recording head 22 used for the recording, as shown in FIG. 3, nozzle rows of 128 nozzles arranged at a pitch of 600 dpi are disposed in the main scanning direction at a distance of 500 μm.
Hereinafter, to simplify the illustration of the multi-pass recording, the nozzles were 16 per color, this was divided into 4 to make a nozzle number per divided area 4, and a mask size corresponding to it was made 4×16. The divided areas corresponding to this are shown as 501 to 504 in FIG. 17. The 4 pass printing is realized by making use of the respective divided areas 501 to 504 separately.
In each pass, a thinning-out mask pattern with about 25% duty, thus, the mask pattern where a printing acceptable rate is about 25% is set for the printing data for each divided area, and a 100% image is made by scanning 4 times. A1 to A4 which are examples of the 4×16 mask patterns used for this are shown in FIG. 15. In each mask pattern A1 to A4, the mask data exist at a position on grids shown by a mesh pattern in the figure, and the mask patterns are configured such that the mask data fill all grids of 4×16 when the respective mask patterns A1 and A4 are overlaid.
For the printing data 800 shown in FIG. 15 (hatching portions indicate that there are the printing data), the above mask patterns A1 to A4 are set. Here, a logical add at the same position of the printing data 800 and each mask pattern A1 to A4 is taken by making the presence of printing data 1 and making the absence of data 0 for the printing data 800 and making the presence of mask data 1 and making the absence of the data 0 for the mask patterns A1 and A4, and jetted data 801 to 804 of the recording heads are produced, respectively. When the 4 jetted data 801 to 804 are overlaid, the same printed image 805 as the original printing data 800 is formed.
FIG. 16 is a view for illustrating the multi-pass printing. Four types of mask data groups of a group of A1 to A4, a group of B1 to B4, a group of C1 and C4 and a group of D1 and D4 are used as one cycle of 4 pass. The pattern in each group is the pattern such that a 100% image is completed when four are overlaid in any cases. In the multi-pass printing, such setting of the mask data is performed in each divided area 501 to 504 of the printing heads 500 in each print scanning.
Print is performed as follows.
In the first printing area on a print image, the mask pattern A1 is set for the divided area 504 of the recording head and the recording is performed in the first record scanning. Subsequently, in the second record scanning, in the first printing area, the mask pattern A2 is used at the divided area 503 of the recording head, and in the second printing area, the print is performed using the mask pattern B1, of which the group is different from that of the mask pattern used in the first printing area, for the divided area 504 of the recording head 22.
Further, in the third record scanning, the print is performed using the mask pattern A3 for the divided area 502 of the recording head in the first printing area, the mask pattern B2 for the divided area 503 of the recording head in the second printing area, and the mask pattern C1, of which the group is different from those of the mask patterns A3 and B2, for the divided area 504 of the recording head in the third printing area.
In the fourth record scanning, the print is performed using the mask pattern A4 for the divided area 501 of the recording head in the first printing area, the mask pattern B3 for the divided area 502 of the recording head in the second printing area, the mask pattern C2 for the divided area 503 of the recording head in the third printing area, and the mask pattern D1, of which the group is different from those of the mask patterns A4, B3 and C2, for the divided area 504 of the recording head for the fourth printing area. At that time, in the first printing area, total four times of printing scanning are performed using 4 mask patterns, A1, A2, A3 and A4, and the image print for this area is completed.
According to the similar procedure, the image formation is made using mask patterns B1, B2, B3 and B4 in the second printing area, using mask patterns C1, C2, C3 and C4 in the third printing area, and using mask patterns D1, D2, D3 and D4 in the fourth printing area. Subsequently, the printing is continued by repeatedly making use of the printing using mask patterns A1, A2, A3 and A4 in the fifth printing area and mask patterns B1, B2, B3 and B4 in the sixth printing area, and the patterns of these 4 groups.
Also, as is shown in FIG. 18 these patterns are four mask patterns each having the blue noise property when the patterns are respectively aligned from the upper in sequence of A4B3C2D1, B4C3D2A1, C4D3A2B1 and D4A3B2C1 configure four 16×16 masks. These four 16×16 masks are those where 0 to 255 are disposed on 16×16 grids to have the blue noise property and the portions corresponding to the values of 0 to 63, 64 to 127, 128 to 191 and 192 to 255 are used as recording acceptable pixels. Those where these four masks are divided into four 4×16 correspond to A1 to A4, B1 to B4, C1 to C4 and D1 to D4. How to make such patterns is described in, for example, U.S. Pat. No. 2,622,429B.
This way, when the blue noise property is given to the dot pattern itself formed by one scanning, there are effects that occurrence of the repeated pattern and particulate deterioration are reduced compared to the case using the patterns produced by the random numbers. This is described in, for example, JP-Tokukai-2002-96461A.
If the acceptable printing rate of the mask is changed, the change can be easily obtained by changing the values of these 0 to 255 depending on a printing rate. For example if making two pairs of 40% and 10% masks, the masks could be made by making the pixels corresponding to 0 to 102, 103 to 127, 128 to 230 and 231 to 255 the printing acceptable pixels, respectively. Examples of such masks are shown in FIGS. 19 to 21.
FIG. 22 is a block diagram showing a configuration of the mask processing circuit, and illustrates the mask processing circuit 108 in FIG. 4 in detail.
In FIG. 22, 301 is a data register connected to a memory data bus, for reading out the printing data accumulated in an image memory 106 in a memory and temporarily storing, 302 is a parallel/serial converter for converting the data stored in the data register 301 into serial data, 303 is an AND gate for applied the masks to the serial data, and 304 is a counter for managing data transfer numbers.
305 is a register connected to CPU 103 through CPU data bus, for storing the mask patterns, 306 is a selector for selecting a digit position of the mask pattern, 307 is a selector for selecting a line position of the mask pattern, and 311 is a counter for managing the digit position.
In a transfer circuit shown in FIG. 22, a serial transfer of printing data to a printer head is performed by printing command signals sent from the CPU 103. The printing data accumulated in the image memory 106 in the memory are temporarily stored in the data register 301, and converted into the serial data by the parallel/serial converter 302. The masks are applied to the converted serial data by the AND gate 303, and subsequently the data are transferred to the printer head. The transfer counter 304 counts a transfer bit number and transfers the data for 16 nozzles.
A mask register 305 is configured by four mask registers, A, B, C and D, mask patterns written by the CPU 103 are housed. Each mask register stores the mask pattern of vertical 16 bits and horizontal 16 bits. A selector 306 selects mask pattern data corresponding to a digit position by making a value of a column counter 311 a selection signal. Also, the selector 307 selects mask pattern data corresponding to a line position by making a value of a transfer counter 304 a selection signal. The masks are applied to the transfer data using the AND gate 303 by the mask pattern data selected by the selectors 306 and 307.
These data are used for injection control of each nozzle of the recording head 22, and an injection is performed by synchronizing with timing signals produced from encoder signals. Hereinafter, these operations are performed in conformity with printing resolution toward to a width direction of the recording medium. In this embodiment, a mask size is 16 in a horizontal direction, and thus, the same mask pattern is repeatedly used every 16 pixels, but it is also possible to make the size in the horizontal direction of the mask the same size as the width of the recording medium. As the present embodiment, it is possible to reduce a capacity of the register which memorizes the masks by repeatedly using the same mask pattern.
In the inkjet recording method and the inkjet recording apparatus of the present embodiment, it is one of characteristics that a nozzle pitch of the recording head is from 10 to 50 μm. If the nozzle pitch is 50 μm or less, when jetted ink droplets are printed side by side one another, the distance between the droplets becomes short, and thus a problem of bronzing by adjacent dots one another easily occurs. Therefore, effects by applying the invention to the case that the nozzle pitch is 50 μm or less are great. This is because the dot diameter on a recording medium generally expands about twice as large as the nozzle diameter and landing position of the dot on a recording medium deviates from the right the right position thereof due to the deviation of jetting angle from the nozzle.
Besides, by making the nozzle pitch short such as 50 μm or less, even when multiple nozzles which exceed 500 nozzles per recording head are made, it is possible to keep an entire recording head length short. This can suppress jetted ink out of the position on the recording medium attributed to a change of a flying distance of the ink droplet from the nozzle in a recording head length direction due to a slope between the nozzle surface of the recording head and the recording head face, and thus it is possible to retain high printing accuracy. By making the nozzle pitch 10 μm or more, it is possible to suppress disturbance in fabrication aptitude, and consequently, it is possible to suppress the color ink out of the position, make it suppress to cause an overlap of dots due to shortening of dot intervals in the recording head length direction, and suppress the problem such as bronzing.
The nozzle pitch referred to here is a separation distance of mutual nozzles in the nozzle group arranged nearly in a line. As FIG. 3, in the case where two rows of the nozzle groups are arranged by shifting at a half pitch, when adjacent dots in a sub scanning direction on the recording medium are formed by nozzles of an A row and a B row, a certain time difference occurs. When the distance between the A row and the B row is relatively long, after a dot which previously adheres is absorbed into the recording medium, then next dot adheres, and thus it is difficult to cause the bronzing due to the aggregation of color ink. This way, when the distance between the A row and the B row is relatively long, the nozzle pitch is a pitch in each A row and B row. On the other hand, when the distance between the A row and the B row is relatively short, the nozzle pitch is the distance between adjacent nozzles between the A row and the B row, and typically a half of the pitch in each A row and B row.
Thus, in the invention, when the distance between the most separate nozzle rows (distance between N1 and N2, i.e., in the case of three rows, the distance between the first row and the third row) of multiple rows (n rows such as N1, N2 . . . Nn) of the nozzle groups is 4 mm or less, the nozzle pitch is 1/n of the pitch in each row, whereas when the distance is more than 4 mm, the nozzle pitch is the pitch in each row because it is preferable to consider influences for aggregation.
In the inkjet recording method of the invention, it is preferred that a printing acceptable rate by the thinning-out pattern is from 15 to 35%. Here, in the invention, the printing acceptable rate is a rate of dot number where jetting of the color ink is acceptable in one main scanning based on total dot number in the pattern when using the thinning-out pattern.
When the printing is performed using multiple thinning-out patterns different in printing acceptable rate in one image, the image quality of the image after the printing is frequently attributed to the thinning-out pattern with high printing acceptable rate. Therefore, in the invention, when the multiple thinning-out patterns different in printing acceptable rate are used in one image, the acceptable rate of the thinning-out pattern with the highest printing acceptable rate in the thinning-out patterns used in one image is the printing acceptable rate.
By making the printing acceptable rate by the thinning-out pattern 15% or more, the probability that the jetted color ink droplets are printed side by side one another becomes high, and therefore the effects obtained by applying the properties of the color inks, the recording medium and the recording method of the invention are great. Thus, by applying the invention, the high-quality images with less bronzing can be obtained. On the other hand, by making it 35% or less, in the portions where adhering liquid amounts are large such as red, blue and dark grey, the high quality images can be obtained.
It is preferred that a dot size formed by the color ink jetted from the first recording head is from 10 to 50 μm on the recording medium. By making the dot size formed by the color ink 10 μm or more, it is possible to maintain a printing efficiency at a certain level or more, and accurately control an ink droplet size. Also, by making it 50 μm or less, it is possible to suppress the degradation of glossiness and transparency color mixing according to protrusion of pigment caused by jetting excessive amount of ink onto a recording medium, and obtain the images at high definition.
Then, a method for jetting an invisible ink is described. The invisible ink can be also adhered on a medium according to the same method as that in the case of the color ink as mentioned above, but such complicated printing control can be not performed. Because, in the case of the invisible ink, gloss of the recording medium surface is enhanced by the adhesion thereof, but dots per se of the invisible ink are scarcely visible, and thus even when jetted positions are not somewhat lined up and the invisible ink dots come together one another to become the dots with large size, eyes of an observer scarcely recognize them. For example, in the case of performing 4 pass printing using the color ink by the method mentioned above, if using the invisible ink, the thinning-out process may be not performed at all for the invisible ink, and all jettings required may be performed at the initial first pass or may be performed at the final forth pass. Higher effects which improve gloss uniformity is obtained by adhering the invisible ink on highlight sections on which the color ink is adhered to some extent in addition to white background sections on which the color ink is not adhered at all, and thus it is preferable to adhere according to the same method as that of the color ink. Also, liquid drop sizes need not be reduced as small as those of the color ink.
Also, with respect to determination of an adhering amount and an adhesion position of the invisible ink, it is possible to use the same halftone process as that of the color ink, but a simpler dither process and the like may be used. The reason is as mentioned above, the eyes of the observer can scarcely recognize the invisible ink and thus it is not necessary to disperse the dots evenly as is the case of the color ink.
In the invention, the invisible ink is jetted in accordance with the adhering amount of the color ink per unit area on a recording medium. For example, in a region where the adhering amount of the color ink is not more than the predetermined amount, the adhering amount of the invisible ink could be increased compared to a region where the amount is more than the predetermined amount. Specifically, it can be realized by making the adhering amounts of the invisible ink on the white background section and the highlight section larger than the adhering amount of the invisible ink on a shadow section.
In this case, the white background section and the section where the adhering amount of the color ink is small do not indicate an ink adhering amount in one pixel unit on the recording medium, and indicate the adhering amount per unit area which is a region where the pixels are integrated to some extent. This is because a pseudo gradation process such as error diffusion is combined when reproducing an image with 256 gradations such as natural pictures by a recording way such as inkjet where a gradation level number of a pixel unit is low. This expresses the gradation in a pseudo-manner by the gradation per pixel and a dot density in a region with size to some extent. For example, when the unit area is 16×16 pixels, the case where there is one dot in it is expressed as 1/256, and the case where there are two dots in it is expressed as 2/256. In the case of 1200 dpi, it corresponds to a region of about 340 μm square. Therefore, the white background indicates the region in which the color ink is not adhered at all when the recording medium face is divided by the region of the unit area. The highlight section indicates the region in which approximately not more than about a half of the color ink adhering amount is adhered.
In a method for controlling an invisible ink amount, each color ink adhering amount per pixel or pixel region where a certain degree of pixels is integrated is calculated from image data used for printing, this is subtracted from a target value, invisible ink amount data are generated by making a portion to become negative zero, and the invisible ink amount can be determined by giving halftone process to this. A relation of image data values and the color ink adhering amounts is shown, for example, in FIG. 25.
Alternatively, it is also possible to give the halftone process to color ink image data, which are then made into dot data jetted on the medium, subsequently calculate the color ink amount per region, and determine a pixel position where the invisible ink should be jetted in the region which comes short of a target value. For example, FIG. 26 shows the highlight section where 25 color ink dots are adhered in the region of 200×200 pixels. FIG. 27 shows the case where the invisible ink is disposed such that one dot of the color ink together with the invisible ink are adhered in 4 pixels in this highlight section, that is one dot of the color ink or the invisible ink are adhered in 4 pixels. When an image resolution is 1200 dpi and a volume of both the color ink and the invisible ink are equally 3 pl, the adhering amount of the case where one drop of either ink is adhered in all pixels is 6.7 ml/m2, and the invisible ink amount is controlled to be the adhering amount of 3.4 ml/m2 which is a half thereof.
In this way, if the dot data of color inks are made and subsequently the position and adhering amount of the invisible ink are determined based thereon, it is possible to control to jet on the mutually separate positions as possible such that the color inks and the invisible ink are not blended in.













TABLE 1





NO.
A
B
C
D
E
F







INK 1
—
—
CYAN
CYAN
CYAN
CYAN


JET-


INK
INK
INK
INK


TING


0.5 ml
1.0 ml
1.5 ml
2.0 ml







AMOUNT


(ml)













INK
CYAN
INVIS-
INVIS-
INVIS-
INVIS-
INVIS-


JET-
INK
IBLE
IBLE
IBLE
IBLE
IBLE


TING

INK
INK
INK
INK
INK







AMOUNT








(ml)
20-DEGREE SPECULAR GLOSS













0.0
23
23
31
39
50
63


0.5
31
29
38
49
62
74


1.0
39
38
47
60
69
82


1.5
50
49
61
69
80
93


2.0
63
60
69
80
91
102


2.5
87
65
74
85
96
116


3.0
98
74
83
94
118
115


3.5
109
87
96
114
112
112


4.0
117
94
115
112
109
104


4.5
120
100
112
109
103
97


5.0
116
105
110
104
101
92









Table 1 shows data obtained from measurement of gloss values when the ink amounts of a cyan ink (A) alone and the invisible ink (B) alone are changed from 0 to 5.0 ml and gloss values when the invisible ink amounts are changed from 0 to 5 ml against the cyan ink amount of 0.5 ml (C), 1.0 ml (D), 1.5 ml (E) and 2.0 ml (F) on recording medium of medium face with white background, where a 20-degree specular gloss value is 23. As is shown from this, when a total adhering amount of the cyan ink and the invisible ink is more than 2 ml/m2, the gloss value exceeds 60, and gloss feeling of the white background section is improved as well as the gloss values are rapidly increased from this up to about 120.
Gloss uniformity due to the increase of gloss in the white background section makes observer recognize transparent feeling, and can give the images which come near silver halide photographs. This tendency is common to the color inks other than the cyan ink.
From the above, it is preferred that the above invisible ink is jetted from the above second recording head such that the total of the color ink adhering amount and the invisible ink adhering amount per unit area on the recording medium is 2 ml/m2 or more. More preferably, the total of the color ink adhering amount and the invisible ink adhering amount per unit area on the recording medium is 2 ml/m2 or more and 25 ml/m2 or less.
Next, an upper limit of the total of the color ink adhering amount and the invisible ink adhering amount per unit area on the recording medium is described.
As the recording medium according to the invention, the recording medium having a micro-porous type ink absorbing layer (also referred to as a micro-porous layer) is preferably used. This micro-porous layer is formed by forming micro-pores in a film using inorganic fine particles and a small amount of a hydrophilic binder (details are described later). The more the voids are, an absorption speed and an absorption capacity are more increased, but at the same time, the medium becomes fragile for a force from the outside. Thus, there is problematic in that when a film thickness is tried to enlarge, cracks easily occur at the manufacture. It is possible to increase the absorption speed and the absorption capacity by increasing a void rate as the film thickness is as it is, but after all, the medium becomes brittle for cracking. Various studies have been performed to overcome that objection, but actually, when making the film thickness or the void rate where the absorption capacity per unit area is more than 25 ml/m2, very small cracklings intensively occur at the manufacture, and consequently it becomes impossible to form the images with high quality level. Thus, it is preferable to design and manufacture the film thickness or the void rate where the absorption capacity per unit area is less than 25 ml/m2 in the recording medium having the micro-porous layer.
Here, when the color ink and invisible ink adhering amounts exceed the absorption capacity per unit area of the recording medium, of course, the ink over the absorption capacity overflows and it leads image defects such as spread of images and color blend.
From such reasons, by making the total of the color ink and invisible ink adhering amounts 25 ml/m2 or less, it is possible to inhibit the overflow of the color inks and the invisible ink from the recording medium, the gloss value becomes high and image quality is improved.
Then, color inks and the invisible ink according to the invention are described.
First, the color inks according to the invention are described. In the inkjet recording method of the invention, it is preferable to use special color ink as well as yellow, magenta, cyan and black inks which are so-called base colors. The special color ink is ink having hues between the above basic colors, such as red, green, violet and orange in conjunction with the basic color inks.
By using the special color inks along with the basic color inks, it is possible to reduce the amounts of jetted inks, consequently, prevent pigment particles which are comprised in jetted ink liquid drop lets from aggregating, and realize color images with high quality level and high definition where glossiness reduction, bronzing and color turbidity are reduced.
In the case of using such special color inks, ink types are increased compared to the print by common CMYK inks, thus a method for separating input image data (RGB or CMYK, etc.) into respective colors has not been established as a common belief, and a know-how suited to each ink used is required. Concerning this, color separation in accordance with the special colors used can be performed using techniques and the like disclosed in JP-Tokukai-2000-32284A by the present applicant. According to this method, it is possible to maximally effectively use a color gamut extended by the special color inks and assure color continuity calorimetrically.
In addition to this, it is also possible to generate special color version data by the method as described in the Japanese Patent No. 2711081. According to this method, it is possible to easily control ink amounts, for example, data for blue ink can be generated from data values of cyan and magenta and depending on this, data value of cyan and magenta are reduced to decrease the total ink amount, or light-colored cyan and magenta are used in the highlight section without using the special colors to reduce rough surface.
The color inks of the invention contain pigments, at least one organic solvent with a high boiling point and water. Additionally, it is preferred that a surface tension of the color inks is from 30 to 50 mN/m and that the pigments are dispersed by a polymeric dispersant.
As the pigments usable in the color inks according to the invention, it is possible to use chromatic organic or chromatic inorganic pigments known in the art. For example, azo pigments such as azo lakes, insoluble azo pigments, condensed azo pigments and chelate azo pigments, polycyclic pigments such as phthalocyanine pigments, perylene pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, thioindigo pigments, isoindolinone pigments and quinophthalone pigments, dye lakes such as basic dye lakes and acid dye lakes, organic pigments such as nitro pigments, nitroso pigments, aniline black and daylight fluorescent pigments, and inorganic pigments such as carbon black are included but the invention is not limited thereto.
Specific organic pigments are exemplified below.
As the pigments for magenta, for example, C.I. Pigment Red 2, C.I. Pigment Red 3, C.I. Pigment Red 5, C.I. Pigment Red 6, C.I. Pigment Red 7, C.I. Pigment Red 15, C.I. Pigment Red 16, C.I. Pigment Red 48:1, C.I. Pigment Red 53:1, C.I. Pigment Red 57:1, C.I. Pigment Red 122, C.I. Pigment Red 123, C.I. Pigment Red 139, C.I. Pigment Red 144, C.I. Pigment Red 166, C.I. Pigment Red 202, C.I. Pigment Red 222, C.I. Pigment Violet 19 and the like are included.
As the pigments for red, for example, C.I. Pigment Red 17, C.I. Pigment Red 49:2, C.I. Pigment Red 112, C.I. Pigment Red 149, C.I. Pigment Red 177, C.I. Pigment Red 178, C.I. Pigment Red 188, C.I. Pigment Red 255, C.I. Pigment Red 264 and the like are included.
As the pigments for yellow, for example, C.I. Pigment Orange 31, C.I. Pigment Yellow 12, C.I. Pigment Yellow 13, C.I. Pigment Yellow 14, C.I. Pigment Yellow 15, C.I. Pigment Yellow 17, C.I. Pigment Yellow 74, C.I. Pigment Yellow 93, C.I. Pigment Yellow 94, C.I. Pigment Yellow 128, C.I. Pigment Yellow 138 and the like are included.
As the pigments for orange, for example, C.I. Pigment Orange 36, C.I. Pigment Orange 43, C.I. Pigment Orange 61 and the like are included.
As the pigments for cyan, for example, C.I. Pigment Blue 15, C.I. Pigment Blue 15:2, C.I. Pigment Blue 15:3, C.I. Pigment Blue 16 and the like are included.
As the pigments for green, for example, C.I. Pigment Green 7, C.I. Pigment Green 36 and the like are included.
As the pigments for blue, for example, C.I. Pigment Blue 60, C.I. Pigment Violet 23 and the like are included.
As the pigment for black, for example, C.I. Pigment Black 1, C.I. Pigment Black 6, C.I. Pigment Black 7 and the like are included.
As methods for dispersing the pigments, it is possible to use various dispersing machines such as a ball mill, sand mill, attritor, roll mill, agitator, Henschel mixer, colloid mill, ultrasonic homogenizer, pearl mill, wet type jet mill and paint shaker. Also it is preferable to use a centrifuging machine and a filter for the purpose of eliminating crude particles of a pigment dispersion.
It is preferred that the surface tension of the color ink according to the invention is from 30 to 50 mN/m. By making the surface tension of the color ink 30 mN/m or more, it is possible to inhibit aggregation of pigment particles one another, and thus it is possible to inhibit an occurrence of bronzing and improve gloss and scratch/abrasion resistance. Also by making the surface tension of the color ink 50 mN/m or less, it is possible to inhibit color turbidity due to long retention of jetted ink liquid drops on the medium, and obtain the image with high definition.
For the surface tension, it is possible to adjust to the desired surface tension by appropriately conditioning types and addition amounts using the various water-soluble organic solvents described above and various surfactants described below.
The method of measuring the surface tension is described in general reference books of surface chemistry and colloid chemistry, for example, Shin Jikken Kagaku Kouza, Vol. 18 (Surface and Colloid) edited by the Chemical Society of Japan and published by Maruzen Co., Ltd.: pages 68 to 117 can be referred, and specifically, it can be obtained by a ring method (DuNouy method) or a plate method (Wilhelmy method).
As one of ways to accomplish the above surface tension, various surfactants can be used. Various surfactants which can be used in the invention are not particularly limited, and for example, include anionic surfactants such as dialkyl sulfosuccinate salts, alkylnaphthalene sulfonate salts and fatty acid salts, nonionic surfactants such as polyoxyethylene alkylethers, polyoxyethylene alkylallylethers, acetyleneglycols, block copolymer of polyoxyethylene and polyoxypropylene, and cationic surfactants such as alkylamine salts, and quaternary ammonium salts. Particularly, the anionic surfactants and the nonionic surfactants can be preferably used.
In the invention, it is preferred that acetylene type surfactant is used as the surfactant in terms of being capable of obtaining the image where the injection stability is good with high print density, having preferable gloss and which is excellent in uniformity.
The acetylene type surfactant is not particularly limited, for example, includes acetylene glycols and acetylene alcohols, is more preferably the surfactant having acetylene group and alkylene oxide chain, and for example, can include Surfynol 465 (supplied from Nisshin Chemical Industry Co., Ltd.).
In the ink according to the invention, it is preferable to use a polymeric dispersant for the dispersion of the pigments. The polymeric dispersant applicable to the invention is not particularly limited, and a water-soluble resin or a water-insoluble resin is used. As these polymeric molecules, it is possible to include polymers made up of a single monomer or copolymers made up of two or more monomers selected from styrene, styrene derivatives, vinylnaphthalene derivatives, acrylic acid, acrylate derivatives, methacrylic acid, methacrylate derivatives, maleic acid, maleate derivatives, itaconic acid, itaconate derivatives, fumaric acid and fumarate derivatives, and salts thereof. Also, it is possible to use water-soluble polymeric molecules such as polyvinyl alcohol, polyvinyl pyrrolidone, cellulose derivatives, gelatin, and polyethyleneglycol.
It is preferred that these polymers have both a hydrophilic moiety and a hydrophobic moiety. The hydrophilic moiety has a function to stabilize the dispersion in water which is a major component of the ink, whereas the hydrophobic moiety has a function to enhance adhesion onto pigment surfaces. Among others, acryl type polymeric dispersants are preferably used in terms of the characteristics such as easiness of molecular structure design and easiness to obtain a performance as the dispersant. The acryl type polymeric dispersant is referred to the polymeric dispersant containing an acryl type monomer at least at 30 mol % or more.
As such an acryl type polymeric dispersant, polymers made up of the hydrophobic monomer and hydrophilic monomer shown below, or copolymers made up of two or more of the monomers, and salts thereof are preferable. The hydrophobic monomers include but are not limited to, for example, styrene, α-methylstyrene, methyl methacrylate (MMA), ethyl methacrylate (EMA), propyl methacrylate, n-butyl methacrylate (BMA or NBMA), hexyl methacrylate, 2-ethylhexyl methacrylate (EHMA), octyl methacrylate, lauryl methacrylate (LMA), stearyl methacrylate, phenyl methacrylate, hydroxyethyl methacrylate (HEMA), hydroxypropyl methacrylate, 2-ethoxyethyl methacrylate, methacrylonitrile, 2-trimethylsiloxyethyl methacrylate, glycidyl methacrylate (GMA), p-tolyl methacrylate, sorbyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, lauryl acrylate, stearyl acrylate, phenyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, acrylonitrile, 2-trimethylsiloxyethyl acrylate, glycidyl acrylate, p-tolyl acrylate, sorbyl acrylate, benzyl acrylate, benzyl methacrylate, 2-phenylethyl methacrylate and the like.
As the hydrophobic monomer, styrene, methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, benzyl methacrylate, 2-phenylethyl methacrylate, or benzyl acrylate is particularly preferable.
The hydrophilic monomers include, but are not limited to, for example, methacrylic acid (MAA), acrylic acid, maleic acid, dimethylaminoethyl methacrylate (DMAEMA), diethylaminoethyl methacrylate, tert-butylaminoethyl methacrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminopropyl methacrylamide, methacrylamide, acrylamide, dimethyl acrylamide and the like.
As the hydrophilic monomer, methacrylic acid, acrylic acid or dimethylaminoethyl methacrylate is preferable.
A polymer containing an acid is manufactured directly from an unsaturated acid or manufactured from a blocked monomer having a blocking group which can be eliminated after polymerization. As examples of the blocked monomer which produces acrylic acid or methacrylic acid after eliminating the blocking group, trimethylsilyl methacrylate (TMS-MAA), trimethylsilyl acrylate, 1-butoxyethyl methacrylate, 1-ethoxyethyl methacrylate, 1-butoxyethyl acrylate, 1-ethoxyethyl acrylate, 2-tetrahydropyranyl acrylate, 2-tetrahydropyranyl methacrylate and the like are included.
Structures of these polymers include random polymer or random copolymer, block copolymer, branched polymer or copolymer, graft polymer or copolymer. Among others, the block copolymer and the branched copolymer are preferable for the object of the invention because the design and control of the hydrophilic and hydrophobic moieties are easy.
The block polymers include structures such as AB, BAB and ABC types (here, A, B and C schematically represent polymer blocks different in structure one another), but there is no restriction of the structure so long as the block moiety is present. Particularly, the block polymer having a hydrophobic block and a hydrophilic block or having a balanced block size which contributes to dispersion stability is preferable. A functional group can be incorporated in the hydrophobic block (block to which a coloring agent is bound) thereby improving the dispersion stability, and thus a specific interaction between the dispersant and the coloring agent is further enforced.
These polymers can be synthesized by conventionally known in the art, and can be synthesized particularly by the methods disclosed in the specification of U.S. Pat. Nos. 5,085,698B, 5,221,334B, 5,272,201B, 5,519,08B5 and 6,117,921B, and the examples in JP Tokukaihei 10-279873A and 11-269418A and JP-Tokukai-2001-115065A, 2001-139849A, 2001-247796A and 2003-260348A.
As the hydrophobic monomers which can be used for the block copolymer, for example, it is possible to include the same monomers as the hydrophobic monomers which can be used for the acryl type polymeric dispersant.
As the hydrophobic monomers, methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, benzyl methacrylate, 2-phenylethyl methacrylate, or benzyl acrylate is particularly preferable. As the hydrophobic polymer block, the polymer made up of the above single monomer or the copolymer block made up of two or more monomers is preferable.
As the hydrophilic monomers which can be used for the block copolymer, for example, it is possible to include the same monomers as the hydrophilic monomers which can be used for the acryl type polymeric dispersant.
The hydrophilic monomer is preferably methacrylic acid, acrylic acid or dimethylaminoethyl methacrylate, and as the hydrophilic polymer block, the polymer made up of the above single monomer or homopolymer and copolymer made up of two or more of the monomers are preferable.
A polymer containing an acid is manufactured directly from an unsaturated acid or manufactured from a blocked monomer having a blocking group which can be eliminated after polymerization. As examples of the blocked monomer which produces acrylic acid or methacrylic acid after eliminating the blocking group, trimethylsilyl methacrylate (TMS-MAA), trimethylsilyl acrylate, 1-butoxyethyl methacrylate, 1-ethoxyethyl methacrylate, 1-butoxyethyl acrylate, 1-ethoxyethyl acrylate, 2-tetrahydropyranyl acrylate, 2-tetrahydropyranyl methacrylate and the like are included.
As the monomers which can be used for the branched polymer or copolymer and the graft polymer or copolymer, it is possible to use those included as the monomers which can be used for the above block copolymer. The branched polymer or copolymer and the graft polymer or copolymer can be easily synthesized by using a macromer having a polymerizable functional group at one end, for example, silicone macromer, styrene type macromer, polyester type macromer, polyurethane type macromer or polyalkylether macromer. As examples of the above macromer, styrene macromers AS-6 and AN-6 supplied from Toagosei Co., Ltd., silicone macromers FM-0711 and FM-0721 supplied from Chisso Corporation, polyethyleneglycol and polyethyleneglycol methacrylate and the like are included.
A weight average molecular weight of these polymeric molecules is preferably in the range of 1,000 to 30,000, and more preferably in the range of 1,500 to 15,000. An acid value is preferably in the range of 10 to 500, and more preferably in the range of 50 to 250.
In the ink according to the invention, a pigment dispersant known in the art, for example, surfactants such as higher fatty acid salts, alkyl sulfate salts, alkyl ester sulfate salts, alkyl sulfonate salts, sulfosuccinate salts, naphthalene sulfonate salts, alkyl phosphate salts, polyoxyalkylenealkylether phosphate salts, polyoxyalkylenealkylphenyl ether, polyoxyethylenepolyoxypropyleneglycol, glycerin ester, sorbitan ester, polyoxyethylene fatty acid amide and amine oxide may be combined along with the above polymeric dispersant.
In the color ink according to the invention, a volume average particle size of a pigment dispersion is preferably from 20 to 200 nm in terms of obtaining preferable color tone, high print density or good gloss, and more preferably from 40 to 140 nm in terms of additionally improving light resistance.
In the invention, the volume average particle size of the pigment dispersion can be obtained by a commercially available particle size measuring instrument using a light scattering method, electrophoresis, a laser Doppler method and the like, and as a specific particle size measuring instrument, for example, it is possible to include Zetasizer 1000HS supplied from Malvern Instruments.
In the inkjet recording method of the invention, it is one of characteristics that the second recording head jets the invisible ink onto an area other than the area where image has been printed with the above-described color ink, i.e. un-printed area. The invisible ink is made of at least water and resin fine particles.
The inorganic ink referred to in the invention can be made of known ink compositions except colorant. As for the additives other than the resin particles, for example, a wetting agent such as polyvalent alcohols, inorganic salt, surfactant, antiseptic agent, mildewproofing agent, pH adjuster, antiforming agent such as silicone series, viscosity modifier, and chelating agent such as EDTA, and furthermore, functional materials such as oxygen absorbing agent such as sulfite, ultraviolet absorbing agent, and lubricant can be added according to need.
Hereinafter, the resin particles used in the invisible ink of the invention is illustrated.
As for the material used for a resin particles, a wax, polyvinyl chloride, poly vinylidene chloride and vinyl chloride-vinylidene chloride copolymer, chlorinated polypropylene, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, ethyl cellulose, cellulose nitrate, polyacrylic acid, linseed oil reforming alkyd resin, rosin modified alkyd resin, phenol modified alkyd resin, phenol resin, polyester, polyvinyl butyral, polyisocyanate resin, polyurethane, polyvinyl acetate, polyamide, chroman resin, rubber dammar, ketone resin, maleic resin, vinyl polymer, polystyrene, copolymer of polyvinyl toluene or vinyl polymer and methacrylate or acrylate, low molecular weight polyethylene, phenol modified pentaerythritol ester, styrene-indene-acrylonitrile copolymer, styrene-indene copolymer, styrene-acrylonitrile copolymer, copolymer with siloxane, poly alkene, and styrene-butadiene copolymer, and the like can be given. They may be used solely or in combination.
As for the invisible ink, it is preferable that MFT (minimum film forming temperature) thereof is not more than 70° C. Also, a volume average particle size of the invisible ink is not more than 100 nm.
Next, the constituents of the color inks and invisible ink of the invention other than the above constituents are illustrated.
Water-soluble organic solvents can be applied to the color inks and invisible ink. Concretely, it includes alcohols (e.g., methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secondary butanol, tertiary butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol, etc.), polyvalent alcohols (e.g., ethyleneglycol, diethyleneglycol, triethyleneglycol, polyethyleneglycol, propyleneglycol, dipropyleneglycol, polypropyleneglycol, butyleneglycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol, etc.), polyvalent alcohol ethers (e.g., ethyleneglycol monomethylether, ethyleneglycol monoethylether, ethyleneglycol monobutylether, ethyleneglycol monophenylether, diethyleneglycol monomethylether, diethyleneglycol monoethylether, diethyleneglycol monobutylether, diethyleneglycol dimethylether, propyleneglycol monomethylether, propyleneglycol monobutylether, ethyleneglycol monomethylether acetate, triethyleneglycol monomethylether, triethyleneglycol monoethylether, triethyleneglycol monobutylether, triethyleneglycol dimethylether, dipropyleneglycol monopropylether, tripropyleneglycol dimethylether, etc.), amines (e.g., ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenediamine, triethylenetetramine, tetraethylenepentamine, polyethyleneimine, pentamethyldiethylenetriamine, tetramethylpropylenediamine, etc.), amides (e.g., formamide, N-N-dimethylformamide, N,N-dimethylacetamide, etc.), heterocycles (e.g., 2-pyrrolidone, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, 2-oxazolidone, 3-dimethyl-2-imidazolidinone, etc.), sulfoxides (e.g., dimethylsulfoxide, etc.), sulfones (e.g., sulforane, etc.), sulfonate salts (e.g., sodium 1-butylsulfonate salt, etc.), acetonitrile, acetone, and the like.
In the color inks and invisible ink of the invention, among the above water-soluble organic solvents, it is one of the characteristics to contain the organic solvent with high boiling point where the boiling point under atmospheric pressure is 150° C. or above, which is preferred aspects in terms of color tone and dispersion stability. Specific examples of the organic solvent with high boiling point include alcohols such as ethyleneglycol, propyleneglycol, diethyleneglycol, triethyleneglycol, glycerin, diethyleneglycol monomethylether, diethyleneglycol monobutylether, triethyleneglycol monobutylether, glycerin monomethylether, 1,2,3-butanetriol, 1,2,4-butanetriol, 1,2,4-pentanetriol, hexanetriols (e.g., 1,2,6-hexanetriol, 1,2,3-hexanetriol, etc.), thiodiglycol, triethanolamine and polyethyleneglycol (average molecular weight is about 300 or less).
In the color inks and invisible ink according to the invention, it is preferred that a content of the above water-soluble organic solvent is from 10 to 50% by mass in terms of being capable of obtaining the image where injection stability is good and print density is high and having a preferable gloss.
It is also preferred that the color inks or the invisible ink according to the invention contain urea or an urea derivative. By containing urea or the urea derivative in the respective color inks or the invisible ink according to the invention, it is preferable because it is possible to inhibit aggregation of the pigment particles in the jetted ink liquid drops on the recording medium and consequently improve glossiness and texture. It is preferred that this urea or urea derivative has appropriately strong interaction for expressing objective effects by the interaction such as hydrogen bonds. As such compounds, urea, thiourea, and urea derivatives substituted with lower alkyl group (such as methylurea, dimethylurea, butylurea, ethyleneurea, phenylurea, etc.) are preferable, and particularly urea and ethyleneurea are preferable.
In the color inks and invisible ink of the invention, the content of urea is preferably 1 to 20 mass % from a viewpoint of fine ejecting stability and obtaining an image of high density having preferable gloss.
It is preferred that pH of the color inks and or the invisible ink according to the invention is 7.0 or more, and more preferably from 8.0 to 10.0. By making the above pH, the image where injection stability is good and print density is high and having a preferable gloss can be obtained, and thus it is preferable.
A pH adjuster used in the color inks or the invisible ink according to the invention includes, for example, various organic amine such as monoethanolamine, diethanolamine and triethanolamine, inorganic alkali agents such as hydroxide of alkali metal such as sodium hydroxide, lithium hydroxide and potassium hydroxide, organic acids, mineral acids and the like.
In the ink according to the invention, in addition to the above illustration, if necessary, various additives known in the art, for example, a viscosity adjuster, specific resistance adjuster, film forming agent, ultraviolet ray absorbent, anti-oxidant, anti-color fading agent, antimicrobials and fungicides, anti-rusting agent and the like can be used for the purpose of the injection stability, compatibility of print head and ink cartridge, storage stability, image permanence, and the other performance improvement. For example, it is possible to include oil droplet fine particles such as liquid paraffin, dioctyl phthalate, tricresyl phosphate and silicon oil, the ultraviolet ray absorbents described in JP Tokukaisho 57-74193A, JP Tokukaisho 57-87988A and JP Tokukaisho 62-261476A, the anti-color fading agents described in JP Tokukaisho 57-74192A, 57-87989A, 60-72785A, 61-146591A, JP Tokukaihei 1-95091A and 3-13376A, the fluorescent brightening agents described in JP Tokukaisho 59-42993A, 59-52689A, 62-280069A, 61-242871A and JP Tokukaihei 4-219266A, and the like.
Then, the recording medium according to the invention is illustrated.
Generally, as an ink absorbing layer, there are a swelling type and a micro-porous type by broadly dividing. As the swelling type, a water-soluble binder, for example, gelatin, polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene oxide and the like is applied alone or in combination, and this is made the ink absorbing layer. However, in the invention, in order to adapt to continuous high speed print, the recording medium where an ink absorption speed is high is more suitable, and thus from this point, the inkjet recording medium having the ink absorbing layer of the micro-porous type is used.
In the recording medium having the ink absorbing layer of the micro-porous type (also referred to as a micro-porous layer) according to the invention, it is one of the characteristics that a transferred amount at 0.04 seconds of absorption time by Bristow method is 10 ml/m2 or more, and it is preferably 10 ml/m2 or more and 25 ml/m2 or less. When the transferred amount is less than 10 ml/m2, the ink absorption speed on the recording medium is reduced, color turbidity occurs when the jetted ink droplets are printed side by side, and it becomes impossible to obtain the image at high definition.
In the recording medium according to the invention, the method to accomplish the transferred amount defined above is not particularly limited, and the transferred amount can be accomplished by appropriately conditioning a thickness of the micro-porous layer, a mean particle size of inorganic fine particles (F) which configure the micro-porous layer, a type of a hydrophilic binder (B), a ratio (F/B) of the inorganic fine particles to the hydrophilic binder (B), a type of a support used and the like.
Bristow method referred to in the invention is the method of measuring liquid absorption behavior of paper and plate paper in a short time. Particularly, according to J. TAPPI paper pulp test method No. 51-87, a method of testing absorbability of the paper or plate paper (Bristow method), the measurement is performed, and the absorption is represented by the transferred amount (ml/m2) at 0.04 sec of the absorption time. In the above method, purified water (ion-exchange water) is used for the measurement. However, in order to make determination of a measurement area easy, in the invention, the measurement is performed using an aqueous solution of 2% C.I. acid red 52.
One example of specific measurement method is illustrated below.
As the method of measuring the transferred amount, after leaving the recording medium under an atmosphere of 25° C. and 50% RH for 12 hours or more, the measurement is performed using a Bristow testing machine II type (press mode) which is a liquid dynamic absorbability testing machine supplied from Kumagai Rikikogyo Co., Ltd. The aqueous solution of 2% C.I. acid red 52 is used for the measurement as mentioned above to enhance measurement accuracy, and the transferred amount can be obtained by measuring an area stained on the recording medium after a defined contact time.
Hereinafter, respective constituent factors of the recording medium according to the invention are illustrated.
Conventionally, various methods of forming micro-pores in a membrane have been known, for example, the method of forming micro-pores by applying a uniform coating solution containing two or more polymeric molecules onto a support and causing phase separation of these polymeric molecules in a drying process, the method of making micro-pores by applying a coating solution containing solid fine particles and a hydrophilic or hydrophobic resin onto a support, after drying, immersing a recording medium in water or a liquid containing an appropriate organic solvent, and dissolving the solid fine particles, the method of forming micro-pores in a membrane by applying a coating solution containing a compound having a nature which foams at the membrane formation, and subsequently foaming this compound in a drying process, the method of forming micro-pores in porous fine particles and between fine particles by applying a coating solution containing porous solid fine particles and a hydrophilic binder on a support, the method of forming micro-pores between solid fine particles by applying a coating solution containing solid fine particles or fine particle oil droplets having a volume nearly equal to or more than that of a hydrophilic binder and the hydrophilic binder on a support, and the like have been known.
The micro-porous layer according to the invention indicates an ink receiving layer with a void rate of 25 to 75% mainly formed from the inorganic fine particles and a small amount of the hydrophilic binder.
In the recording medium of the invention, it is the characteristics that the micro-porous layer is formed by containing the inorganic fine particles with a mean particle size of 15 to 100 nm, and preferably the mean particle size is from 20 to 80 nm. When the mean particle size exceeds 100 nm, deterioration of surface gloss of a coating occurs. Further, it becomes difficult to give sufficiently large ink absorbing rate in the case of the mean particle size of less than 15 nm.
As the inorganic fine particles used for the above purpose, it is possible to include white inorganic pigments such as calcium carbonate light, calcium carbonate heavy, magnesium carbonate, kaolin, clay, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc hydroxide, zinc sulfide, zinc carbonate, hydrotalcite, aluminium silicate, diatomite, calcium silicate, magnesium silicate, synthetic amorphous silica, colloidal silica, alumina, colloidal alumina, pseudoboehmite, aluminium hydroxide, lithopone and magnesium hydroxide.
The mean particle size of the inorganic fine particles in the invention is obtained as the simple mean value (number mean) by observing cross sections and surfaces of the micro-porous layer in the recording medium by an electron microscope and randomly measuring the particle size of 1,000 particles. Here, the particle size of individual particle is a diameter when a circle equal to a projection area thereof is supposed. As the inorganic fine particle, it is preferable to use silica or alumina.
As the silica which can be used in the invention, silica synthesized by a usual wet method, colloidal silica or silica synthesized by a vapor phase method or the like is preferably used, and as the silica preferably used in the invention, colloidal silica or fine particle silica synthesized by the vapor phase method is preferable. Among others, the fine particle silica synthesized by the vapor phase method has a characteristics that a so-called soft aggregation structure is formed by coexisting with the hydrophilic binder to give a high void rate. Further when it is added to a cationic polymeric molecule used for the purpose of immobilizing colorants, rough and large aggregation is difficult to be formed, and thus it is preferable.
Alumina or alumina hydrate which can be used in the invention may be crystalline or amorphous, and it is possible to use those with any shape such as undefined shaped particles, spherical particles and needle particles. Among others, the alumina hydrate having a plate shape where an average aspect ratio is from 1 to 4 is preferable. There are those having a fibrous shape and those having a plate shape in the alumina hydrate. When the fibrous alumina hydrate is used, it is prone to orientate in parallel with a substrate surface at the application, and thus formed micropores become small. On the contrary, in the case of the plate alumina hydrate, tendency to orientate to a certain direction by the application is small, and a relatively large void rate can be obtained.
As the hydrophilic binder which can be used in the micro-porous layer according to the invention, for example, polyvinyl alcohol, gelatin, polyethylene oxide, polyvinyl pyrrolidone, polyacrylic acid, polyacrylamide, polyurethane, dextran, dextrin, carrageenan (κ, ι, λ, etc.) agar, pullulan, water-soluble polyvinyl butyral, hydroxyethylcellulose, carboxymethylcellulose, and the like are included. It is possible to combine two or more of these water-soluble binders, but polyvinyl alcohol or derivatives thereof are particularly preferable in terms of relatively small moisture absorption property of the binder, smaller curl of the medium and being high binder performance by the use of a small amount with excellent crack and velation.
As polyvinyl alcohol preferably used in the invention, modified polyvinyl alcohol such as polyvinyl alcohol where the end is modified with cation, and anion modified polyvinyl alcohol having anionic group are included in addition to common polyvinyl alcohol obtained by hydrolyzing polyvinyl acetate.
As polyvinyl alcohol obtained by hydrolyzing polyvinyl acetate, those with an average polymerization degree of 300 or more are preferably used, and particularly those with an average polymerization degree of 1,000 to 5,000 are preferably used. A saponification degree is preferably from 70 to 100%, and particularly preferably 80 to 99.8%.
The cation modified polyvinyl alcohol is, for example, the polyvinyl alcohol having primary to tertiary amino groups and quaternary amino groups in a backbone or side chains as described in JP Tokukaisho 61-10483A, and this is obtained by saponifying a copolymer of an ethylenic unsaturated monomer having cationic group and vinyl acetate.
As the ethylenic unsaturated monomer having cationic group, for example, trimethyl-(2-acrylamide-2,2-dimethylethyl)ammonium chloride, trimethyl-(3-acrylamide-3,3-dimethylpropyl)ammonium chloride, N-vinylimidazole, N-methylvinylimidazole, N-(3-dimethylaminopropyl)methacrylamide, hydroxyethyltrimethylammonium chloride, trimethyl-(3-methacrylamidepropyl)ammonium chloride and the like are included.
A percentage of cation modified group-containing monomer of the cation modified polyvinyl alcohol is from 0.1 to 10 mol %, and preferably from 0.2 to 5 mol % based on vinyl acetate.
As anion modified polyvinyl alcohol, for example, polyvinyl alcohol having anionic group described in JP Tokukaihei 1-206088A, copolymers of vinyl alcohol and a vinyl compound having water-soluble group described in JP Tokukaisho 61-237681A and 63-307979, and modified polyvinyl alcohol having water-soluble group described in JP Tokukaihei 7-285265A are included.
As nonionic modified polyvinyl alcohol, for example, polyvinyl alcohol derivatives where polyalkyleneoxide group is added to a part of vinyl alcohol described in JP Tokukaihei 7-9758A, block copolymer of a vinyl compound having hydrophobic group and vinyl alcohol described in JP Tokukaihei 8-25795A, and the like are included.
Polyvinyl alcohol can be also used in combination with two or more depending on difference in polymerization degree and modification type. Particularly when polyvinyl alcohol with a polymerization degree of 2,000 or more, is used, if it is precedently added at 0.05 to 10% by mass, preferably from 0.1 to 5% by mass based on the inorganic fine particles and then polyvinyl alcohol with a polymerization degree of 2,000 or more is added, there is no remarkable thickening and it is preferable.
A ratio of the inorganic fine particles to the hydrophilic binder in the micro-porous layer is preferably from 2 to 20 at a mass ratio. When the mass ratio is 2 times or more, a porous membrane with sufficient void rate is obtained, a sufficient void capacity is easily obtained, micro-pores are not occupied by swelling of retainable hydrophilic binder at the inkjet recording, and thus it becomes a factor capable of retaining a high ink absorption speed. On the other hand, if this ratio is 20 times or less, when the micro-porous layer is formed by applying a thick membrane, it becomes difficult to cause cracks. The particularly preferable ratio of the inorganic fine particles to the hydrophilic binder is from 2.5 to 12 times, and most preferably it is from 3 to 10 times.
It is preferred that a total amount of the micro-pores (void capacity) in the micro-porous layer is 16 ml or more per m2 of the recording medium. By making the void capacity 16 ml/m2 or more, even when an ink amount becomes large, it is possible to make an ink absorbability good, and thus it is possible to improve the image quality and suppress reduction of drying. Further, the upper limit of the void space is preferably 25 ml/m2 or less.
The void capacity in the invention indicates a saturated water absorption amount obtained by Bristow method. When the transferred amount obtained by Bristow method is plotted versus a square root of the absorption time, a line with a certain slope is obtained. This represents changes of absorption amounts of the recording medium versus the absorption time. When the ink (here, referred to the aqueous solution of 2% C.I. acid red 52) is absorbed to fill up the void capacity, there becomes no room, and thus the slope is 0. The water absorption amount at that time is the saturated water absorption amount, and is considered as a value which represents the void capacity. In the case of the recording medium having an absorbable support preferably used in the invention, it sometimes represents the absorption of the support in addition to the ink absorption by the ink absorbing layer. In the recording medium used in the invention, the absorption speed of the ink in the ink absorbing layer is overwhelmingly much faster than that in the support, and thus, even when the absorption by the support is measured, a curve has double slopes and discrimination of both is easy.
In the invention, the micro-porous layer is referred to the layer with a void rate of 25 to 75%, and the void rate is preferably from 30 to 70%. When the void rate is 25% or more, the desired ink absorption speed can be accomplished without making a membrane thickness thick unnecessarily. When it is 75% or less, the ink absorption speed does not become excessively fast, and additionally it is possible to prevent obstacle (cracks) at a coating and drying steps and stably obtain the image at high definition.
The void rate referred to in the invention indicates the rate of a total volume of the micro-pores in a volume of the micro-porous layer. The void capacity obtained by the above Bristow method can be used as it is for the total volume of the micro-pores. The volume of the micro-porous layer can be obtained as the volume per m2 of the recording medium by measuring the dried membrane thickness. The aimed void rate can be obtained as a ratio of both volumes by calculation. The total volume of the micro-pores can be easily obtained by the saturated transferred amount and the water absorption amount measurement by Bristow method.
For the above micro-porous layer, various additives can be used in addition to the inorganic fine particles and the binder. Among others, a cationic polymeric molecule, hardener, urea or a derivative thereof plays important roles in terms of improving bleeding resistance, bronzing resistance, and scratch/abrasion resistance.
Examples of the cationic polymeric molecules include polyethyleneimine, polyallylamine, polyvinylamine, dicyandiamidepolyalkylenepolyamine condensates, polyalkylenepolyaminedicyandiamide ammonium condensates, dicyandiamideformaline condensates, epichlorohydrin/dialkylamine addition polymers, diallyldimethylammonium chloride polymers, diallyldimethylammonium chloride/SO2 copolymers, polyvinylimidazole, vinylpyrrolidone/vinylimidazole copolymers, polyvinylpyridine, polyamidine, chitosan, cationized starch, vinylbenzyltrimethylammonium chloride polymers, (2-methacroyloxyethyl)trimethylammonium chloride polymers, dimethylaminoethyl methacrylate polymers, and the like.
Cationic polymeric molecules described in Kagaku Kogyo Jiho (Aug. 15 and 25, 1998) and polymeric dye fixing agents described in “Kobunshi Yakuzai Nyumon” published by Sanyo Chemical Industries Ltd. are included as the examples.
In the recording medium according to the invention, it is preferable to add the hardener of the water-soluble binder which forms the micro-porous layer.
The hardener which can be used for a hard membrane of the water-soluble binder which forms the micro-porous layer in the invention is not particularly limited so long as it performs a hardening reaction with the water-soluble binder. Boric acid and salts thereof are preferable, but the other known in the art can be also used. Generally it is the compound having groups capable of reacting with the water-soluble binder or the compound which facilitates a reaction of different groups one another which the water-soluble binder has, and is appropriately used depending on the type of water-soluble binder. Specific examples of the hardener include epoxy type hardeners (diglycidylethylether, ethyleneglycol diglycidylether, 1,4-butanediol diglycidylether, 6-diglycidylcyclohexane, N,N-diglycidyl-4-glycidyloxyaniline, sorbitol polyglycidylether, etc.), aldehyde type hardeners (formaldehyde, glyoxazol, etc.), active halogen type hardeners (2,4-dichloro-4-hydroxy-1,3,5-s-triadine, etc.), active vinyl type compounds (1,3,5-trisacryloyl-hexahydro-s-triadine, bisvinylsulfonylmethylether, etc.), aluminium alum, and the like.
Boric acid and salts thereof are referred to oxyacids where boron atom is a central atom and salts thereof, and specifically, ortho-boric acid, diboric acid, metaboric acid, tetraboric acid, pentaboric acid and octaboric acid and salts thereof are included.
Boric acid having boron atoms and the salts thereof as the hardeners may be used as an aqueous solution thereof alone or in mixture with two or more. Particularly preferable is a mixed aqueous solution of boric acid and borax. Aqueous solutions of boric acid and borax are each added only by relatively diluted aqueous solutions, but it is possible to make a thick aqueous solution by mixing the both, and concentrate the coating solution. Besides there is an advantage that pH of the added aqueous solutions can be controlled relatively freely. A total use amount of the above hardener is preferably from 1 to 600 mg per g of the above water-soluble binder.
It is possible to add polyvalent metal ions to the recording medium according to the invention. The polyvalent metal ion is not particularly limited so long as it is bivalent or more metal ion, and preferable polyvalent ions include aluminium ion, zirconium ion, titanium ion and the like. These polyvalent metal ions can be contained in the micro-porous layer in a water-soluble or water-insoluble salt form.
These polyvalent metal ions may be used alone or in combination with different two or more. The compound comprising the polyvalent metal ions may be added to a coating solution which forms the micro-porous layer or supplied to the micro-porous layer by an over coat method after once applying the micro-porous layer, particularly after once applying and drying the micro-porous layer. As the former, when the compound comprising the polyvalent metal ions is added to the coating solution which forms the ink absorbing layer, it is possible to use the method of adding by uniformly dissolving in water or an organic solvent or a mix solvent thereof or the method of adding by dispersing into fine particles by a wet pulverizing method of a sand mill, an emulsifying dispersion method and the like. When the micro-porous layer is made up of multiple layers, they may be added to the coating solution for only one layer or can be added to the coating solutions for two or more layer or all constitutive layers. As the latter, when they are added by the over coat method after once forming the micro-porous layer, it is preferred that the compound comprising the polyvalent metal ions is uniformly dissolved in the solvent, and subsequently supplied to the micro-porous layer.
These polyvalent metal ions are used in the range of about 0.05 to 20 mmol, and preferably from 0.1 to 10 mmol per m2 of the recording medium.
To the micro-porous layer according to the invention, various additives other than the above can be added. For example, it is possible to contain various additives known in the art such as polystyrene, polyacrylate esters, polymethacrylate esters, polyacrylamides, polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, or copolymers thereof, urea resins, or organic latex fine particles of melamine resins, various cationic or nonionic surfactants, ultraviolet ray absorbents described in JP Tokukaisho 57-74193A, 57-87988A and 62-261476A, anti-color fading agents described in JP Tokukaisho 57-74192A, 57-87989A, 60-71785A, 61-146591A, JP Tokukaihei 1-95091A and 3-13376A, fluorescent brightening agents described in JP Tokukaisho 59-42993A, 59-52689A, 62-280069A, 61-242871A and JP Tokukaihei 4-219266A, pH adjusters such as sulfuric acid, phosphoric acid, citric acid sodium hydroxide, potassium hydroxide and potassium carbonate, ant-foaming agent, preservative, thickening agent, anti-electrostatic agent and matting agent.
Both an absorbable support and non-absorbable support can be used as the support of the recording medium according to the invention. As for the absorbable support, for example, paper support such as regular paper, baryta paper, art paper, coated paper, cast-coated paper and the like can be given. As for the non-absorbable support, RC paper in which polyethylene resin coats both side of a paper support, PET and white PET, polyvinyl chloride, Yupo (Yupo Corp.) and the like can be given. Among them, the absorbable support is preferably used form a viewpoint of bringing out the effect of the invention.
The absorbable support of the invention can include, for example, sheet, plate and the like having common paper, synthetic paper, fabrics, wood materials and the like, and particularly the paper is the most preferable because it is excellent in absorbability of the substrate itself and cost. The paper support is illustrated below.
As basic materials of the paper support, it is possible to use those where a major basic material is wood pulps such as chemical pulps such as LBKP and NBKP, mechanical pulps such as GP, CGP, RMP, TMP, CTMP, CMP and PGW, and used paper pulps such as DIP, and it is preferable to use hardwood pulps. As the hardwood pulps, kraft pulp, sulfate pulp, chemithermomechanical pulp, chemimechanical pulp and the like may be used alone or in combination with several types. If necessary, paper making is performed by using synthetic pulp such as polypropylene or synthetic fibers such as nylon and polyester in addition to the wood pulps.
In terms of improving whiteness degree, it is preferred that a bleaching treatment by peroxide and the like is given to the pulp which is a basic material. It is preferred that the bleaching treatment is given after digesting the pulp, subsequent chlorine treatment, alkali treatment or extraction, hypochlorite bleaching, chlorine dioxide bleaching, and multistage bleaching by combination thereof, further if necessary reduction bleaching by hydrosulfite and sodium borohydride. More preferably, peroxide bleaching treatment in alkali could be given as the final pulp bleaching treatment after the pulp bleaching treatments known in the art after digesting the pulp, but the alkali treatment or extraction or purification may be further given.
Various additives conventionally known in the art such as a sizing agent, pigments, paper power enhancer, fixing agents, fluorescent brightening agent, wet paper power agent and cationizing agent can be added to the paper support if necessary. As the sizing agent, the sizing agents such as a higher fatty acid, alkylketene dimer, rosin, paraffin wax, alkenylsuccinic acid and petroleum resin emulsion can be added if necessary. The pigments include calcium carbonate, talc, titanium oxide, urea resin fine particles and the like, the paper power enhancers include starch, polyacrylamide, polyvinyl alcohol and the like, and the fixing agents include sulfate band and cationic polymeric electrolytes, but they are not limited thereto.
The paper support can be manufactured by mixing the above fiber substances such as wood pulps and various additives and using various paper making machines such as a fourdrinier machine, cylinder machine and twin wire paper making machine. If necessary, it is also possible to give a size press treatment by starch, polyvinyl alcohol and the like, various coating treatments and calendar treatment in the paper making stage or after the paper making.
A paper density is generally from 0.7 to 1.2 g/cm3 (JIS-P-8118). A base paper stiffness is preferably from 20 to 200 g under the condition defined in JIS-P-8143.
A paper pH is preferably from 5 to 9 when measured a hot water extraction method defined in JIS-P-8113.
In the invention, for the purpose of increasing an adhesion strength of the support and the ink receiving layer, it is possible to give corona discharge treatment, undercoating treatment and application of an intermediate layer prior to the application of the ink receiving layer.
For the recording medium according to the invention comprising the above constitution, it is preferred that a 20-degree specular gloss is from 20 to 45%.
The 20-degree specular gloss referred to in the invention is a 20-degree specular gloss value (%) measured according to the method defined in JIS-Z-8741. The specular gloss correlates with smoothness of the recording medium surface, and the smoother the surface is, the higher the specular gloss is. Thus, when the 20-degree specular gloss is less than 20%, the smoothness of recording medium surface is insufficient and the gloss of whole image is reduced when a pigment image is formed thereon. Also, as is shown in Table 1, when the adhering amount of the pigment ink is increased, the specular gloss is raised. At that time, when the specular gloss of the white background section (surface of recording medium) on which no pigment ink is adhered is less than 20%, gloss difference between an image section and a non-image section becomes large and only the image section stands out in bold relief.
Meanwhile, when trying to manufacture the recording medium where the 20-degree specular gloss exceeds 45%, numerous energy is required to make the surface smooth, and it becomes unrealistic. Furthermore, when the surface is made smooth such that the 20-degree specular gloss exceeds 45%, the micro-porous layer of the recording medium is crushed, the absorption speed and the absorption capacity are reduced consequently leading to color turbidity at the image formation, and it becomes impossible to obtain the image with high definition. Thus, by making the 20-degree specular gloss between 20% and 45%, it is possible to inhibit a phenomenon where only the image section stands out in bold relief, which is unique for the image formed by the pigment inks, and improve depth feel of the whole image. Also, it is possible to form the image with high definition without causing the color turbidity. As a result, it becomes possible to obtain the images which come near the silver halide photographs.
The 20-degree specular gloss according to the invention can be measured using, for example, precision glossmeters GM-26D, True Gloss GM-26DPRO and a variable angle glossmeter GM-3D (supplied from Murakami Color Research Laboratory), variable angle glossmeters VGS-10001DP, VG-2000 (supplied from Nippon Denshoku Industries Co., Ltd.), a digital variable angle glossmeter (supplied from Suga Test Instruments Co., Ltd.) and the like.
In the recording medium according to the invention, a way for realizing the 20-degree specular gloss value (%) within the scope defined in the invention is not particularly limited, but, for example, the desired 20-degree specular gloss value (%) can be obtained by the method of previously giving a smoothing treatment to a support surface and forming an ink absorption layer thereon, the method of installing the ink absorption layer on the smooth support where boric acid has been previously impregnated, the method of installing a polymer fine particle layer on an ink absorption layer surface and smoothing by treatment with heat and pressure, the method of installing a gloss layer made up of inorganic fine particles and a binder on the ink absorption layer surface, the method of applying the ink absorption layer and subsequently performing the smoothing treatment such as a calendar treatment, and the like. For example, in the case of surface smoothing by a specular roll, it is preferable to perform typically at about 20 to 100° C. with a line pressure of 0.5 to 4 kN/cm, at a feeding velocity of 10 to 500 m/min as a calendar condition and dry at about 20 to 100° C. for about 0.1 to 10 min.
Next, the method of manufacturing the recording medium of the invention is illustrated.
As the method of manufacturing the recording medium of the invention, it is possible to manufacture by appropriately selecting an application mode from the application modes known in the art and applying and drying respective constituent layers comprising the ink absorbing layer onto the support separately or simultaneously. As the application mode, for example, a roll coating method, rod bar coating method, air knife coating method, spray coating method, curtain application method, or a slide bead application method using a hopper described in U.S. Pat. Nos. 2,761,419 and 2,761,791, an extrusion coat method and the like are preferably used.
As a viscosity when a simultaneous overlaying application is performed, in the case of using the slide bead application mode, it is preferably in the range of 5 to 100 mPa·s, and more preferably from 10 to 70 mPa·s. In the case of using the curtain application mode, it is preferably in the range of 5 to 1200 mPa·s, and more preferably from 25 to 500 mPa·s.
The viscosity of the coating solution at 15° C. is preferably 100 mPa·s or more, more preferably from 100 to 30,000 mPa·s, still preferably from 3,000 to 30,000 mPa·s, and most preferably from 10,000 to 30,000 mPa·s.
As the applying and drying methods, it is preferred that the coating solution is heated to 30° C. or above, the simultaneous overlaying application is performed, subsequently a temperature of a formed coating film is once cooled to 1 to 15° C., and the drying is performed at 10° C. or above. More preferably, a drying condition is that the drying is performed at the condition in the range of a wet bulb temperature of 5 to 50° C. and a membrane surface temperature of 10 to 50° C. Cooling immediately after the application is preferably performed by a horizontal set mode in terms of formed coating film uniformity.
EXAMPLES
Hereinafter, the present invention is specifically illustrated by referring to Examples, but the invention is not limited thereto.
Example 1
<<Manufacture of Recording Medium>>
[Manufacture of Recording Medium 1]
[Manufacture of Support]
Base paper was made by preparing a slurry solution containing 1 part of polyacrylamide, 4 parts of ash (talc), 2 parts of cationized starch, 0.5 parts of polyamide epichlorohydrin resin and various addition amounts of alkylketene dimer (sizing agent) for 100 parts of wood pulp (LBKP/NBSP=50/50) and using a fourdrinier machine such that a weighing is 170 g/m2. A support 1, which was an absorbable support and has a smooth surface, was made by giving a calendar treatment to this base paper.
After giving corona discharge to this support 1, a hardener-containing gelatin undercoating layer was applied at 0.04 g/m2 in terms of a solid content, and on a back face, a styrene/acryl type emulsion containing silica fine particles (matting agent) with a mean particle size of 1 μm and a small amount of a cationic polymeric molecule (conducting agent) was applied such that a dried film thickness is about 0.5 μm.
[Preparation of Coating Solution for Ink Absorbing Layer]
A coating solution for an ink absorbing layer (micro-porous layer) was prepared according to the following procedure.
(Preparation of Titanium Oxide Dispersion)
Titanium oxide (20 kg) (W-10 supplied from Ishihara Sangyo Co., Ltd.) with a mean particle size of 0.25 μm was added to 90 L of an aqueous solution at pH 7.5 containing 150 g of sodium tripolyphosphate, 500 g of polyvinyl alcohol (PVA235 supplied from Kuraray Co., Ltd.), 150 g of cationic polymeric molecule (P-1) and 10 g of anti-foaming agent SN 381 supplied from San nobuko KK, dispersed by a high pressure homogenizer (Sanwa Industries Co., Ltd.), and subsequently a total amount was filled up to 100 L to yield a uniform titanium oxide dispersion.
















(PREPARATION OF SILICA DISPERSION 1)

















Water
71
L


Boric acid
0.27
kg


Borax
0.24
kg


Ethanol
2.2
L


Aqueous solution of 25% cationic polymeric molecule P-1
17
L


Aqueous solution of 10% anti-color fading agent (AF1 *1)
8.5
L


Aqueous solution of fluorescent brightening agent (*2)
0.1
L









A total amount was filled up to 100 L with purified water.
As inorganic fine particles, 50 kg of silica fine particles (mean primary particle size: about 35 nm) were prepared, the above additives were added thereto, and subsequently the dispersion was performed by a dispersion method described in Example 5 of JP-Tokukai-2002-47454A to yield a silica dispersion 1.
1: Anti-color fading agent (AF-1) HO—N(C2H4SO3Na)2 
2: UVITEX NFW LIQUID supplied from Ciba Specialty Chemicals Inc.
(Preparation of Silica Dispersion 2)
A silica dispersion 2 was prepared as is the case with the preparation of the above silica dispersion 1, except that the cationic polymeric molecule (P-1) was changed to a cationic polymeric molecule (P-2).




(Preparation of Coating Solution)

Respective coating solutions of the first, second, third and fourth layers were prepared by the following procedures.
<Coating Solution for First Layer>
The following additives were sequentially added to 610 ml of the silica dispersion 1 at 40° C. with stirring.

















Aqueous solution of 5% polyvinyl alcohol (PVA235
220
ml



supplied from Kuraray Co., Ltd.)



Aqueous solution of 5% polyvinyl alcohol (PVA245
80
ml



supplied from Kuraray Co., Ltd.)



Titanium oxide dispersion
30
ml



Polybutadiene dispersion (mean particle size: about
15
ml



0.5 μm, solid concentration: 40%)



Aqueous solution of 5% surfactant (SF1)
1.5
ml










A total amount was filled up to 1000 ml with purified water.
<Coating Solution for Second Layer>
The following additives were sequentially added to 630 ml of the silica dispersion 1 at 40° C. with stirring.

















Aqueous solution of 5% polyvinyl alcohol (PVA235
180
ml



supplied from Kuraray Co., Ltd.)



Aqueous solution of 5% polyvinyl alcohol (PVA245
80
ml



supplied from Kuraray Co., Ltd.)



Polybutadiene dispersion (mean particle size: about
15
ml



0.5 μm, solid concentration: 40%)










A total amount was filled up to 1000 ml with purified water.
<Coating Solution for Third Layer>
The following additives were sequentially added to 650 ml of the silica dispersion 2 at 40° C. with stirring.

















Aqueous solution of 5% polyvinyl alcohol (PVA235
180
ml



supplied from Kuraray Co., Ltd.)



Aqueous solution of 5% polyvinyl alcohol (PVA245
80
ml



supplied from Kuraray Co., Ltd.)










A total amount was filled up to 1000 ml with purified water.
<Coating Solution for Fourth Layer>
The following additives were sequentially added to 650 ml of the silica dispersion 2 at 40° C. with stirring.

















Aqueous solution of 5% polyvinyl alcohol (PVA235
180
ml



supplied from Kuraray Co., Ltd.)



Aqueous solution of 5% polyvinyl alcohol (PVA245
80
ml



supplied from Kuraray Co., Ltd.)



Aqueous solution of 50% saponin
4
ml



Aqueous solution of 5% surfactant (SF1)
6
ml










A total amount was filled up to 1000 ml with purified water.




The two step filtration of the respective coating solutions prepared as above was performed with a 20 μm filter capable of collecting.
All of the above coating solution exhibited viscosity property of 30 to 80 mPa·s at 40° C. and 30,000 to 100,000 mPa·s at 15° C.
(Application)
The respective coating solutions obtained in this way were simultaneously applied on an upper side of the above support made above to arrange in order of the first layer (35 μm), the second layer (45 μm), the third layer (45 μm) and the fourth layer (40 μm). A number in a parenthesis indicates a wet film thickness. The application was simultaneously performed at an application width of about 1.5 m at an application speed of 100 m/min using each coating solution at 40° C. and using a 4 layer type curtain coater.
Immediately after the application, cooling was performed in a cooling zone retained at 8° C. for 20 sec, and subsequently drying was performed by blowing respective drying winds at 20 to 30° C. and a relative humidity of 20% or less for 30 sec, at 60° C. and a relative humidity of 20% or less for 120 sec, and at 55° C. and a relative humidity of 20% or less for 60 sec. The film temperature was 8 to 30° C. in the constant rate of drying. After the film temperature gradually increases in the constant rate of drying, recording medium 1 was obtained by performing air conditioning in an air conditioning zone at 23° C. and relative humidity of 40 to 60%, and rolling up in a roll shape. The obtained recording medium 1 was then stored in a roll shape at 40° C. for 5 days with being humidified, and subsequently cut into a given size. As a result of measuring by the method described below, the void rate of the recording medium was 55%. Also as a result of measuring by the method described below, the transferred amount at 0.04 sec of absorption time and the void capacity by Bristow method were respectively 20 ml/m2 and 25 ml/m2. According to JIS-Z-8741, 20-degree specular gloss on the side where the ink absorbing layer is coated is measured by variable angle gloss meter VGS-1001DP (supplied by Nippon Denshoku Industries Co., Ltd). It was 17%.
It is to be noted that the other recording media are prepared to have the void capacity of 25 ml/m2 by controlling the amount of silica fine particles and polyvinyl alcohols and the like constituting the ink absorbing layer.
[Manufacture of Recording Medium 2]
A recording medium 2 where the transferred amount at 0.04 sec of absorption time by Bristow method was 8 ml/m2 was made by changing the support 1 to the following support 2 and appropriately changing a constituent ratio (F/B) of silica fine particles (F) to polyvinyl alcohol (B) in the respective ink absorbing layers in the manufacture of the above recording medium 1.
(Manufacture of Support 2)
Base paper was made by preparing a slurry solution containing 1 part of polyacrylamide, 4 parts of ash (talc), 2 parts of cationized starch, 0.5 parts of polyamide epichlorohydrin resin and various addition amount of alkylketene dimer (sizing agent) for 100 parts of wood pulp (LBKP/NBSP=50/50) and using a fourdrinier machine such that a weighing is 170 g/m2. After giving a calendar treatment to this base paper, a low density polyethylene resin with a density of 0.92 containing 7% anatase type titanium oxide and a small amount of a color tone adjuster was coated on a single side of the base paper by a melting extrusion coating method such that a thickness is 28 μm at 320° C. Immediately after the melting extrusion application, various fine particle typing treatments was given to the surface of polyethylene by pressing/cooling a cooling roll having various regular concavoconvex height. Difference of the typing was made by conditioning the density and the concavoconvex height.
Then, a support 2 which was non-absorbable support was made by coating a melted matter where high density polyethylene with a density of 0.96 and low density polyethylene with a density of 0.92 were mixed at 70/30 on an opposite side face similarly by the melting extrusion coating method such that a thickness was 32 μm.
After giving corona discharge to a face side of the layer containing titanium oxide of this support 2, a hardener-containing gelatin undercoating layer was applied at 0.04 g/m2 in terms of a solid content, and on a back face, a styrene/acryl type emulsion containing silica fine particles (matting agent) with a mean particle size of 1 μm and a small amount of a cationic polymeric molecule (conducting agent) was applied such that a dried film thickness was about 0.5 μm.
[Manufacture of Recording Medium 3]
A recording medium 3 where the transferred amount at 0.04 sec of absorption time by Bristow method was 20 ml/m2 was prepared by appropriately changing a constituent ratio (F/B) of silica fine particles to polyvinyl alcohol in the respective ink absorbing layers in the manufacture of the above recording medium 2.
[Manufacture of Recording Medium 4]
A recording medium 4 where the transferred amount at 0.04 sec of absorption time by Bristow method was 11 ml/m2 was made by appropriately changing a constituent ratio (F/B) of silica fine particles to polyvinyl alcohol in the respective ink absorbing layers in the manufacture of the above recording medium 1.
The void rate was measured by the method described below, and it was 35%.
[Manufacture of Recording Medium 5]
(Preparation of Application Solution)

















Alumina hydrate (Disperal HP18 supplied from
0.50
kg



Sasol Ltd.)



Purified water
10
L










Hydrochloric acid at 1 mol/L was added to the above dispersion to adjust pH to 4, and this was stirred at 95° C. for 2 hours. Then, an aqueous solution of sodium hydroxide at 1 mol/L was added to adjust pH to 10, and further stirred for 8 hours. After stirring, the solution was cooled to room temperature, pH was adjusted to 7 to 8, desalting treatment was given, and further acetic acid was added to deflocculate. After concentrating until a solid content became 17%, an aqueous solution of 9% polyvinyl alcohol (PVA117 supplied from Kuraray Co., Ltd.) was mixed such that a solid content ratio of alumina to polyvinyl alcohol was 10:1 at a weight ratio, and stirred to yield a coating solution.
The coating solution prepared as the above was filtrated with a 20 μl filter capable of collecting. This coating solution was applied onto the baryta layer of a substrate having the baryta layer (whiteness degree: 89%) by a die coater such that a dried film thickness was 30 g/m2. An applying speed at that time was 50 m/min and the drying was performed at a temperature of 150° C. to make a recording medium 5.
The mean particle size of the alumina particles in the recording medium 5 was 30 nm. The transferred amount at 0.04 sec of absorption time by Bristow method was 20 ml/m2 and the void rate was 55%.
[Manufacture of Recording Media 6 to 9]
Recording media 6 to 9 were made as was the case with the manufacture of the recording medium 1, except that the silica particles (primary mean particle size: about 35 nm) used for the preparation of the respective ink absorbing layer coating solutions were changed to silica particles with mean particle size described in Tables 2 and 3. The transferred amounts and the void rates of these recording media were as was shown in tables 2 and 3.
[Manufacture of Recording Medium 10]
A recording medium 10 was made as was the case with the manufacture of the recording medium 1, except that boric acid and borax used for the preparation of the respective ink absorbing layer coating solutions were removed.
[Manufacture of Recording Media 11 and 12]
A recording media 11 and 12 were made as was the case with the manufacture of the recording medium 1, except the constitution ratio (F/B) of the silica fine particles and the polyvinyl alcohol is changed properly so that the void rate of the ink absorbing layer is respectively 25 and 75%.
[Manufacture of Recording Medium 13]
A recording medium 13 was made as was the case with the manufacture of the recording medium 1, except the calender treatment was given after the application. The 20-degree specular gloss of this recording medium was 23%.
[Manufacture of Recording Medium 14]
A recording medium 14 was made as was the case with the manufacture of the recording medium 5, except the support was previously given to the super calender treatment so that the surface of the baryta layer is smooth. The 20-degree specular gloss of this recording medium was 32%.
[Manufacture of Recording Medium 15]
A recording medium 15 was made as was the case with the manufacture of the recording medium 14, except the calender treatment is given after the application. The 20-degree specular gloss of this recording medium was 42%.
<<Preparation of Color Ink Set>>
[Preparation of Polymeric Dispersant]
(Preparation of Polymeric Dispersant SA-1)
A3 L four neck flask was equipped with a three one motor, a thermometer, a nitrogen introduction tube and a drop funnel with a dry tube. Tetrahydrofuran (780.0 g) and p-xylene (3.6 g) were introduced thereto with running a dried nitrogen gas. With stirring, tetrabutylammonium m-benzoate (1 mol/L solution: 3.2 ml) was added thereto, and further 1,1-bis(methylsiloxy)-2-methylpropene (144.0 g) was added.
Next, tetrabutylammonium m-benzoate (1 mol/L solution: 3.2 ml) was dripped from the drop funnel over 130 min with stirring. After dripping, a mixture of benzyl methacrylate (272.6 g) and trimethylsilyl methacrylate (489.8 g) was dripped from the drop funnel over 40 min with stirring. After stirring for 30 min, benzyl methacrylate (545.4 g) was dripped from the drop funnel over 30 min with stirring.
After stirring as it is for 240 min, methanol anhydrate (216 g) was added and stirred. The drop funnel was replaced with Liebig cooling tube, an entire vessel was heated, and a distillate (210 g) at a boiling point of 55° C. or below which evaporated was eliminated. Distillation was further continued, at the time point when the boiling point was 76° C., 2-propanol (900 g) was added, and heating/distillation was continued. The heating was continued until a total amount of 1440 g of solvents flowed out to yield a solution 1 of a target block copolymer (BzMA//BzMA/MAA=5//2.5/5). A part thereof was dried, a molecular weight and an acid value were measured, which were then 1,500 and 70, respectively.
N,N-dimethylethanolamine was added to this solution and neutralized to yield a target polymer surfactant SA-1.
(Preparation of Polymeric Dispersant SA-2)
The polymeric dispersant SA-2 was prepared as is the case with the preparation of the above polymeric dispersant SA-1, except that the neutralization was performed using potassium hydroxide in place of N,N-dimethylethanolamine.
(Preparation of Polymeric Dispersant SA-3)
An 1 L four-necked flask was equipped with a three one motor, a thermometer, a reflux tube with a nitrogen introduction tube and a drop funnel. The following monomer mixture 1 was introduced thereto with running a dried nitrogen gas, and the temperature was raised to 65° C.
Next, the following monomer mixture 2 was dripped over 2.5 hours with stirring. Further, a mixed solution of azobisdimethylvaleronitrile (0.8 g) and methylethylketone (22 ml) was dripped over 0.5 hours. Azobisdimethylvaleronitrile (0.8 g) was added and further heated/stirred for one hour.
After the completion of the reaction, methylethylketone (450 ml) was added to yield a polymeric dispersant SA-3 solution with solid content of 50%. A part thereof was dried, the molecular weight and the acid value were measured, which were then 1,500 and 55, respectively.










(MONOMER MIXTURE 1)

















Styrene
11.2
g


Lauryl methacrylate
12.0
g


Polyethyleneglycol methacrylate (Light Ester 130MA
4.0
g


supplied from Kyoeisha Chemical Co., Ltd.)


Styrene macromer (Macromonomer AS-6 supplied from
4.0
g


Toagosei Co., Ltd.)


Acrylic acid
2.8
g


Mercaptoethanol
0.4
g



















(MONOMER MIXTURE 2)

















Styrene
100.8
g


Lauryl methacrylate
108.0
g


Hydroxyethyl methacrylate
60.0
g


Polyethyleneglycol methacrylate (Light Ester 130MA
36.0
g


supplied from Kyoeisha Chemical Co., Ltd.)


Styrene macromer (Macromonomer AS-6 supplied from
36.0
g


Toagosei Co., Ltd.)


Acrylic acid
25.2
g


Mercaptoethanol
3.6
g


Azobisdimethylvaleronitrile
2.4
g


Methylethylketone
22
ml









[Preparation of Color Ink Set 1]

(Preparation of Pigment Dispersion)











<PREPARATION OF YELLOW PIGMENT DISPERSION 1>


















C.I. Pigment Yellow 74
20% by mass



Polymeric dispersant SA-1
10% by mass




(as a solid content)



Glycerine
15% by mass



Ion-exchange water
residual quantity










The above respective additives were mixed and a quantity was adjusted with ion-exchange water such that a total quantity was 100% by mass. This was dispersed using a horizontal type bead mill (System Zeta mill supplied from Ashizawa Finetech Ltd.) in which zirconia beads of 0.3 mm were filled at a volume rate of 60% to yield a yellow pigment dispersion 1. A mean particle size of the resulting yellow pigments was 112 nm. Zetasizer 1000 (supplied from Malvern Instruments) was used for the measurement of the mean particle size.










<PREPARATION OF MAGENTA PIGMENT DISPERSION 1>


















C.I. Pigment Red 122
25% by mass



Polymeric dispersant SA-2
16% by mass




(as a solid content)



Glycerine
15% by mass



Ion-exchange water
residual quantity










The above respective additives were mixed and a quantity was adjusted with ion-exchange water such that a total quantity was 100% by mass. This was dispersed using a horizontal type bead mill (System Zeta mill supplied from Ashizawa Finetech Ltd.) in which zirconia beads of 0.3 mm were filled at a volume rate of 60% to yield a magenta pigment dispersion 1. The mean particle size of the resulting magenta pigments was 105 nm.










<PREPARATION OF CYAN PIGMENT DISPERSION 1>


















C.I. Pigment Blue 15:3
25% by mass



Polymeric dispersant SA-1
13% by mass




(as a solid content)



Diethyleneglycol
10% by mass



Ion-exchange water
residual quantity










The above respective additives were mixed and a quantity was adjusted with ion-exchange water such that a total quantity was 100% by mass. This was dispersed using a horizontal type bead mill (System Zeta mill supplied from Ashizawa Finetech Ltd.) in which zirconia beads of 0.3 mm were filled at a volume rate of 60% to yield a cyan pigment dispersion 1. The mean particle size of the resulting cyan pigments was 87 nm.










<PREPARATION OF BLACK PIGMENT DISPERSION 1>


















Carbon black
20% by mass



Polymeric dispersant SA-2
 9% by mass




(as a solid content)



Glycerine
10% by mass



Ion-exchange water
residual quantity










The above respective additives were mixed and a quantity was adjusted with ion-exchange water such that a total quantity was 100% by mass. This was dispersed using a horizontal type bead mill (System Zeta mill supplied from Ashizawa Finetech Ltd.) in which zirconia beads of 0.3 mm were filled at a volume rate of 60% to yield a black pigment dispersion 1. The mean particle size of the resulting black pigments was 75 nm.










<PREPARATION OF BLUE PIGMENT DISPERSION 1>


















C.I. Pigment Violet 23
25% by mass



Polymeric dispersant SA-1
13% by mass




(as a solid content)



Glycerin
10% by mass



Ion-exchange water
residual quantity










The above respective additives were mixed and a quantity was adjusted with ion-exchange water such that a total quantity was 100% by mass. This was dispersed using a horizontal type bead mill (System Zeta mill supplied from Ashizawa Finetech Ltd.) in which zirconia beads of 0.3 mm were filled at a volume rate of 60% to yield a blue pigment dispersion 1. The mean particle size of the resulting black pigments was 107 nm.










<PREPARATION OF RED PIGMENT DISPERSION 1>


















C.I. Pigment Red 177
25% by mass



Polymeric dispersant SA-2
16% by mass




(as a solid content)



Glycerin
15% by mass



Ion-exchange water
residual quantity










The above respective additives were mixed and a quantity was adjusted with ion-exchange water such that a total quantity was 100% by mass. This was dispersed using a horizontal type bead mill (System Zeta mill supplied from Ashizawa Finetech Ltd.) in which zirconia beads of 0.3 mm were filled at a volume rate of 60% to yield a blue pigment dispersion 1. The mean particle size of the resulting black pigments was 98 nm.
(Preparation of Color Ink Set)
A color ink set 1 composed of a yellow ink 1, a magenta ink 1, a cyan ink 1, a black ink 1, blue ink 1 and red ink 1 was prepared using the respective pigment dispersions prepared above according to the following procedure.










<PREPARATION OF YELLOW INK 1>
















Yellow pigment dispersion 1
  15% by mass


Ethyleneglycol
  4% by mass


Glycerine
3.75% by mass


2-Pyrrolidone
  5% by mass


Surfactant 1 (Surfynol 465 supplied from Nisshin
 0.5% by mass


Chemical Industry Co., Ltd.)


Surfactant 2 (Pelex OT-P, supplied from Kao
the following required


Corporation)
amount


Ion-exchange water
residual quantity









The surfactant 2 was added such that the surface tension was 26 mN/m and a quantity was adjusted with ion-exchange water such that a total quantity was 100% by mass. A yellow ink 1 which was a pigment ink was prepared by mixing the above compositions, stirring and filtrating with a 1 μm filter. The mean particle size of pigments in the ink was 122 nm.










<PREPARATION OF MAGENTA INK 1>
















Magenta pigment dispersion 1
  15% by mass


Glycerine
  8% by mass


Diethyleneglycol
1.75% by mass


2-Pyrrolidone
  3% by mass


Surfactant 1 (Surfynol 465 supplied from Nisshin
 0.5% by mass


Chemical Industry Co., Ltd.)


Surfactant 2 (Pelex OT-P, supplied from Kao
the following required


Corporation)
amount


Ion-exchange water
residual quantity









The surfactant 2 was added such that the surface tension was 26 mN/m and a quantity was adjusted with ion-exchange water such that a total quantity was 100% by mass. A magenta ink 1 which was a pigment ink was prepared by mixing the above compositions, stirring and filtrating with a 1 μm filter. The mean particle size of pigments in the ink was 122 nm.










<PREPARATION OF CYAN INK 1>
















Cyan pigment dispersion 1
 10% by mass


Ethyleneglycol
  8% by mass


Diethyleneglycol
  4% by mass


Glycerine
  5% by mass


2-Pyrrolidone
  2% by mass


Surfactant 1 (Surfynol 465 supplied from Nisshin
0.5% by mass


Chemical Industry Co., Ltd.)


Surfactant 2 (Pelex OT-P, supplied from Kao
the following required


Corporation)
amount


Ion-exchange water
residual quantity









The surfactant 2 was added such that the surface tension was 26 mN/m and a quantity was adjusted with ion-exchange water such that a total quantity was 100% by mass. A cyan ink 1 which was a pigment ink was prepared by mixing the above compositions, stirring and filtrating with a 1 μm filter. The mean particle size of pigments in the ink was 88 nm.










<PREPARATION OF BLACK INK 1>
















Black pigment dispersion 1
 10% by mass


Glycerine
  5% by mass


Diethyleneglycol
  7% by mass


2-Pyrrolidone
  2% by mass


Surfactant 1 (Surfynol 465 supplied from Nisshin
0.5% by mass


Chemical Industry Co., Ltd.)


Surfactant 2 (Pelex OT-P, supplied from Kao
the following required


Corporation)
amount


Ion-exchange water
residual quantity









The surfactant 2 was added such that the surface tension was 26 mN/m and a quantity was adjusted with ion-exchange water such that a total quantity was 100% by mass. A black ink 1 which was a pigment ink was prepared by mixing the above compositions, stirring and filtrating with a 1 μm filter. The mean particle size of pigments in the ink was 93 nm.










<PREPARATION OF BLUE INK 1>
















Blue pigment dispersion 1
  15% by mass


Glycerine
  8% by mass


Diethyleneglycol
1.75% by mass


2-Pyrrolidone
  3% by mass


Surfactant 1 (Surfynol 465 supplied from Nisshin
 0.5% by mass


Chemical Industry Co., Ltd.)


Surfactant 2 (Pelex OT-P, supplied from Kao
the following required


Corporation)
amount


Ion-exchange water
residual quantity









The surfactant 2 was added such that the surface tension was 26 mN/m and a quantity was adjusted with ion-exchange water such that a total quantity was 100% by mass. A blue ink 1 which was a pigment ink was prepared by mixing the above compositions, stirring and filtrating with a 1 μm filter. The mean particle size of pigments in the ink was 121 nm.










<PREPARATION OF RED INK 1>
















Red pigment dispersion 1
  15% by mass


Glycerine
  8% by mass


Diethyleneglycol
1.75% by mass


2-Pyrrolidone
  3% by mass


Surfactant 1 (Surfynol 465 supplied from Nisshin
 0.5% by mass


Chemical Industry Co., Ltd.)


Surfactant 2 (Pelex OT-P, supplied from Kao
the following required


Corporation)
amount


Ion-exchange water
residual quantity









The surfactant 2 was added such that the surface tension was 26 mN/m and a quantity was adjusted with ion-exchange water such that a total quantity was 100% by mass. A red ink 1 which was a pigment ink was prepared by mixing the above compositions, stirring and filtrating with a 1 μm filter. The mean particle size of pigments in the ink was 119 nm.
[Preparation of Color Ink Set 2]
A color ink set 2 composed of the base inks (yellow ink 1, magenta ink 1, cyan ink 1 and black ink 1) was prepared as is the case with the preparation of the above color ink set 1, except that blue ink 1 and red ink 1, which were special color inks, were excluded.
[Preparation of Color Ink Set 3]
A color ink set 3 was prepared as is the case with the preparation of the above color ink set 2, except a green ink 1, which is special color ink and prepared according to the following procedure, was added.










<PREPARATION OF GREEN PIGMENT DISPERSION 1>


















C.I. Pigment Green 7
25% by mass



Polymeric dispersant SA-1
13% by mass




(as a solid content)



Glycerin
15% by mass



Ion-exchange water
residual quantity










The above respective additives were mixed and a quantity was adjusted with ion-exchange water such that a total quantity was 100% by mass. This was dispersed using a horizontal type bead mill (System Zeta mill supplied from Ashizawa Finetech Ltd.) in which zirconia beads of 0.3 mm were filled at a volume rate of 60% to yield a blue pigment dispersion 1. The mean particle size of the resulting black pigments was 117 nm.










<PREPARATION OF GREEN INK 1>
















Green pigment dispersion 1
15% by mass 


Glycerine
8% by mass


Diethyleneglycol
3% by mass


2-Pyrrolidone
3% by mass


Surfactant 1 (Surfynol 465 supplied from Nisshin
0.5% by mass  


Chemical Industry Co., Ltd.)


Surfactant 2 (Pelex OT-P, supplied from Kao
the following


Corporation)
required amount


Ion-exchange water
residual quantity









The surfactant 2 was added such that the surface tension was 26 mN/m and a quantity was adjusted with ion-exchange water such that a total quantity was 100% by mass. A green ink 1 which was a pigment ink was prepared by mixing the above compositions, stirring and filtrating with a 1 μm filter. The mean particle size of pigments in the ink was 127 nm.
[Preparation of Color Ink Set 4]
A color ink set 4 was prepared as is the case with the preparation of the above color ink set 1, except that the polymeric dispersants (SA-1, SA-2) used for the preparation of respective pigment dispersions were changed to SA-4 (acrylic type randomly polymerized polymeric dispersant; Johncryl 61, supplied from Johnson Polymer Inc.).
[Preparation of Color Ink Set 5]
A color ink set 3 was prepared as is the case with the preparation of the above color ink set 1, except that the polymeric dispersants (SA-1, SA-2) used for the preparation of respective pigment dispersions were changed to SA-5 (polyvinyl alcohol; PVA210 supplied from Kuraray Co., Ltd.) and an addition amount was doubled.
[Preparation of Color Ink Set 6]
A color ink set 6 was prepared as is the case with the preparation of the above color ink set 1, except that the polymeric dispersants (SA-1, SA-2) used for the preparation of respective pigment dispersions were changed to SA-6 (sodium naphthalene sulfonate).
[Preparation of Color Ink Sets 7 to 10]
Color ink sets 7 to 10 were prepared as is the case with the preparation of the above color ink set 1, except that the addition amounts of the polymeric dispersant used for the preparation of each pigment dispersion and the surfactants 1 and 2 used for the preparation of the ink were appropriately regulated to make the surface tensions of respective inks 31 mN/n, 36 mN/m, 48 mN/m and 54 mN/m, respectively.
[Preparation of Color Ink Set 11]
A color ink set 11 was prepared as is the case with the preparation of the above color ink set 1, except that the cyan ink 1 was changed to a cyan ink 2 prepared according to the following procedure.
(Preparation of Pigment Dispersion)










<PREPARATION OF CYAN PIGMENT DISPERSION>


















C.I. Pigment Blue 15:3
26 g



SA-3 solution
28 g



Aqueous solution of potassium hydroxide at 1 mol/L
13.6 g  



Methylethylketone
20 g



Ion-exchange water
30 g










The above additives were mixed and kneaded 20 times using a three roll mill. The obtained paste was added into ion-exchange water (200 g), stirred thoroughly, and subsequently methylethylketone and water were distilled off using a rotary evaporator such that the solid content was 20% to yield a cyan pigment dispersion 2.
The above additives were mixed and dispersed using a horizontal type bead mill (System Zeta mill supplied from Ashizawa Finetech Ltd.) in which zirconia beads of 0.3 mm were filled at a volume rate of 60% to yield a cyan pigment dispersion 2. The mean particle size of the obtained yellow pigments was 87 nm.










<PREPARATION OF CYAN INK 2>
















Cyan pigment dispersion 2
10% by mass 


Ethyleneglycol
8% by mass


Diethyleneglycol
6% by mass


Glycerine
4% by mass


2-Pyrrolidone
3% by mass


Surfactant 1 (Surfynol 465 supplied from Nisshin
0.5% by mass  


Chemical Industry Co., Ltd.)


Surfactant 2 (Pelex OT-P, supplied from Kao
the following


Corporation)
required quantity


Ion-exchange water
residual quantity









The surfactant 2 was added such that the surface tension was 26 mN/m and a quantity was adjusted with ion-exchange water such that a total quantity was 100% by mass. A cyan ink 2 was prepared by mixing the above compositions, stirring and filtrating with a 1 μm filter. The mean particle size of pigments in the ink was 98 nm.
[Preparation of Color Ink Set 12]
(Preparation of Pigment Dispersion)
<Preparation of Yellow Pigment Dispersion 2>
After 1.5 g of anthranilic acid was added to 10 g of 6 mol/L hydrochloric acid solution, the temperature was cooled to 5° C., 1.8 g of sodium nitrite was added, and stirred. Thereto, 5 g of C.I. Pigment Yellow 74 powder was added, the liquid temperature was raised up to 80° C. with stirring, heating was continued until the production of nitrogen gas was stopped, and subsequently the temperature was cooled. Then, acetone was added, pigment particles were filtrated and washed with ion-exchange water. Subsequently, the ion-exchange water was added, manipulations of ion exchange, ultrafiltration and centrifugation were performed, and a pigment content was adjusted with the ion-exchange water to 20% by mass to yield a yellow pigment dispersion 2.
<Preparation of Magenta Pigment Dispersion 2>
After 1.5 g of anthranilic acid was added to 10 g of 6 mol/L hydrochloric acid solution, the temperature was cooled to 5° C., 1.8 g of sodium nitrite was added, and stirred. Thereto, 5 g of C.I. Pigment Red 122 powder was added, the liquid temperature was raised up to 80° C. with stirring, the heating was continued until the production of nitrogen gas was stopped, and subsequently the temperature was cooled. Then, acetone was added, pigment particles were filtrated and washed with ion-exchange water. Subsequently, the ion-exchange water was added, the manipulations of ion exchange, ultrafiltration and centrifugation were performed, and the pigment content was adjusted with the ion-exchange water to 25% by mass to yield a magenta pigment dispersion 2.
<Preparation of Cyan Pigment Dispersion 3>
After 1.5 g of anthranilic acid was added to 10 g of 6 mol/L hydrochloric acid solution, the temperature was cooled to 5° C., 1.8 g of sodium nitrite was added, and stirred. Thereto, 5 g of C.I. Pigment Blue 15:3 powder was added, the liquid temperature was raised up to 80° C. with stirring, the heating was continued until the production of nitrogen gas was stopped, and subsequently the temperature was cooled. Then, acetone was added, pigment particles were filtrated and washed with ion-exchange water. Subsequently, the ion-exchange water was added, the manipulations of ion exchange, ultrafiltration and centrifugation were performed, and a pigment content was adjusted with the ion-exchange water to 25% by mass to yield a cyan pigment dispersion 3.
<Preparation of Black Pigment Dispersion 2>
After 1.5 g of anthranilic acid was added to 10 g of 6 mol/L hydrochloric acid solution, the temperature was cooled to 5° C., 1.8 g of sodium nitrite was added, and stirred. Thereto, 5 g of carbon black powder was added, the liquid temperature was raised up to 80° C. with stirring, the heating was continued until the production of nitrogen gas was stopped, and subsequently cooled. Then, acetone was added, pigment particles were filtrated and washed with ion-exchange water. Subsequently, the ion-exchange water was added, the manipulations of ion exchange, ultrafiltration and centrifugation were performed, and the pigment content was adjusted with the ion-exchange water to 20% by mass to yield a black pigment dispersion 2.
<Preparation of Blue Pigment Dispersion 2>
After 1.5 g of anthranilic acid was added to 10 g of 6 mol/L hydrochloric acid solution, the temperature was cooled to 5° C., 1.8 g of sodium nitrite was added, and stirred. Thereto, 5 g of C.I. Pigment Violet 23 was added, the liquid temperature was raised up to 80° C. with stirring, the heating was continued until the production of nitrogen gas was stopped, and subsequently cooled. Then, acetone was added, pigment particles were filtrated and washed with ion-exchange water. Subsequently, the ion-exchange water was added, the manipulations of ion exchange, ultrafiltration and centrifugation were performed, and the pigment content was adjusted with the ion-exchange water to 25% by mass to yield a blue pigment dispersion 2.
<Preparation of Red Pigment Dispersion 2>
After 1.5 g of anthranilic acid was added to 10 g of 6 mol/L hydrochloric acid solution, the temperature was cooled to 5° C., 1.8 g of sodium nitrite was added, and stirred. Thereto, 5 g of C.I. Pigment Red 177 was added, the liquid temperature was raised up to 80° C. with stirring, the heating was continued until the production of nitrogen gas was stopped, and subsequently cooled. Then, acetone was added, pigment particles were filtrated and washed with ion-exchange water. Subsequently, the ion-exchange water was added, the manipulations of ion exchange, ultrafiltration and centrifugation were performed, and the pigment content was adjusted with the ion-exchange water to 25% by mass to yield a red pigment dispersion 2.
(Preparation of Color Ink Set)
A color ink set 12 was prepared as is the case with the preparation of the above color ink set 1, except using the yellow pigment dispersion 2, the magenta pigment dispersion 2, the cyan pigment dispersion 3, the black pigment dispersion 2, the blue pigment dispersion 2 and the red pigment dispersion 2 prepared above in place of the yellow pigment dispersion 1, the magenta pigment dispersion 1, the cyan pigment dispersion 1, and the black pigment dispersion 1.
[Preparation of Color Ink Set 13]
A color ink set 13 was prepared as is the case with the preparation of the above color ink set 5, except that ethyleneurea added to the respective color inks at 5% by mass was.
[Preparation of Color Ink Set 14]
A color ink set 13 was prepared as is the case with the preparation of the above color ink set 8, except that ethyleneurea added to the respective color inks at 5% by mass was.
<<Preparation of Invisible Ink>>
An invisible ink made up of the following composition was prepared.













SF110 (urethane resin fine particle, Superflex 110,
10% by mass


MFT = 5° C., volume mean particle size = 90 nm,


supplied from Dai-ichi Kogyo Seiyaku Co., Ltd.)


Surfynol 465 (supplied from Nisshin Chemical
0.4% by mass 


Industry Co., Ltd.)


Ethyleneglycol
20% by mass


Glycerine
10% by mass


Urea
 3% by mass


Pure water
56.6% by mass  









<<Measurement of Property Values of Recording Medium and Inks>>

[Recording Medium: Measurement of Transferred Amount]

The transferred amount at 0.04 seconds of absorption time by Bristow method was measured in each recording medium made above according to the following method.
In the method of measuring the transferred amount, after leaving each recording medium under an atmosphere at 25° C. and 50% RH for 12 hours or more, the measurement was performed using a Bristow testing machine II type (press mode) which was a liquid dynamic absorbability testing machine supplied from Kumagai Rikikogyo Co., Ltd. The aqueous solution of 2% C.I. acid red 52 was used for the measurement and the transferred amount was obtained by measuring an area stained with magenta on the recording medium after 0.04 sec of absorption time. Also, the transferred amount when the absorption speed was saturated (a slope of a transferred amount curve against a time change is zero) was obtained to render a void capacity.
[Calculation of Void Rate]
The void rate of each recording medium made above was calculated by calculation from a void capacity obtained from Bristow method and a total volume of the micro-porous layer obtained from a dried film thickness.
[Color Ink Set: Measurement of Surface Tension]
For the surface tension of the ink which configures the ink set, a surface tension value (mN/m) at an ink temperature of 25° C. was measured by a platinum plate method using a tensiometer (CBVP-Z supplied from Kyowa Interface Science Co., Ltd.)
[20-Degree Specular Gloss]
According to JIS-Z-8741, 20-degree specular gloss of ink absorption layer-applied both sides of each recording medium was measured using a digital variable angle glossmeter (supplied from Suga Test Instruments Co., Ltd.).
<<Printing Methods>>
[Printing Method 1]
Each color ink set and the invisible ink prepared above were set in an on-demand type inkjet printer with a maximum recording density main scanning 1200×sub scanning 1200 dpi, and for the color inks, one-pass printing was performed without using the thinning-out pattern, using thermal type heads (first recording heads) which arrange two rows with 1 mm distance of nozzle rows and enable to effectively form 256 dots with 1200 dpi pitch on a recording medium by arraying the nozzles in two rows with a shift of 21.2 μm in a sub scanning direction, where a nozzle pore size was 15 μm, a driving frequency was 20 kHz, an amount of an ink liquid drop was 3 pl, a dot size after jetted on the recording medium was 35 μm, a nozzle number in one row was 128 and a nozzle pitch was 42.3 μm. The invisible ink prepared above was adhered from second recording heads onto white background sections where the above color inks were not adhered at all and highlight sections where the adhering amount was 5 ml/m2 or less so that a total adhering amount of the color inks and the invisible ink was 5 ml/m2. No invisible ink was adhered on the sections where the color inks were adhered at 5 ml/m2 or more. The adhering amounts of the color inks were controlled as shown in FIG. 25. Dpi referred to here represents a dot number per 2.54 cm.
[Printing Method 2]
Each color ink set and the invisible ink prepared above were set in an on-demand type inkjet printer with a maximum recording density main scanning 1200×sub scanning 1200 dpi, and for the color inks, the formation of thinned-out image was performed by four-pass printing using the regular thinning-out pattern at a printing acceptable rate of 25% by the thermal type heads (first recording heads) which arrange two rows with 1 mm distance of nozzle rows and enable to effectively form 256 dots with 1200 dpi pitch on a medium by arraying nozzles in two rows with a shift of 21.2 μm in a sub scanning direction where a nozzle pore size was 15 μm, a driving frequency was 20 kHz, an amount of an ink liquid drop was 3 pl which was the ink liquid drop to produce a dot size of 35 μm after jetted on the recording medium, the dot size after jetted on the recording medium was 35 μm, a nozzle number in one row was 128 and a nozzle pitch was 42.3 μm. The masks used are shown in FIG. 23.
The invisible ink prepared above was adhered from the second recording heads onto the white background sections where the above color inks were not adhered at all and the highlight sections where the adhering amount was 5 ml/m2 or less so that the total adhering amount of the color inks and the invisible ink was 5 ml/m2. No invisible ink was adhered on the sections where the color inks were adhered at 5 ml/m2 or more. The adhering amounts of the color inks were controlled as shown in FIG. 25.
[Printing Method 3]
Each ink set and the invisible ink prepared above were set in an on-demand type inkjet printer with a maximum recording density main scanning 1200×sub scanning 1200 dpi, and for the color inks, the formation of thinned-out image was performed by four-pass printing using the thinning-out pattern without regularity at a printing acceptable rate of 25% by the thermal type heads (first recording heads) which arrange two rows with 1 mm distance of nozzle rows and enable to effectively form 256 dots with 1200 dpi pitch by arraying nozzles in two rows with a shift of 21.2 μm in a sub scanning direction where a nozzle pore size was 15 μm, a driving frequency was 20 kHz, an amount of an ink liquid drop was 3 pl, a dot size after jetted on the recording medium was 35 μm, a nozzle number in one row was 128 and a nozzle pitch was 42.3 μm. The masks used are shown in FIG. 18.
The invisible ink prepared above was adhered from the second recording heads onto the white background sections where the above color inks were not adhered at all and the highlight sections where the adhering amount was 5 ml/m2 or less so that the total adhering amount of the color inks and the invisible ink was 5 ml/m2. No invisible ink was adhered on the sections where the color inks were adhered at 5 ml/m2 or more. The adhering amounts of the color inks were controlled as shown in FIG. 25.
[Printing Method 4]
The image formation was performed as was the case with the above printing method 3, except that the invisible ink was not used, and this was rendered the printing method 4.
[Printing Method 5]
A printing method 5 was performed as was the case with the above printing method 3, except that effectively heads of 2400 dpi were made to make printing resolution of the maximum recording density main scanning 2400×sub scanning 2400 dpi by appropriately changing the nozzle pore size to make the ink liquid drop (about 0.75 pl) such that the dot size after jetted on the recording medium was 15 μm, making the nozzle pitch of one row 21.2 μm and making the shift between the two rows 10.6 μm when color images were printed using the color ink sets.
[Printing Method 6]
A printing method 6 was performed as was the case with the above printing method 3, except that the nozzle pore size was appropriately changed such that the ink liquid drop amount was about 5 pl which corresponded to the dot size of 40 μm after jetted on the recording medium when color images were printed using the color ink sets. The image data were precedently conditioned such that ink adhering amounts on the medium were nearly identical to those in the printing method 3.
[Printing Method 7]
A printing method 7 was performed as was the case with the above printing method 3, except that the nozzle pore size was appropriately changed such that the ink liquid drop amount was about 14 pl which corresponded to the dot size of 60 μm after jetted on the recording medium when color images were printed using the color ink sets. The image data were precedently conditioned such that the ink adhering amounts on the medium were nearly identical to those in the printing method 3.
[Printing Method 8]
A printing method 8 was performed as was the case with the above printing method 3, except that the heads were changed to the heads where the nozzle pitch was 15 μm and 256 nozzles were arranged in one row to make the maximum recording density main scanning 850×sub scanning 1690 dpi when color images were printed using the color ink sets. The sub scanning resolution corresponded to the head nozzle pitch, and the main scanning resolution was changed depending on this such that the ink adhering amounts on the medium were nearly identical to those in the printing method 3.
[Printing Method 9]
A printing method 9 was performed as was the case with the above printing method 3, except changing to the maximum recording density main scanning 1570×sub scanning 920 dpi by changing to the nozzle heads where the nozzle groups where 256 nozzles were arranged in one row with a nozzle pitch of 55 μm were separated by 2 cm, two rows for each color were arranged with a shift of 27.5 μm in the subscanning direction and 512 nozzles per color were arranged, when color images were printed using the color ink sets. In this case, the nozzle pitch is 55 μm. The sub scanning resolution corresponded to the head nozzle pitch on the medium, and the main scanning resolution was changed depending on this such that the ink adhering amounts on the medium were nearly identical to those in the printing method 3.
[Printing Method 10]
A printing method 10 was performed as was the case with the above printing method 3, except changing the printing acceptable rate to a repeat of four types of 40%, 40%, 10% and 10% (thus the printing acceptable rate was 40%), when color images were printed using the color ink sets.
[Printing Method 11]
A printing method 11 was performed as was the case with the above printing method 3, except changing to the maximum recording density main scanning 1200×sub scanning 1200 dpi by changing to the nozzle heads where the nozzle groups where 256 nozzles were arranged in one row with a nozzle pitch of 42.3 μm were separated by 2 cm, two rows for each color were arranged with a shift of 21.2 μm in the subscanning direction and 512 nozzles per color were arranged, when color images were printed using the color ink sets. In this case, the nozzle pitch is 42.3 μm.
[Printing Method 12]
The invisible ink prepared above was adhered from the second recording heads onto the white background sections where the above color inks were not adhered at all and the highlight sections where the adhering amount was 1.7 ml/m2 or less so that the total adhering amount of the color inks and the invisible ink was 1.7 ml/m2. No invisible ink was adhered on the sections where the color inks were adhered at 1.7 ml/m2 or more.
[Printing Method 13]
A printing method 13 was performed as was the case with the above printing method 3, except that the invisible ink prepared above was adhered from the second recording heads onto the white background sections where the above color inks were not adhered at all and the highlight sections where the adhering amount was 23 ml/m2 or less so that the total adhering amount of the color inks and the invisible ink was 23 ml/m2.
[Printing Method 14]
A printing method 14 was performed as was the case with the above printing method 3, except that the invisible ink prepared above was adhered from the second recording heads onto the white background sections where the above color inks were not adhered at all and the sections where the adhering amount was 27 ml/m2 or less so that the total adhering amount of the color inks and the invisible ink was 27 ml/m2.
In the case of using special color inks, image data were developed using the methods described in paragraph numbers [0038] to [0059] in JP-Tokukai-2000-32284A.
A relation of the image data with the ink amount used in this case was shown in FIG. 24 by citing blue hue as an example.
In FIG. 24, on the white background section, the invisible ink D is adhered at 5 ml/m2, and as the cyan ink A and the magenta ink B are adhered, the amount of the invisible ink is reduced. At the gradation level 5 or higher, the amount of the color inks exceeds 5 ml/m2, and thus the invisible ink D is not adhered. At the gradation level 7 or higher, the blue ink C is used and the magenta ink B is reduced. The cyan ink A is not reduced, but an increment amount thereof is decreased compared to the case where the blue ink C is not used. At the gradation level 16, solid of the blue ink C is adhered, and the use amount of total inks is 20.5 ml/m2. It is for creating visually preferable colors that the cyan ink A and some magenta ink B are used even on the solid of blue ink C.
<<Formation of Inkjet Recording Image>>
Respective solid images of yellow, magenta, cyan, green, red, blue and black, and High Definition Color Digital Standard Image Data “N2 Cafeteria” and “N5 Bicycle” (published in December, 1995) published by Japan Standards Association were printed by combining the above printing method, recording medium, color ink set and invisible ink according to the description in Tables 2, 3, 4A and 4B to make the images 1 to 50, and the following evaluations were performed for the obtained images.









TABLE 2









RECORDING MEDIUM












PRINTING METHOD

INORGANIC FINE














PRINT-
PRINT-

PARTICLE
























ING
ING




MEAN









DOT
ACCEPT-




PARTI-




NOZZLE
DIAM-
ABLE




CLE


VOID


IMAGE

PITCH
ETER
RATE




SIZE

HARD-
RATE


NO.
NO.
(μm)
(μm)
(%)
*2
NO.
SUPPORT
KIND
(nm)
*3
ENER
(%)
*4























1
1
21.2
35
—
3.4
1
WATER-ABSORBABLE
SILICA
35
20
PRESENT
55
17


2
2
21.2
35
25
3.4
1
WATER-ABSORBABLE
SILICA
35
20
PRESENT
55
17


3
3
21.2
35
25
3.4
1
WATER-ABSORBABLE
SILICA
35
20
PRESENT
55
17


4
4
21.2
35
25
3.4
1
WATER-ABSORBABLE
SILICA
35
20
PRESENT
55
17


5
3
21.2
35
25
3.4
1
WATER-ABSORBABLE
SILICA
35
20
PRESENT
55
17


6
3
21.2
35
25
3.4
1
WATER-ABSORBABLE
SILICA
35
20
PRESENT
55
17


7
3
21.2
35
25
3.4
2
NON-WATERABSORBABLE
SILICA
35
8
PRESENT
55
17


8
3
21.2
35
25
3.4
3
NON-WATER-ABSORBABLE
SILICA
35
20
PRESENT
55
17


9
3
21.2
35
25
3.4
4
WATER-ABSORBABLE
SILICA
35
11
PRESENT
35
17


10
3
21.2
35
25
3.4
4
WATER-ABSORBABLE
SILICA
35
11
PRESENT
35
17


11
3
21.2
35
25
3.4
5
WATER-ABSORBABLE
ALUMINA
30
20
PRESENT
55
18


12
3
21.2
35
25
3.4
6
WATER-ABSORBABLE
SILICA
15
16
PRESENT
46
18


13
3
21.2
35
25
3.4
7
WATER-ABSORBABLE
SILICA
20
18
PRESENT
48
17


14
3
21.2
35
25
3.4
7
WATER-ABSORBABLE
SILICA
20
18
PRESENT
48
17


15
3
21.2
35
25
3.4
8
WATER-ABSORBABLE
SILICA
80
22
PRESENT
61
13


16
3
21.2
35
25
3.4
8
WATER-ABSORBABLE
SILICA
80
22
PRESENT
61
13


17
3
21.2
35
25
3.4
9
WATER-ABSORBABLE
SILICA
120
26
PRESENT
68
11


18
3
21.2
35
25
3.4
10
WATER-ABSORBABLE
SILICA
35
14
ABSENT
55
17


19
3
21.2
35
25
3.4
11
WATER-ABSORBABLE
SILICA
35
4
PRESENT
25
17


20
3
21.2
35
25
3.4
12
WATER-ABSORBABLE
SILICA
35
28
PRESENT
75
17


21
3
21.2
35
25
3.4
13
WATER-ABSORBABLE
SILICA
35
16
PRESENT
45
23


22
3
21.2
35
25
3.4
14
WATER-ABSORBABLE
ALUMINA
30
22
PRESENT
55
32


23
3
21.2
35
25
3.4
15
WATER-ABSORBABLE
ALUMINA
30
14
PRESENT
34
47


24
3
21.2
35
25
3.4
15
WATER-ABSORBABLE
ALUMINA
30
14
PRESENT
34
47


25
3
21.2
35
25
3.4
1
WATER-ABSORBABLE
SILICA
35
20
PRESENT
55
17





*2: TOTAL ADHEARING AMOUNT OF COLOR INK AND INVISIBLE INK (ml/m2)


*3: TRANSFERRED AMOUNT (ml/m2)


*4: 20-DEGREE SPECULAR GLOSS















TABLE 3









RECORDING MEDIUM












PRINTING METHOD

INORGANIC FINE













PRINT-

PARTICLE
























PRINT-
ING




MEAN









ING
ACCEPT-




PARTI-








NOZZLE
DOT DI-
ABLE




CLE


VOID


IMAGE

PITCH
AMETER
RATE




SIZE

HARD-
RATE


NO.
NO.
(μm)
(μm)
(%)
*2
NO.
SUPPORT
KIND
(nm)
*3
ENER
(%)
*4























26
3
21.2
35
25
3.4
1
WATER-ABSORBABLE
SILICA
35
20
PRESENT
55
17


27
3
21.2
35
25
3.4
1
WATER-ABSORBABLE
SILICA
35
20
PRESENT
55
17


28
3
21.2
35
25
3.4
1
WATER-ABSORBABLE
SILICA
35
20
PRESENT
55
17


29
3
21.2
35
25
3.4
1
WATER-ABSORBABLE
SILICA
35
20
PRESENT
55
17


30
3
21.2
35
25
3.4
1
WATER-ABSORBABLE
SILICA
35
20
PRESENT
55
17


31
3
21.2
35
25
3.4
1
WATER-ABSORBABLE
SILICA
35
20
PRESENT
55
17


32
3
21.2
35
25
3.4
1
WATER-ABSORBABLE
SILICA
35
20
PRESENT
55
17


33
3
21.2
35
25
3.4
1
WATER-ABSORBABLE
SILICA
35
20
PRESENT
55
17


34
3
21.2
35
25
3.4
1
WATER-ABSORBABLE
SILICA
35
20
PRESENT
55
17


35
3
21.2
35
25
3.4
1
WATER-ABSORBABLE
SILICA
35
20
PRESENT
55
17


36
3
21.2
35
25
3.4
13
WATER-ABSORBABLE
SILICA
35
16
PRESENT
45
23


37
3
21.2
35
25
3.4
14
WATER-ABSORBABLE
ALUMINA
30
22
PRESENT
55
32


38
5
21.2
15
25
3.4
1
WATER-ABSORBABLE
SILICA
35
20
PRESENT
55
17


39
5
21.2
15
25
3.4
1
WATER-ABSORBABLE
SILICA
35
20
PRESENT
55
17


40
6
21.2
40
25
3.4
1
WATER-ABSORBABLE
SILICA
35
20
PRESENT
55
17


41
7
21.2
60
25
3.4
1
WATER-ABSORBABLE
SILICA
35
20
PRESENT
55
17


42
8
15.0
35
25
3.4
1
WATER-ABSORBABLE
SILICA
35
20
PRESENT
55
17


43
8
15.0
35
25
3.4
1
WATER-ABSORBABLE
SILICA
35
20
PRESENT
55
17


44
9
55.0
35
25
3.4
1
WATER-ABSORBABLE
SILICA
35
20
PRESENT
55
17


45
10
21.2
35
*1
3.4
1
WATER-ABSORBABLE
SILICA
35
20
PRESENT
55
17


46
11
42.3
35
25
3.4
1
WATER-ABSORBABLE
SILICA
35
20
PRESENT
55
17


47
11
42.3
35
25
3.4
1
WATER-ABSORBABLE
SILICA
35
20
PRESENT
55
17


48
12
21.2
35
25
1.7
1
WATER-ABSORBABLE
SILICA
35
20
PRESENT
55
17


49
13
21.2
35
25
23
1
WATER-ABSORBABLE
SILICA
35
20
PRESENT
55
17


50
14
21.2
35
25
27
1
WATER-ABSORBABLE
SILICA
35
20
PRESENT
55
17





*1: 40, 40, 10, 10 (EQUIVALENT TO 40%)


*2: TOTAL ADHEARING AMOUNT OF COLOR INK AND INVISIBLE INK (ml/m2)


*3: TRANSFERRED AMOUNT (ml/m2)


*4: 20-DEGREE SPECULAR GLOSS
















TABLE 4A









COLOR INK SET

















PRINTING
PRINTING



SURFACE




IMAGE
METHOD
MEDIUM

PIGMENT

TENSION


NO.
NO.
NO.
NO.
DISPERSANT
UREA
(mN/m)
INVISIBLE INK
REMARK


















1
1
1
1
SA-1, 2
ABSENT
26
PRESENT
COMPARATIVE EXAMPLE


2
2
1
1
SA-1, 2
ABSENT
27
PRESENT
COMPARATIVE EXAMPLE


3
3
1
2
SA-1, 2
ABSENT
28
PRESENT
COMPARATIVE EXAMPLE


4
4
1
1
SA-1, 2
ABSENT
29
ABSENT
COMPARATIVE EXAMPLE


5
3
1
1
SA-1, 2
ABSENT
30
PRESENT
PRESENT INVENTION


6
3
1
3
SA-1, 2
ABSENT
31
PRESENT
PRESENT INVENTION


7
3
2
1
SA-1, 2
ABSENT
32
PRESENT
COMPARATIVE EXAMPLE


8
3
3
1
SA-1, 2
ABSENT
33
PRESENT
PRESENT INVENTION


9
3
4
1
SA-1, 2
ABSENT
36
PRESENT
PRESENT INVENTION


10
3
4
8
SA-1, 2
ABSENT
26
PRESENT
PRESENT INVENTION


11
3
5
1
SA-1, 2
ABSENT
26
PRESENT
PRESENT INVENTION


12
3
6
1
SA-1, 2
ABSENT
26
PRESENT
PRESENT INVENTION


13
3
7
1
SA-1, 2
ABSENT
26
PRESENT
PRESENT INVENTION


14
3
7
8
SA-1, 2
ABSENT
36
PRESENT
PRESENT INVENTION


15
3
8
1
SA-1, 2
ABSENT
26
PRESENT
PRESENT INVENTION


16
3
8
8
SA-1, 2
ABSENT
36
PRESENT
PRESENT INVENTION


17
3
9
1
SA-1, 2
ABSENT
26
PRESENT
COMPARATIVE EXAMPLE


18
3
10
1
SA-1, 2
ABSENT
26
PRESENT
PRESENT INVENTION


19
3
11
1
SA-1, 2
ABSENT
26
PRESENT
COMPARATIVE EXAMPLE


20
3
12
1
SA-1, 2
ABSENT
26
PRESENT
PRESENT INVENTION


21
3
13
1
SA-1, 2
ABSENT
26
PRESENT
PRESENT INVENTION


22
3
14
1
SA-1, 2
ABSENT
26
PRESENT
PRESENT INVENTION


23
3
15
1
SA-1, 2
ABSENT
26
PRESENT
PRESENT INVENTION


24
3
15
8
SA-1, 2
ABSENT
36
PRESENT
PRESENT INVENTION


25
3
1
4
SA-4
ABSENT
26
PRESENT
PRESENT INVENTION



















TABLE 4B









COLOR INK SET

















PRINTING
PRINTING



SURFACE




IMAGE
METHOD
MEDIUM

PIGMENT

TENSION


NO.
NO.
NO.
NO.
DISPERSANT
UREA
(mN/m)
INVISIBLE INK
REMARK


















26
3
1
5
SA-5
ABSENT
26
PRESENT
PRESENT INVENTION


27
3
1
6
SA-6
ABSENT
26
PRESENT
PRESENT INVENTION


28
3
1
7
SA-1, 2
ABSENT
31
PRESENT
PRESENT INVENTION


29
3
1
8
SA-1, 2
ABSENT
36
PRESENT
PRESENT INVENTION


30
3
1
9
SA-1, 2
ABSENT
48
PRESENT
PRESENT INVENTION


31
3
1
10
SA-1, 2
ABSENT
54
PRESENT
PRESENT INVENTION


32
3
1
11
SA-1 to 3
ABSENT
26
PRESENT
PRESENT INVENTION


33
3
1
12
—
ABSENT
26
PRESENT
PRESENT INVENTION


34
3
1
13
SA-1, 2
PRESENT
26
PRESENT
PRESENT INVENTION


35
3
1
14
SA-1, 2
PRESENT
36
PRESENT
PRESENT INVENTION


36
3
13
14
SA-1, 2
PRESENT
36
PRESENT
PRESENT INVENTION


37
3
14
14
SA-1, 2
PRESENT
36
PRESENT
PRESENT INVENTION


38
5
1
1
SA-1, 2
ABSENT
26
PRESENT
PRESENT INVENTION


39
5
1
8
SA-1, 2
ABSENT
36
PRESENT
PRESENT INVENTION


40
6
1
1
SA-1, 2
ABSENT
26
PRESENT
PRESENT INVENTION


41
7
1
1
SA-1, 2
ABSENT
26
PRESENT
COMPARATIVE EXAMPLE


42
8
1
1
SA-1, 2
ABSENT
26
PRESENT
PRESENT INVENTION


43
8
1
8
SA-1, 2
ABSENT
36
PRESENT
PRESENT INVENTION


44
9
1
1
SA-1, 2
ABSENT
26
PRESENT
COMPARATIVE EXAMPLE


45
10
1
1
SA-1, 2
ABSENT
26
PRESENT
PRESENT INVENTION


46
11
1
1
SA-1, 2
ABSENT
26
PRESENT
PRESENT INVENTION


47
11
1
8
SA-1, 2
ABSENT
36
PRESENT
PRESENT INVENTION


48
12
1
1
SA-1, 2
ABSENT
26
PRESENT
PRESENT INVENTION


49
13
1
1
SA-1, 2
ABSENT
26
PRESENT
PRESENT INVENTION


50
14
1
1
SA-1, 2
ABSENT
26
PRESENT
PRESENT INVENTION









<<Evaluation of Inkjet Recording Image>>

[Evaluation of Bronzing Resistance]

After the black solid image formed above was stored under an atmosphere at 23° C. and relative humidity of 80% for a week, a condition (occurrence of bronzing) of the print image was visually observed and bronzing resistance was evaluated according to the following criteria.
A: No occurrence of bronzing
B: Occurrence of slight bronzing but no problem
C: Occurrence of partial bronzing but practically no problem
D: Occurrence of intensive bronzing
[Evaluation of Gloss Difference]
Images of High Definition Color Digital Standard Image Data “N5 Bicycle” (published in December, 1995) published by Japan Standards Association obtained by combining the above (printing method, recording medium and inks) were visually observed, and the image quality was evaluated according to the following criteria.
A: No difference is felt between the gloss of a clock section with high image density and a color chart section and the gross of a peripheral white background section, and the clock and the color chart are looked evenly without standing out in bold relief from the periphery.
B: Some difference is felt between the gloss of the clock section with high image density and the color chart section and the gross of the peripheral white background section, but the clock and the color chart are looked evenly without standing out in bold relief from the periphery.
C: Difference is felt between glosses of the clock section with high image density and the color chart section and the gross of the peripheral white background section, and further the clock and the color chart somewhat stand out in bold relief, but practically no problem.
D: Large gloss difference is felt between the gloss of the clock section with high image density and the color chart section and the gloss of the peripheral white background section, and further the clock and the color chart stand out in bold relief from the periphery.
[Evaluation of Image Quality]
Images of High Definition Color Digital Standard Image Data “N5 Bicycle” (published in December, 1995) published by Japan Standards Association obtained by combining the above (printing method, recording medium and inks) were visually observed, and the image quality was evaluated according to the following criteria.
A: No occurrence of color turbidity and an image with extremely high definition is obtained.
B: Occurrence of slight color turbidity and an image with high definition is obtained.
C: Occurrence of rather turbid color and an image with rather less distinction, but practically no problem.
D: Obvious color turbidity is observed and an image lacks distinction.
[Evaluation of Transparent Feeling]
Images of High Definition Color Digital Standard Image Data “N4 Wine and table wares” (published in December, 1995) published by Japan Standards Association obtained by combining the above (printing method, recording medium and inks) were visually observed, and transparent feeling was evaluated according to the following criteria.
A: An image from which transparent feeling and accentual feeling are strongly felt.
B: An image having the transparent feeling and the accentual feeling are felt.
C: An image which slightly lacks the transparent feeling and the accentual feeling but is in the practically acceptable range.
D: An image which obviously lacks the transparent feeling and the accentual feeling and is off from practical use.
The results obtained from the above are shown in Tables 5A and 5B.










TABLE 5A









EVALUATION RESULTS



















RECORD-
COLOR



IMAGE





PRINTING
ING
INK



QUALITY
TRANS-


IMAGE
METHOD
MEDIUM
SET
INVISIBLE

GLOSS
(HIGH
PARENT


NO.
NO.
NO.
NO.
INK
BRONZING
DIFFERENCE
DEFINITION)
FEELING
REMARKS



















1
1
1
5
PRESENT
D
D
D
D
COMPARATIVE EXAMPLE


2
2
1
6
PRESENT
D
D
D
D
COMPARATIVE EXAMPLE


3
3
1
7
PRESENT
D
C
D
C
COMPARATIVE EXAMPLE


4
4
1
8
ABSENT
B
D
B
D
COMPARATIVE EXAMPLE


5
3
1
9
PRESENT
B
C
B
B
PRESENT INVENTION


6
3
1
10
PRESENT
C
C
B
B
PRESENT INVENTION


7
3
2
11
PRESENT
C
D
D
D
COMPARATIVE EXAMPLE


8
3
3
12
PRESENT
C
C
B
C
PRESENT INVENTION


9
3
4
13
PRESENT
B
C
C
B
PRESENT INVENTION


10
3
4
14
PRESENT
B
B
B
B
PRESENT INVENTION


11
3
5
14
PRESENT
B
B
B
B
PRESENT INVENTION


12
3
6
14
PRESENT
C
C
C
B
PRESENT INVENTION


13
3
7
1
PRESENT
B
C
C
B
PRESENT INVENTION


14
3
7
8
PRESENT
B
B
B
B
PRESENT INVENTION


15
3
8
1
PRESENT
B
C
B
C
PRESENT INVENTION


16
3
8
1
PRESENT
B
B
B
B
PRESENT INVENTION


17
3
9
1
PRESENT
C
D
C
D
COMPARATIVE EXAMPLE


18
3
10
8
PRESENT
C
C
C
C
PRESENT INVENTION


19
3
11
1
PRESENT
C
D
D
C
COMPARATIVE EXAMPLE


20
3
12
1
PRESENT
C
C
C
C
PRESENT INVENTION


21
3
13
1
PRESENT
B
B
B
B
PRESENT INVENTION


22
3
14
8
PRESENT
B
A
B
B
PRESENT INVENTION


23
3
15
1
PRESENT
B
C
C
B
PRESENT INVENTION


24
3
15
1
PRESENT
B
B
B
B
PRESENT INVENTION


25
3
1
1
PRESENT
C
C
B
B
PRESENT INVENTION



















TABLE 5B









EVALUATION RESULTS



















RECORD-
COLOR



IMAGE





PRINTING
ING
INK



QUALITY
TRANS-


IMAGE
METHOD
MEDIUM
SET
INVISIBLE

GLOSS
(HIGH
PARENT


NO.
NO.
NO.
NO.
INK
BRONZING
DIFFERENCE
DEFINITION)
FEELING
REMARKS



















26
3
1
1
PRESENT
B
C
B
B
PRESENT INVENTION


27
3
1
1
PRESENT
C
C
B
C
PRESENT INVENTION


28
3
1
2
PRESENT
B
B
B
B
PRESENT INVENTION


29
3
1
1
PRESENT
A
B
B
B
PRESENT INVENTION


30
3
1
1
PRESENT
B
B
B
B
PRESENT INVENTION


31
3
1
3
PRESENT
B
B
C
B
PRESENT INVENTION


32
3
1
1
PRESENT
B
C
B
B
PRESENT INVENTION


33
3
1
1
PRESENT
C
C
C
C
PRESENT INVENTION


34
3
1
1
PRESENT
A
B
B
B
PRESENT INVENTION


35
3
1
8
PRESENT
A
A
B
B
PRESENT INVENTION


36
3
13
1
PRESENT
A
B
A
A
PRESENT INVENTION


37
3
14
1
PRESENT
A
A
A
A
PRESENT INVENTION


38
5
1
1
PRESENT
C
B
C
B
PRESENT INVENTION


39
5
1
8
PRESENT
B
B
B
B
PRESENT INVENTION


40
6
1
1
PRESENT
B
C
B
B
PRESENT INVENTION


41
7
1
8
PRESENT
C
D
D
D
COMPARATIVE EXAMPLE


42
8
1
1
PRESENT
C
C
B
B
PRESENT INVENTION


43
8
1
1
PRESENT
B
B
B
B
PRESENT INVENTION


44
9
1
1
PRESENT
C
D
D
D
COMPARATIVE EXAMPLE


45
10
1
1
PRESENT
C
C
C
C
PRESENT INVENTION


46
11
1
1
PRESENT
B
C
C
B
PRESENT INVENTION


47
11
1
1
PRESENT
B
B
B
B
PRESENT INVENTION


48
12
1
1
PRESENT
C
C
B
B
PRESENT INVENTION


49
13
1
8
PRESENT
B
C
B
B
PRESENT INVENTION


50
14
1
4
PRESENT
B
C
C
B
PRESENT INVENTION









As is obvious from the results in Tables 5A and 5B, compared with Comparative Examples, it is shown that the gloss difference between printing sections and non-printing sections in the obtained image is small and the image which is excellent in depth feeling, no bronzing occurs and the image with high definition without color turbidity are obtained in the inkjet recording method made up of the combination of the recording heads, the inks and the recording medium defined in the invention.
According to the present embodiment, even if pigment is printed onto the recording medium according to the thinning-out pattern without regularity, the inkjet recording method and inkjet recording apparatus can be provided, in which an image at high definition with no color turbidity is obtained and glossiness uniformity, bronzing resistance and texture of the formed image is improved.

## Claims

1. An inkjet recording method comprising the step of:
forming a color image with color inks and an invisible ink onto a recording medium by
while scanning a first recording head multiple times on a same recording area of the recording medium, forming a thinned-out image according to an thinning-out pattern without regularity in each scanning, the first recording head having a plurality of nozzle sections for jetting color inks, and
jetting an invisible ink from a second recording head in accordance with an adhering amount of the color inks per unit area on the recording medium,
wherein a nozzle pitch of the first recording head is from 10 to 50 μm,
the color inks comprise cyan, magenta, yellow and black inks and at least one special color ink, the color inks contain pigments, at least one organic solvent with high boiling point and water,
a dot formed by jetting the color inks with the first recording head has a size of 10 to 50 μm on the recording medium,
the invisible ink contains water, at least one organic solvent with high boiling point and a resin fine particle, and
the recording medium has a transferred amount at 0.04 seconds of absorption time by Bristow method of 10 ml/m2 or more, a micro-porous layer containing inorganic fine particles having a mean particle size of 15 to 100 nm and a hydrophilic binder.

2. The inkjet recording method of claim 1, wherein an adhering amount of the invisible ink at an area where the adhering amount of the color inks is not more than a predetermined amount is more than the adhering amount of the invisible ink at an area where the adhering amount of the color inks is more than the predetermined amount.

3. The inkjet recording method of claim 2, wherein the second recording head jets the invisible ink so that a total amount of the adhering amount of the color inks and the invisible ink per unit area is 2 ml/m2 or more.

4. The inkjet recording method of claim 1, wherein a printing acceptable rate of the thinning-out pattern is from 15 to 35%.

5. The inkjet recording method of claim 1, wherein a surface tension of the color inks is 30 to 50 mN/m.

6. The inkjet recording method of claim 1, wherein the pigment of the color inks is dispersed by a polymeric dispersant.

7. The inkjet recording method of claim 1, wherein the recording medium comprises an absorbable support, on which the micro-porous layer is provided.

8. The inkjet recording method of claim 1, wherein the hydrophilic binder is polyvinyl alcohol or a derivative of polyvinyl alcohol.

9. The inkjet recording method of claim 1, wherein the hydrophilic binder is hardened.

10. The inkjet recording method of claim 1, wherein a void rate of the micro-porous layer is 30 to 70%.

11. The inkjet recording method of claim 1, wherein the inorganic fine particles contain silica or alumina.

12. The inkjet recording method of claim 1, wherein the inorganic fine particle has the mean particle size of 20 to 80 nm.

13. The inkjet recording method of claim 1, wherein the recording medium has a 20-degree specular gloss according to JIS-Z-8741 of 20 to 45%.

14. The inkjet recording method of claim 1, wherein at least one of the color inks and the invisible ink contains urea or a urea derivative.

15. An inkjet recording apparatus for forming a color image on a recording medium by jetting color inks and an invisible ink, comprising:
a first recording head having a plurality of nozzle sections to jet the color inks, the nozzle sections being arrayed in a pitch of 10 to 50 μm;
a scanning section to make the first recording head scan multiple times on one recording area of the recording medium;
a second recording head having a plurality of nozzle sections to jet the invisible ink and
a control section to allow the first recording head to jet the color inks from the plurality of nozzle sections so that a thinned-out image according to a thinning-out pattern without regularity in each scanning is formed on the recording medium and the second recording head to jet the invisible ink in accordance with an adhering amount of the color inks per unit area on the recording medium,
wherein the color inks comprise at least cyan, magenta, yellow and black inks and at least one special color ink, the color inks contain pigments, at least one organic solvent with high boiling point and water,
a dot formed by jetting the color inks with the first recording head has a size of 10 to 50 μm on the recording medium,
the invisible ink contains water, at least one organic solvent with high boiling point and a resin fine particle, and
the recording medium has a transferred amount at 0.04 seconds of absorption time by Bristow method is 10 ml/m2 or more, a micro-porous layer containing inorganic fine particles having a mean particle size of 15 to 100 nm and a hydrophilic binder.

16. The inkjet recording apparatus of claim 15, wherein an adhering amount of the invisible ink at an area where the adhering amount of the color inks is not more than a predetermined amount is more than the adhering amount of the invisible ink at an area where the adhering amount of the color inks is more than the predetermined amount.

17. The inkjet recording apparatus of claim 16, wherein the second recording head jets the invisible ink so that a total amount of the adhering amount of the color inks and the invisible ink per unit area is 2 ml/m2 or more.

18. The inkjet recording apparatus of claim 15, wherein a printing acceptable rate of the thinning-out pattern is from 15 to 35%.

19. The inkjet recording apparatus of claim 15, wherein a surface tension of the color inks is 30 to 50 mN/m.

20. The inkjet recording apparatus of claim 15, wherein the pigment of the color inks is dispersed by a polymeric dispersant.

21. The inkjet recording apparatus of claim 15, wherein the recording medium comprises an absorbable support, on which the micro-porous layer is provided.

22. The inkjet recording apparatus of claim 15, wherein the hydrophilic binder is polyvinyl alcohol or a derivative of polyvinyl alcohol.

23. The inkjet recording apparatus of claim 15, wherein the hydrophilic binder is hardened.

24. The inkjet recording apparatus of claim 15, wherein a void rate of the micro-porous layer is 30 to 70%.

25. The inkjet recording apparatus of claim 15, wherein the inorganic fine particles contain silica or alumina.

26. The inkjet recording apparatus of claim 15, wherein the inorganic fine particle has the mean particle size of 20 to 80 nm.

27. The inkjet recording apparatus of claim 15, wherein the recording medium has a 20-degree specular gloss according to JIS-Z-8741 of 20 to 45%.

28. The inkjet recording apparatus of claim 15, wherein at least one of the color inks and the invisible ink contains urea or a urea derivative.