# Patent

## Title
Aqueous ink composition, ink jet recording method, and recorded matter

## Abstract

An ink jet recording method includes ejecting droplets of an aqueous ink composition from an ink jet recording apparatus onto a non-ink-absorbing or low-ink-absorbing recording medium, and heating the recording medium to 40° C. or more to dry the aqueous ink composition deposited on the recording medium, wherein the first solvent content (W1) is 3% by mass or more and 6% by mass or less of the mass of the aqueous ink composition, the ratio (W2/W1) of the second solvent content (W2) to the first solvent content (W1) is one or more, and the ratio [(W2+W3)/(W1)] of the total (W2+W3) of the second solvent content (W2) and the third solvent content (W3) to the first solvent content (W1) is three or more.

## Background
BACKGROUND
1. Technical Field
The present invention relates to an aqueous ink composition, an ink jet recording method, and recorded matter produced by the ink jet recording method using the aqueous ink composition.
2. Related Art
Non-aqueous ink compositions containing organic solvent are quick to dry and cause little bleeding or blurring and have therefore been used in recording on nonabsorbing media, such as plastics, that do not absorb ink. From the standpoints of global environment protection and safety, however, aqueous ink compositions containing water as solvent are becoming widespread.
Some aqueous ink compositions containing a yellow pigment as a coloring material contain C.I. pigment yellow 74 as the yellow pigment. However, C.I. pigment yellow 74 has insufficient light resistance. Thus, C.I. pigment yellow 180 is being studied to improve light resistance.
However, aqueous ink compositions containing C.I. pigment yellow 180 may have low storage stability at low temperature. More specifically, thawing of aqueous ink compositions containing C.I. pigment yellow 180 in a frozen state stored at a low temperature of −10° C. or less can cause the agglomeration of the pigment. For example, in JP-A-2005-60411, JP-A-2005-60419, and JP-A-2007-154087, a moisturizing component, such as glycerin, is added to aqueous ink compositions containing a yellow pigment to prevent the freezing of the aqueous ink compositions. The addition of a moisturizing component, such as glycerin, to aqueous ink compositions containing a yellow pigment sometimes improves low-temperature storage stability.
The formation of images on recording media, such as plastics, using aqueous ink compositions containing a yellow pigment may cause blurring of the images by contact with another color pigment, thereby producing low-quality images. In order to avoid this problem, it is known that an alkanediol is added to an aqueous ink composition to reduce blurring of images.
For example, JP-A-2007-154087 discloses that the addition of 1,2-hexanediol to an aqueous ink composition can produce high-quality images without chrominance non-uniformity in some recorded images.
However, the addition of a moisturizing component, such as glycerin, to aqueous ink compositions containing C.I. pigment yellow 180 has sometimes reduced the abrasion resistance of images formed on recording media, such as plastics, thereby producing low-quality images.
Furthermore, the addition of an alkanediol to aqueous ink compositions containing C.I. pigment yellow 180 has sometimes reduced the low-temperature storage stability of the aqueous ink compositions.
SUMMARY
An advantage of some aspects of the invention is that it provides an ink jet recording method that can ensure low-temperature storage stability of an aqueous ink composition, produce high ejection stability, reduce blurring of images formed on a particular recording medium, and produce images having high abrasion resistance.
The invention has been achieved to solve at least part of the problems described above and can be implemented in accordance with the following aspects or applications.
Application 1
An ink jet recording method according to an aspect of the invention is an ink jet recording method including

    
    
        ejecting droplets of an aqueous ink composition from an ink jet recording apparatus onto a non-ink-absorbing or low-ink-absorbing recording medium, and
        heating the recording medium to 40° C. or more to dry the aqueous ink composition deposited on the recording medium,
        wherein the aqueous ink composition contains a pigment containing C.I. pigment yellow 180,
        a first solvent containing at least one selected from 1,2-hexanediol and 1,2-pentanediol,
        a second solvent containing at least one selected from the group consisting of 2-pyrrolidone, N-methyl-2-pyrrolidone, N,N′-dimethylpropyleneurea, 1,3-dimethyl-2-imidazolidinone, tetramethylurea, dimethyl sulfoxide, and hexamethylphosphoric triamide, and
        a third solvent containing at least one selected from propylene glycol and 1,3-propanediol,
        the first solvent content (W1) is 3% by mass or more and 6% by mass or less of the mass of the aqueous ink composition,
        the ratio (W2/W1) of the second solvent content (W2) to the first solvent content (W1) is one or more, and
        the ratio [(W2+W3)/(W1)] of the total (W2+W3) of the second solvent content (W2) and the third solvent content (W3) to the first solvent content (W1) is three or more.
    
    


The ink jet recording method according to Application 1 can ensure low-temperature storage stability of an aqueous ink composition, produce high ejection stability, reduce blurring of images formed on a non-ink-absorbing or low-ink-absorbing recording medium, and produce images having high abrasion resistance. The term “low temperature”, as used herein, refers to a temperature of −10° C. or less at which an aqueous ink composition freezes.
Application 2
In Application 1, the total (W2+W3) of the second solvent content (W2) and the third solvent content (W3) may be 9% by mass or more and 25% by mass or less of the aqueous ink composition.
Application 3
In Application 1 or 2, the pigment content may be 1% by mass or more and 10% by mass or less of the aqueous ink composition.
Application 4
In any one of Applications 1 to 3, the aqueous ink composition may have a viscosity of 2 mPa·s or more and 10 mPa·s or less at a measurement temperature of 20° C.
Application 5
Recorded matter according to an aspect of the invention is prepared by an ink jet recording method according to any one of Applications 1 to 4.
Application 6
An aqueous ink composition according to an aspect of the invention is an aqueous ink composition for use in an ink jet recording method, the aqueous ink composition including

    
    
        a pigment containing C.I. pigment yellow 180,
        a first solvent containing at least one selected from 1,2-hexanediol and 1,2-pentanediol,
        a second solvent containing at least one selected from the group consisting of 2-pyrrolidone, N-methyl-2-pyrrolidone, N,N′-dimethylpropyleneurea, 1,3-dimethyl-2-imidazolidinone, tetramethylurea, dimethyl sulfoxide, and hexamethylphosphoric triamide, and
        a third solvent containing at least one selected from propylene glycol and 1,3-propanediol,
        wherein the first solvent content (W1) is 3% by mass or more and 6% by mass or less of the mass of the aqueous ink composition,
        the ratio (W2/W1) of the second solvent content (W2) to the first solvent content (W1) is one or more, and
        the ratio [(W2+W3)/(W1)] of the total (W2+W3) of the second solvent content (W2) and the third solvent content (W3) to the first solvent content (W1) is three or more.
    
    


The aqueous ink composition according to Application 6 can ensure low-temperature storage stability of an aqueous ink composition, produce high ejection stability, reduce blurring of images formed on a non-ink-absorbing or low-ink-absorbing recording medium, and produce images having high abrasion resistance.
Application 7
In Application 6, the ink jet recording method may include ejecting droplets of the aqueous ink composition from an ink jet recording apparatus onto a non-ink-absorbing or low-ink-absorbing recording medium, and heating the recording medium to 40° C. or more to dry the aqueous ink composition deposited on the recording medium.


DESCRIPTION OF EXEMPLARY EMBODIMENTS
Preferred embodiments of the invention will be described in detail below. These embodiments are offered by way of illustration only. The invention is not limited to these embodiments and includes various modifications thereof without departing from the gist of the invention.
1. Ink Jet Recording Method
An ink jet recording method according to an embodiment of the invention includes ejecting droplets of an aqueous ink composition from an ink jet recording apparatus onto a non-ink-absorbing or low-ink-absorbing recording medium, and heating the recording medium to 40° C. or more to dry the aqueous ink composition deposited on the recording medium, wherein the aqueous ink composition contains a pigment containing C.I. pigment yellow 180, a first solvent containing at least one selected from 1,2-hexanediol and 1,2-pentanediol, a second solvent containing at least one selected from the group consisting of 2-pyrrolidone, N-methyl-2-pyrrolidone, N,N′-dimethylpropyleneurea, 1,3-dimethyl-2-imidazolidinone, tetramethylurea, dimethyl sulfoxide, and hexamethylphosphoric triamide, and a third solvent containing at least one selected from propylene glycol and 1,3-propanediol, the first solvent content (W1) is 3% by mass or more and 6% by mass or less of the mass of the aqueous ink composition, the ratio (W2/W1) of the second solvent content (W2) to the first solvent content (W1) is one or more, and the ratio [(W2+W3)/(W1)] of the total (W2+W3) of the second solvent content (W2) and the third solvent content (W3) to the first solvent content (W1) is three or more. The term “image”, as used herein, refers to a printed pattern formed of dots and includes text printing and solid printing.
1.1. Ink Jet Recording Process
An ink jet recording method according to an embodiment of the invention includes ejecting droplets of an aqueous ink composition from an ink jet recording apparatus onto a non-ink-absorbing or low-ink-absorbing recording medium, and heating the recording medium to 40° C. or more to dry the aqueous ink composition deposited on the recording medium.
The ink jet recording apparatus may be any ink jet recording apparatus that can eject ink droplets onto a recording medium for recording and preferably has a function of heating the recording medium during printing. The term “during printing”, as used herein, refers to a period from the time at which ink droplets ejected from an ink jet recording apparatus adhere to a recording medium to the time at which the ink is dried.
The function of heating a recording medium may be a print heater function in which a recording medium is directly heated with a heat source in contact with the recording medium or a dryer function in which the recording medium is irradiated with infrared rays or a microwave (an electromagnetic wave having the maximum wavelength at approximately 2,450 MHz) or is blown by a warm current of air without contact between the recording medium and the heat source. The print heater function and the dryer function may be utilized alone or in combination. Such a heating function can control drying temperature during printing.
A recording medium on which ink droplets ejected from an ink jet recording apparatus are deposited may be dried with a dryer or in a thermostat oven or bath at a predetermined temperature.
A recording medium is a non-ink-absorbing or low-ink-absorbing recording medium (hereinafter also referred to simply as a “plastic medium”). Examples of the non-ink-absorbing recording medium include plastic films that are not surface-treated for ink jet printing (that is, plastic films having no ink-absorbing layer) and substrates, such as paper sheets, to which a plastic is applied or on which a plastic film is laminated. The plastics include poly(vinyl chloride), poly(ethylene terephthalate), polycarbonate, polystyrene, polyurethane, polyethylene, and polypropylene. Examples of the low-ink-absorbing recording medium include actual printing paper, such as art paper, coated paper, and matte paper.
The phrase “non-ink-absorbing or low-ink-absorbing recording medium”, as used herein, refers to a recording medium that absorbs 10 mL/m2 or less of water for a contact time of 30 msec/1/2 as determined by a Bristow method. The Bristow method is the most widely used method for measuring the amount of liquid absorbed for a short period of time. The Bristow method has been adopted by Japan Technical Association of the Pulp and Paper Industry (JAPAN TAPPI). The details of the Bristow method is described in specification No. 51 “Kami Oyobi Itagami—Ekitai Kyushusei Siken Houhou—Buristo Hou (Paper and paperboard—liquid absorption test method—Bristow method)” in “JAPAN TAPPI Test Methods”, 2000.
An ink jet recording method using an ink jet recording apparatus can be performed as described below. An aqueous ink composition (described below) is ejected as droplets onto a plastic medium to form an image on the plastic medium. An ink jet ejection method may be any conventionally known method. In particular, a method for ejecting droplets utilizing the vibration of a piezoelectric element (a recording method using an ink jet head that can form ink droplets by the mechanical deformation of an electrostrictive element) enables excellent image recording.
The plastic medium is then heated to 40° C. or more with a print heater of the ink jet recording apparatus and a dryer to dry the aqueous ink composition (described below) deposited on the plastic medium. This step rapidly evaporates water in the aqueous ink composition deposited on the plastic medium, and resin particles (described below) in the aqueous ink composition form a film. This produces high-quality images even on the plastic medium in a short period of time with reduced occurrence of inconsistencies in density and bleeding or blurring. The formation of the film formed of the resin particles allows dried ink to adhere to the plastic medium, thus fixing the images.
The heating temperature of the plastic medium is 40° C. or more, preferably 40° C. or more and 80° C. or less, more preferably 40° C. or more and 60° C. or less. Heating the plastic medium to 40° C. or more can effectively promote the evaporation of a liquid medium in the aqueous ink composition. The heating temperature of the plastic medium higher than 80° C. may cause defects, such as deformation, in some plastic media or defects, such as contraction, in some plastic media cooled to room temperature.
The heating time of the plastic medium is not particularly limited provided that a liquid medium in the aqueous ink composition can evaporate and a resin fixative can form a film. The heating time is appropriately determined in consideration of the types of solvent and resin particles and the printing speed employed.
1.2. Aqueous Ink Composition
An aqueous ink composition for use in an ink jet recording method according to an embodiment of the invention will be described in detail below.
1.2.1. Pigment
An aqueous ink composition for use in an ink jet recording method according to the present embodiment contains C.I. pigment yellow 180 as a pigment. C.I. pigment yellow 180 has high light resistance and, in combination with a first solvent described below, can form high-quality images.
In general, thawing of aqueous ink compositions containing C.I. pigment yellow 180 in a frozen state stored at low temperature tends to cause the agglomeration of the pigment. However, thawing of an aqueous ink composition according to the present embodiment having a composition described below stored at low temperature causes less agglomeration of C.I. pigment yellow 180. Thus, the aqueous ink composition has excellent low-temperature storage stability.
The C.I. pigment yellow 180 content is preferably 1% by mass or more and 10% by mass or less, more preferably 3% by mass or more and 7% by mass or less, of the total mass of the aqueous ink composition. The C.I. pigment yellow 180 content within the range described above results in excellent dispersibility of C.I. pigment yellow 180 in the aqueous ink composition and excellent color reproduction of images formed on plastic media.
1.2.2. Solvent
An aqueous ink composition for use in an ink jet recording method according to the present embodiment contains a first solvent, a second solvent, and a third solvent.
The first solvent contains at least one selected from 1,2-hexanediol and 1,2-pentanediol. The first solvent improves the wettability of the aqueous ink composition on plastic media and can reduce ink bleeding in images formed on the plastic media.
The first solvent content (W1) is 3% by mass or more and 6% by mass or less of the total mass of the aqueous ink composition. The first solvent content (W1) within the range described above results in high-quality images with less ink bleeding. The first solvent content (W1) below the lower limit may cause ink bleeding, resulting in low-quality images. The first solvent content (W1) above the upper limit may cause the agglomeration of pigment in the aqueous ink composition at low temperature, resulting in low storage stability.
The second solvent contains at least one selected from the group consisting of 2-pyrrolidone, N-methyl-2-pyrrolidone, N,N′-dimethylpropyleneurea, 1,3-dimethyl-2-imidazolidinone, tetramethylurea, dimethyl sulfoxide, and hexamethylphosphoric triamide.
The third solvent contains at least one selected from propylene glycol and 1,3-propanediol.
The second solvent and the third solvent have excellent compatibility with the first solvent and can improve the low-temperature storage stability of the aqueous ink composition. The second solvent and the third solvent can reduce an increase in the viscosity of the aqueous ink composition and the agglomeration of pigment after the thawing of the aqueous ink composition in a frozen state. Thus, the aqueous ink composition after thawing can be used with high ejection stability.
The second solvent content (W2) is preferably 3% by mass or more, more preferably 3% by mass or more and 24% by mass or less, of the total mass of the aqueous ink composition. The third solvent content (W3) is preferably 22% by mass or less, more preferably 1% by mass or more and 22% by mass or less, of the total mass of the aqueous ink composition. Preferably, the total (W2+W3) of the second solvent content (W2) and the third solvent content (W3) is 9% by mass or more and 25% by mass or less.
The second solvent content (W2) of 3% by mass or more and the total content (W2+W3) of the second solvent and the third solvent of 9% by mass or more result in the aqueous ink composition having excellent low-temperature storage stability. In contrast, the second solvent content (W2) below 3% by mass and the total content (W2+W3) of the second solvent and the third solvent below 9% by mass may result in poor low-temperature storage stability of the aqueous ink composition. The second solvent content (W2) above 24% by mass may result in poor drying characteristics of images formed on plastic media. The third solvent content (W3) above 22% by mass may result in poor drying characteristics or low abrasion resistance of images formed on plastic media. The total (W2+W3) of the second solvent content (W2) and the third solvent content (W3) above 25% by mass may result in poor drying characteristics or low abrasion resistance of images.
In an aqueous ink composition for use in an ink jet recording method according to the present embodiment, the ratio (W2/W1) of the second solvent content (W2) to the first solvent content (W1) is one or more, preferably one or more and eight or less, and the ratio [(W2+W3)/(W1)] of the total (W2+W3) of the second solvent content (W2) and the third solvent content (W3) to the first solvent content (W1) is three or more, preferably three or more and eight or less. The ratios (W2/W1) and [(W2+W3)/(W1)] within the ranges described above result in excellent low-temperature storage stability, high ejection stability, and high-quality images formed on plastic media with less blurring.
The (W2/W1) of one or more and the [(W2+W3)/(W1)] of three or more result in excellent low-temperature storage stability of the aqueous ink composition. However, the (W2/W1) below one or the [(W2+W3)/(W1)] below three may result in low ejection stability of the aqueous ink composition or poor low-temperature storage stability due to an increase in viscosity or the agglomeration of pigment. The (W2/W1) above eight or the [(W2+W3)/(W1)] above eight may result in poor drying characteristics and blurring of images, although the aqueous ink composition has good low-temperature storage stability.
Preferably, an aqueous ink composition for use in an ink jet recording method according to the present embodiment does not contain glycerin. Glycerin can impart moisture retainability to aqueous ink compositions or improve the low-temperature storage stability of aqueous ink compositions. This can reduce nozzle clogging in ink jet recording apparatuses and improve the ejection stability of ink. However, the addition of glycerin may result in poor drying characteristics of images formed on plastic media and low abrasion resistance of images after drying.
Preferably, an aqueous ink composition for use in an ink jet recording method according to the present embodiment does not contain glycol ethers. Glycol ethers can improve the wettability of aqueous ink compositions on plastic media and can reduce ink bleeding in images formed on the plastic media. However, glycol ethers may lower the storage stability or the ejection stability of aqueous ink compositions.
Examples of the glycol ethers include ethylene glycol monobutyl ether, ethylene glycol mono-t-butyl ether, ethylene glycol mono-iso-propyl ether, 1-methyl-1-methoxybutanol, diethylene glycol monobutyl ether, diethylene glycol mono-t-butyl ether, diethylene glycol monopropyl ether, diethylene glycol mono-iso-propyl ether, triethylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol mono-iso-propyl ether, propylene glycol monobutyl ether, propylene glycol mono-t-butyl ether, dipropylene glycol monopropyl ether, dipropylene glycol mono-iso-propyl ether, and dipropylene glycol monobutyl ether.
Without the addition of glycerin or glycol ethers, when the ratios and the amounts of the first solvent, the second solvent, and the third solvent are within the ranges described above, an aqueous ink composition for use in an ink jet recording method according to the present embodiment has high ejection stability and low-temperature storage stability, can reduce blurring of images formed on plastic media, and can produce images having high abrasion resistance.
1.2.3. Water
An aqueous ink composition for use in an ink jet recording method according to the present embodiment contains water. Water is the main medium of the aqueous ink composition and evaporates in the drying process described above.
Preferably, the water contains only a minimal amount of ionic impurities and may be pure water or ultrapure water, such as ion-exchanged water, ultrafiltered water, reverse osmosis water, or distilled water. Use of water sterilized, for example, by ultraviolet irradiation or the addition of hydrogen peroxide can prevent the generation of mold or bacteria in pigment dispersions or aqueous ink compositions containing the pigment dispersions during long-term storage.
1.2.4. Other Components
An aqueous ink composition for use in an ink jet recording method according to the present embodiment can further contain resin particles, a resin dispersant, a silicon surfactant, a pH-adjusting agent, a preservative or fungicide, an anticorrosive, and a chelator.
Resin particles can solidify images formed on plastic media and firmly fix the images on the plastic media. Preferably, an aqueous ink composition for use in an ink jet recording method according to the present embodiment contains resin particles in emulsion or suspension. Resin particles in emulsion or suspension can facilitate control of the viscosity of the aqueous ink composition within an appropriate range for an ink jet recording method according to the present embodiment, thus ensuring the storage stability and the ejection stability of the aqueous ink composition.
A resin dispersant can stably disperse the pigment described above (C.I. pigment yellow 180) in the aqueous ink composition.
Examples of the components of the resin particles and the resin dispersant include homopolymers and copolymers of acrylic acid, acrylate, methacrylic acid, methacrylate, acrylonitrile, cyanoacrylate, acrylamide, olefin, styrene, vinyl acetate, vinyl chloride, vinyl alcohol, vinyl ether, vinylpyrrolidone, vinylpyridine, vinylcarbazole, vinylimidazole, and vinylidene chloride, fluorocarbon resin, and natural resin. The copolymers may be random copolymers, block copolymers, alternating copolymers, or graft copolymers.
The resin particles may be manufactured by a known method using known materials. For example, resin particles described in JP-B-62-1426, JP-A-3-56573, JP-A-3-79678, JP-A-3-160068, and JP-A-4-18462 may be used. The resin particles may be a commercial product, for example, Microgel E-1002 or E-5002 (trade names, manufactured by Nippon Paint Co., Ltd.), Voncoat 4001 or 5454 (trade names, manufactured by Dainippon Ink and Chemicals, Inc.), SAE1014 (trade name, manufactured by ZEON Co.), Saibinol SK-200 (trade name, manufactured by Saiden Chemical Industry Co., Ltd.), or Joncryl 7100, 390, 711, 511, 7001, 632, 741, 450, 840, 74J, HRC-1645J, 734, 852, 7600, 775, 537J, 1535, PDX-7630A, 352J, 352D, PDX-7145, 538J, 7640, 7641, 631, 790, 780, or 7610 (trade names, manufactured by BASF Japan Ltd.).
The resin dispersant may be a commercial product, for example, Joncryl 67, 678, 586, 611, 680, 682, 683, or 690 (trade names, manufactured by BASF Japan Ltd.).
A silicon surfactant can uniformly spread ink on plastic media to prevent inconsistencies in density and bleeding of ink. The silicon surfactant content preferably ranges from 0.1% by mass to 1.5% by mass of the total mass of the aqueous ink composition. The silicon surfactant content below 0.1% by mass may result in insufficient wettability of ink on plastic media, often causing inconsistencies in density or bleeding of ink. The silicon surfactant content above 1.5% by mass may result in low storage stability and ejection stability of the aqueous ink composition.
The silicon surfactant is preferably a polysiloxane compound, for example, polyether-modified organosiloxane. The silicon surfactant may be a commercial product, for example, BYK-306, BYK-307, BYK-333, BYK-341, BYK-345, BYK-346, or BYK-348 (trade names, manufactured by BYK Japan KK), or KF-351A, KF-352A, KF-353, KF-354L, KF-355A, KF-615A, KF-945, KF-640, KF-642, KF-643, KF-6020, X-22-4515, KF-6011, KF-6012, KF-6015, or KF-6017 (trade names, manufactured by Shin-Etsu Chemical Co., Ltd.).
Examples of the pH-adjusting agent include potassium dihydrogen phosphate, disodium hydrogen phosphate, sodium hydroxide, lithium hydroxide, potassium hydroxide, ammonia, diethanolamine, triethanolamine, triisopropanolamine, potassium carbonate, sodium carbonate, and sodium hydrogen carbonate.
Examples of the preservative and fungicide include sodium benzoate, sodium pentachlorophenol, sodium 2-pyridinethiol-1-oxide, sodium sorbate, sodium dehydroacetate, and 1,2-dibenzisothiazolin-3-one. The preservative and fungicide may be a commercial product, such as Proxel XL2 or GXL (trade names, manufactured by Avecia Ltd.) or Denicide CSA or NS-500W (trade names, manufactured by Nagase ChemteX Co.).
Examples of the anticorrosive include benzotriazole.
Examples of the chelator include ethylenediaminetetraacetic acid and salts thereof (disodium dihydrogen ethylenediaminetetraacetate).
1.2.5. Physical Properties
The viscosity of an aqueous ink composition for use in an ink jet recording method according to the present embodiment at 20° C. is preferably 2 mPa·s or more and 10 mPa·s or less, more preferably 3 mPa·s or more and 6 mPa·s or less. The viscosity of the aqueous ink composition at 20° C. within the range described above allows a proper number of droplets of the aqueous ink composition to be ejected from a nozzle, further reducing the flight deviation and scattering of droplets. Thus, the aqueous ink composition can be suitably used in ink jet recording apparatuses. The viscosity of an aqueous ink composition can be measured with an oscillation viscometer VM-100AL (manufactured by Yamaichi Electronics Co., Ltd.) while the temperature of the aqueous ink composition is maintained at 20° C.
2. Recorded Matter
Recorded matter according to an embodiment of the invention is prepared by an ink jet recording method described above. Images recorded on plastic media using an aqueous ink composition described above are of good quality with less ink bleeding and high abrasion resistance.
3. Examples
Although the invention is further described in the following examples, the invention is not limited to these examples.
3.1. Preparation of Pigment Dispersion
A pigment dispersion containing pigment dispersed with a resin dispersant was used in an aqueous ink composition used in the present example.
The pigment dispersion was prepared as described below. First, 100 parts by mass of a mixture containing 5.0 parts by mass of an acrylic acid-acrylate copolymer as a resin dispersant, 20 parts by mass of C.I. pigment yellow 180 as pigment, and ion-exchanged water was prepared. The mixture, together with zirconia beads (having a diameter of 1.5 mm), was dispersed in a sand mill (manufactured by Yasukawa Seisakusho Co., Ltd.) for six hours. The zirconia beads were separated with a separator to prepare the pigment dispersion.
In Example 3, the pigment dispersion was prepared in the same manner except that 4.5 parts by mass of the acrylic acid-acrylate copolymer and 17.5 parts by mass of C.I. pigment yellow 180 were used.
In Comparative Example 1, the pigment dispersion was prepared in the same manner except that C.I. pigment yellow 74 was used in place of C.I. pigment yellow 180 as pigment.
3.2. Preparation of Aqueous Ink Composition
A first solvent, a second solvent, a third solvent, a silicon surfactant, and ion-exchanged water were added to the pigment dispersion in accordance with the compositions described in Tables 1 and 2. The solution was then mixed at normal temperature for one hour and was filtered through a membrane filter having a pore size of 5 μm to prepare an aqueous ink composition.
In Comparative Example 6, the aqueous ink composition was prepared in the same manner except that the third solvent was not added but glycerin was added.
In Comparative Example 7, the aqueous ink composition was prepared in the same manner except that the third solvent was not added but ethylene glycol monobutyl ether was added.
The components in the tables were as follows:

    (1) Pigment
    
        C.I. pigment yellow 180
        C.I. pigment yellow 74
    
    
    (2) First Solvent
    
        1,2-hexanediol
        1,2-pentanediol
    
    
    (3) Second Solvent
    
        1,3-dimethyl-2-imidazolidinone
        N,N′-dimethylpropyleneurea
        2-pyrrolidone
        N-methyl-2-pyrrolidone
    
    
    (4) Third Solvent
    
        Propylene glycol
        1,3-propanediol
    
    
    (5) Other Solvents
    
        Glycerin
        Diethylene glycol monobutyl ether
    
    
    (6) Silicon Surfactant
    
        Silicon surfactant (manufactured by BYK Japan KK, trade name “BYK-348”, polyether-modified siloxane)
    
    
    (7) Resin Dispersant
    
        Acrylic acid-acrylate copolymer
    
    
    (8) Resin Particles
    
        Styrene-acrylic acid copolymer

3.3. Evaluation Test

3.3.1. Evaluation of Storage Stability

    
    


An aqueous ink composition hermetically sealed in a sample bottle was stored at −20° C. for three days and then at 20° C. for four hours. The storage stability was evaluated by comparing the viscosity of the aqueous ink composition at 20° C. and the particle size of the pigment before storage with the viscosity of the aqueous ink composition at 20° C. and the particle size of the pigment after storage.
The viscosity was measured with an oscillation viscometer VM-100AL (manufactured by Yamaichi Electronics Co., Ltd.) after the aqueous ink composition was maintained at 20° C. for one hour. The particle size of pigment was measured as the average particle size with a laser Doppler particle size distribution analyzer Microtrac UPA150 (manufactured by Nikkiso Co., Ltd.).
The evaluation criteria were described below.
Viscosity Change


    
    
        Good: The viscosity change was −0.3 mPa·s or more and +0.3 mPa·s or less.
        Poor: The viscosity change was less than −0.3 mPa·s or more than +0.3 mPa·s.

Particle Size Change

        Good: The rate of change in average particle size was less than 5%.
        Poor: The rate of change in average particle size was 5% or more.

3.3.2. Evaluation of Bleeding or Blurring

(1) Preparation of Recorded Matter

    
    


A temperature adjustable heater that could heat a recording medium during recording of images was installed on a paper guide of an ink jet printer PX-G930 (manufactured by Seiko Epson Co.).
The nozzles of the modified printer were filled with aqueous ink compositions of four colors (C, M, Y, and K). A solid pattern image was formed on a plastic medium (trade name “Cold laminate film PG-50L”, manufactured by Lami Corporation Inc., PET film) at normal temperature and pressure such that each of C, M, and K was in contact with Y. The plastic medium was heated to 45° C. with the heater on the paper guide to dry the solid pattern image. The plastic medium was then placed in a dryer at 60° C. to dry the solid pattern image for another one minute. Thus, recorded matter containing the solid pattern image formed on the plastic medium was prepared.
The solid pattern image was formed in 720 dpi by 720 dpi resolution at 50% duty. The term “duty”, as used herein, refers to the percentage (%) of ink-dotted partitions. In 720 dpi by 720 dpi resolution, the duty is the percentage of ink-dotted partitions in 720×720=518,400 partitions per square inch.
The yellow (Y) aqueous ink composition was prepared above in “3.2. Preparation of Aqueous Ink Composition”.
For the C, M, and K aqueous ink compositions, the pigment dispersion was prepared as described above in “3.1. Preparation of Pigment Dispersion” except that the following pigments were used in place of C.I. pigment yellow 180. The C, M, and K aqueous ink compositions were prepared as described above in “3.2. Preparation of Aqueous Ink Composition” using these pigment dispersions.

    
    
        Cyan (C) ink composition: C.I. pigment blue 15:3
        Magenta (M) ink composition: C.I. pigment red 122
        Black (K) ink composition: C.I. pigment black 7

(2) Method for Evaluating Recorded Matter

    
    


In the recorded matter prepared in (1), bleeding or blurring in contact portions between Y and other colors (C, M, and K) at different duties was observed.
The evaluation criteria were described below.

    
    
        Good: No bleeding or blurring was observed in the contact portions.
        Poor: Bleeding or blurring was observed in the contact portions.

3.3.3. Evaluation of Ejection Stability

(1) Preparation of Recorded Matter

    
    


The nozzles of the ink jet printer PX-G930 used in “3.3.2. Evaluation of Bleeding or Blurring” were filled with the aqueous ink composition prepared above in “3.2. Preparation of Aqueous Ink Composition”. The aqueous ink compositions were continuously ejected onto plain paper (Fuji Xerox P paper etc.) for 10 minutes without heating the plain paper to check that the aqueous ink compositions were properly ejected from all the nozzles. A mixed pattern image of text and a figure was then continuously printed on plain paper heated to 45° C. at an average duty of 10% for a predetermined time to prepare recorded matter. The weight of ink ejected per dot was 20 ng. The resolution was 720 dpi by 720 dpi.
(2) Method for Evaluating Recorded Matter
The “missing dots” and “deviation” of the resulting recorded matter were evaluated. The term “deviation”, as used herein, refers to the displacement of the ink landing position on the recorded matter.
The evaluation criteria were described below.

    
    
        Good: No missing dot and no deviation were observed one hour after the start of printing.
        Fair: One hour after the start of printing, no missing dot was observed but deviation occurred.
        Poor: One hour after the start of printing, missing dots and deviation occurred frequently.

3.3.4. Evaluation of Abrasion Resistance

(1) Preparation of Recorded Matter

    
    


The nozzles of the ink jet printer PX-G930 used in “3.3.2. Evaluation of Bleeding or Blurring” were filled with the aqueous ink composition (yellow ink) prepared in “3.2. Preparation of Aqueous Ink Composition”. A solid pattern image was formed on a plastic medium (trade name “Cold laminate film PG-50L”, manufactured by Lami Corporation Inc., PET film) heated to 45° C. The plastic medium was then left still in a dryer at 60° C. to dry the solid pattern image for another one minute. Thus, recorded matter containing the solid pattern image formed on the plastic medium was prepared. The solid pattern image was formed in 720 dpi by 720 dpi resolution at 60% duty.
(2) Method for Evaluating Recorded Matter
After the resulting recorded matter was held at 20° C. for 16 hours, the recorded matter was rubbed 50 times under a load of 500 g against a white cotton cloth attached to a friction block on a Gakushin-type rubbing fastness tester AB-301 (manufactured by Tester Sangyo Co., Ltd.). The surface state of an image was visually inspected.
The evaluation criteria were described below.

    
    
        Good: No scratch was observed on the surface of the image.
        Fair: Slight scratches were observed on the surface of the image.
        Poor: A large scratch was observed on the surface of the image.

3.3.5. Evaluation of Light Resistance

(1) Preparation of Recorded Matter

    
    


The nozzles of an ink jet printer PX-5500 (manufactured by Seiko Epson Co.) were filled with the aqueous ink composition (yellow ink) prepared in “3.2. Preparation of Aqueous Ink Composition”. Recorded matter was prepared by printing a 10 mm×10 mm solid image on a photo paper (manufactured by Seiko Epson Co., model number “KA420PSKR”, glossy paper) at normal temperature and pressure at an optical density (OD) of 1.0.
(2) Method for Evaluating Recorded Matter
After exposure at an illuminance of 70,000 Lux for 600 hours in a xenon arc weatherometer XL75 (manufactured by Suga Test Instruments Co., Ltd.), the OD of the solid image of the recorded matter was measured with GRETAG SPM-50 (manufactured by GretagMacbeth). The light resistance of the image was evaluated by the ratio of the OD after exposure to the OD before exposure.
The evaluation criteria were described below.

    
    
        Good: The decrease in OD was less than 20%.
        Poor: The decrease in OD was 20% or more.

3.4. Evaluation Results

    
    


Tables 1 and 2 show the evaluation test results.

















TABLE 1








Example
Example
Example
Example
Example
Example
Example
Example





1
2
3
4
5
6
7
8

























Pigment
P.Y. 180

4.0
4.0
3.5
4.0
4.0
4.0
4.0
4.0


(mass %)
P.Y. 74











1st solvent
1,2-hexanediol

3.0
3.0

3.0
3.0
6.0
6.0
6.0


(mass %)
1,2-pentanediol



3.0







2nd solvent
1,3-dimethyl-2-imidazolidinone

3.0

3.0
3.0

3.0




(mass %)
N,N′-dimethylpropyleneurea


4.0









2-pyrrolidone

4.5


4.5
3.0
3.0
5.0
3.0



N-methyl-2-pyrrolidone


5.0
4.0



5.0
3.0


3rd solvent
Propylene glycol

5.0
5.0
7.0

6.0
12.0
15.0
19.0


(mass %)
1,3-propanediol




5.0






Other
Glycerin











solvents
Diethylene glycol











(mass %)
monobutyl ether











Silicon
Polyether-

0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5


surfactant
modified











(mass %)
siloxane











Resin
Acrylic acid-

1.0
1.0
0.9
1.0
1.0
1.0
1.0
1.0


dispersant
acrylate copolymer











(mass %)












Resin particle
Styrene-acrylic acid

2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0


(mass %)
copolymer











Remainder
Ion-exchanged

77.0
75.5
76.1
77.0
80.5
68.5
61.5
61.5


(mass %)
water
























2nd solvent/1st solvent (content ratio)
2.50
3.00
2.33
2.50
1.00
1.00
1.67
1.00


(2nd solvent + 3rd solvent)/1st solvent (content ratio)
4.17
4.67
4.67
4.17
3.00
3.00
4.17
4.17

















Evaluation
Storage stability
Viscosity change
Good
Good
Good
Good
Good
Good
Good
Good


results

Particle size
Good
Good
Good
Good
Good
Good
Good
Good




change











Bleeding or
Bleeding or
Good
Good
Good
Good
Good
Good
Good
Good



blurring
blurring











Ejection stability
Missing dots,
Good
Good
Good
Good
Good
Good
Good
Good




deviation











Abrasion
Scratches
Good
Good
Poor
Good
Good
Good
Good
Good



resistance












Light resistance
Evaluation results
Good
Good
Good
Good
Good
Good
Good
Good
























TABLE 2










Compar-
Compar-
Compar-
Compar-
Compar-
Compar-





ative
ative
ative
ative
ative
ative





Exam-
Exam-
Exam-
Exam-
Exam-
Exam-





ple 1
ple 2
ple 3
ple 4
ple 5
ple 6





Pigment
P.Y. 180


4.0
4.0
4.0
4.0
4.0


(mass %)
P.Y. 74

4.0







1st solvent
1,2-hexanediol

3.0
3.0
6.0
7.0
2.0
3.0


(mass %)
1,2-pentanediol









2nd solvent
1,3-dimethyl-2-

3.0

2.0


3.0


(mass %)
imidazolidinone










N,N′-










dimethylpropyleneurea










2-pyrrolidone

4.5
2.0
2.0
5.0
2.0
4.5



N-methyl-2-










pyrrolidone









3rd solvent
Propylene glycol

5.0
7.0
14.0
4.0
7.0



(mass %)
1,3-propanediol









Other solvents
Glycerin






5.0


(mass %)
Diethylene glycol










monobutyl ether









Silicon
Polyether-modified

0.5
0.5
0.5
0.5
0.5
0.5


surfactant
siloxane









(mass %)










Resin
Acrylic acid-acrylate

1.0
1.0
1.0
1.0
1.0
1.0


dispersant
copolymer









(mass %)










Resin
Styrene-acrylic acid

2.0
2.0
2.0
2.0
2.0
2.0


particle
copolymer









(mass %)










Remainder
Ion-exchanged water

77.0
80.5
68.5
76.5
81.5
77.0


(mass %)





















2nd solvent/1st solvent (content ratio) 
2.50
0.67
0.67
0.71
1.00
2.50


(2nd solvent + 3rd solvent)/1st solvent (content ratio)
4.17
3.00
3.00
1.29
4.50
—















Evaluation
Storage stability
Viscosity change
Good
Poor
Poor
Poor
Good
Good


results

Particle size
Good
Poor
Poor
Poor
Good
Good




change









Bleeding or blurring
Bleeding or blurring
Good
Good
Good
Good
Poor
Poor



Ejection stability
Missing dots,
Good
Good
Good
Poor
Fair
Good




deviation









Abrasion resistance
Scratches
Good
Good
Poor
Good
Good
Poor



Light resistance
Evaluation results
Poor
Good
Good
Good
Good
Good




















Compar-
Compar-
Compar-






ative
ative
ative






Exam-
Exam-
Exam-






ple 7
ple 8
ple 9






Pigment
P.Y. 180

4.0
4.0
4.0



(mass %)
P.Y. 74







1st solvent
1,2-hexanediol

3.0
6.5
3.0



(mass %)
1,2-pentanediol







2nd solvent
1,3-dimethyl-2-

3.0





(mass %)
imidazolidinone








N,N'-








dimethylpropyleneurea








2-pyrrolidone

4.5
7.0
3.0




N-methyl-2-








pyrrolidone







3rd solvent
Propylene glycol


13.0
5.0



(mass %)
1,3-propanediol







Other solvents
Glycerin







(mass %)
Diethylene glycol

5.0






monobutyl ether







Silicon
Polyether-modified

0.5
0.5
0.5



surfactant
siloxane







(mass %)








Resin
Acrylic acid-acrylate

1.0
1.0
1.0



dispersant
copolymer







(mass %)








Resin
Styrene-acrylic acid

2.0
2.0
2.0



particle
copolymer







(mass %)








Remainder
Ion-exchanged water

77.0
66.0
81.5



(mass %)

















2nd solvent/1st solvent (content ratio) 
2.50
1.08
1.00



(2nd solvent + 3rd solvent)/1st solvent (content ratio)
—
3.08
2.67














Evaluation
Storage stability
Viscosity change
Poor
Poor
Poor



results

Particle size
Poor
Poor
Poor





change







Bleeding or blurring
Bleeding or blurring
Good
Good
Good




Ejection stability
Missing dots,
Fair
Good
Good





deviation







Abrasion resistance
Scratches
Good
Good
Good




Light resistance
Evaluation results
Good
Good
Good









The evaluation results of storage stability show that the aqueous ink compositions according to Examples 1 to 8 shown in Table 1 have high storage stability with small changes in viscosity and particle size. The evaluation results of bleeding or blurring show that the aqueous ink compositions according to Examples 1 to 8 produced the image on the plastic medium with less blurring. The evaluation results of light resistance show that the aqueous ink compositions according to Examples 1 to 8 have high light resistance with a small decrease in the OD of the image. The evaluation results of ejection stability show that the aqueous ink compositions according to Examples 1 to 8 have high ejection stability in the continuous printing with less missing dots of the image and displacement of the ink landing position.
The evaluation results of abrasion resistance show that the aqueous ink compositions according to Examples 1 and 2 and Examples 4 to 8 have high abrasion resistance with no scratch on the surface of the image. Although the aqueous ink composition according to Example 3 shown in Table 1 had slight scratches on the surface of the image in the abrasion resistance test, the scratches were not significant for practical applications.
The aqueous ink composition according to Comparative Example 1 shown in Table 2 did not contain C.I. pigment yellow 180. For this reason, the image recorded had low light resistance.
The aqueous ink compositions according to Comparative Examples 2 and 3 shown in Table 2 had a ratio (W2/W1) of the second solvent content (W2) to the first solvent content (W1) below one. For this reason, the aqueous ink compositions had low storage stability.
The aqueous ink composition according to Comparative Example 4 shown in Table 2 had a first solvent content (W1) above 6% by mass. The aqueous ink composition according to Comparative Example 4 had a ratio (W2/W1) of the second solvent content (W2) to the first solvent content (W1) below one and a ratio [(W2+W3)/(W1)] of the total (W2+W3) of the second solvent content (W2) and the third solvent content (W3) to the first solvent content (W1) below three. For this reason, the aqueous ink composition according to Comparative Example 4 had low storage stability and ejection stability.
The aqueous ink composition according to Comparative Example 5 shown in Table 2 had a first solvent content below 3% by mass. For this reason, the image recorded had blurring.
The aqueous ink composition according to Comparative Example 6 shown in Table 2 contained glycerin. For this reason, the aqueous ink composition according to Comparative Example 6 produced a blurred image having low abrasion resistance in the bleeding or blurring test and the abrasion resistance test.
The aqueous ink composition according to Comparative Example 7 shown in Table 2 contained one of glycol ethers, diethylene glycol monobutyl ether. For this reason, the aqueous ink composition according to Comparative Example 7 had low storage stability.
The aqueous ink composition according to Comparative Example 8 shown in Table 2 had a first solvent content above 6% by mass. For this reason, the aqueous ink composition according to Comparative Example 8 had low storage stability.
The aqueous ink composition according to Comparative Example 9 shown in Table 2 had a ratio (W2/W1) of the second solvent content (W2) to the first solvent content (W1) of one or more and a ratio [(W2+W3)/(W1)] of the total (W2+W3) of the second solvent content (W2) and the third solvent content (W3) to the first solvent content (W1) below three. For this reason, the aqueous ink composition according to Comparative Example 9 had low storage stability.
The invention is not limited to the embodiments described above, and various modifications may be made therein. For example, the invention includes substantially the same constitutions as those described in the embodiments (for example, constitutions having the same functions, methods, and results, and constitutions having the same objects and advantages). The invention also includes constitutions in which unessential portions of the constitutions described in the embodiments are substituted. The invention also includes other constitutions that have the operation and effect of the constitutions described in the embodiments and other constitutions with which the same objects can be achieved. The invention also includes constitutions in which the constitutions described in the embodiments are combined with known techniques.

## Claims

1. An ink jet recording method comprising:
ejecting droplets of an aqueous ink composition from an ink jet recording apparatus onto a non-ink-absorbing or low-ink-absorbing recording medium; and
heating the recording medium to 40° C. or more to dry the aqueous ink composition deposited on the recording medium,
wherein the aqueous ink composition contains a pigment containing C.I. pigment yellow 180,
a first solvent containing at least one selected from 1,2-hexanediol and 1,2-pentanediol,
a second solvent containing at least one selected from the group consisting of 2-pyrrolidone, N-methyl-2-pyrrolidone, N,N′-dimethylpropyleneurea, 1,3-dimethyl-2-imidazolidinone, tetramethylurea, dimethyl sulfoxide, and hexamethylphosphoric triamide, and
a third solvent containing at least one selected from propylene glycol and 1,3-propanediol,
the first solvent content (W1) is 3% by mass or more and 6% by mass or less of the mass of the aqueous ink composition,
the ratio (W2/W1) of the second solvent content (W2) to the first solvent content (W1) is one or more, and
the ratio [(W2+W3)/(W1)] of the total (W2+W3) of the second solvent content (W2) and the third solvent content (W3) to the first solvent content (W1) is three or more.

2. Recorded matter prepared by the ink jet recording method according to claim 1.

3. The ink jet recording method according to claim 1, wherein the total (W2+W3) of the second solvent content (W2) and the third solvent content (W3) is 9% by mass or
more and 25% by mass or less of the aqueous ink composition.

4. Recorded matter prepared by the ink jet recording method according to claim 3.

5. The ink jet recording method according to claim 1, wherein the pigment content is 1% by mass or more and 10% by mass or less of the aqueous ink composition.

6. Recorded matter prepared by the ink jet recording method according to claim 5.

7. The ink jet recording method according to claim 1, wherein the aqueous ink composition has a viscosity of 2 mPa·s or more and 10 mPa·s or less at a measurement temperature of 20° C.

8. Recorded matter prepared by the ink jet recording method according to claim 7.