# Patent

## Title
Inkjet recording medium and method of manufacturing the same

## Abstract

An inkjet recording medium having on a substrate an ink-receiving layer containing inorganic fine particles and organic nitrogen-containing cationic polymer, with the organic nitrogen-containing cationic polymer being contained in a greater quantity in a half of the ink-receiving layer at a side nearer to the substrate (a near-substrate side) than in a half of the ink-receiving layer at a side further from the substrate (a far-substrate side) when the ink-receiving layer is divided into two equal parts by a plane parallel to the substrate.

## Background
CROSS-REFERENCE TO RELATED APPLICATION
This application claims priority under 35 USC 119 from Japanese Patent Application No. 2007-094271, the disclosure of which is incorporated by reference herein.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to an inkjet recording medium and a manufacturing method thereof.
2. Description of the Related Art
A wide variety of information-processing systems have been developed as the information-technology industry has made rapid strides forward, and recording methods and apparatus suitable for the information-processing systems have also been developed and put to practical use.
Of these recording methods, an inkjet recording method has come to be widely used not only in offices but also at home for at-home recording because it has the advantages that recording can be performed on various kinds of recording materials and the hardware (apparatus) required is relatively low priced, compact, and outstandingly quiet.
In addition, with the improvement in resolution of images printed by recent inkjet printers, it has become possible to obtain recorded matter of photograph-like high quality, and with this evolution of the hardware (apparatus), various kinds of media for inkjet recording have been developed.
Properties required of recording sheets for inkjet recording generally include (1) a property of drying quickly (having a high ink absorption speed), (2) a property of ensuring ink dots of a correct and uniform diameter (being free of bleeding), (3) a property of ensuring good graininess, (4) a property of ensuring ink dots of high roundness, (5) a property of ensuring high color densities, (6) a property of ensuring high color saturation (no dullness), (7) a property of ensuring high resistance to water, light and ozone in the printed portion, (8) a property of having a high degree of whiteness in the background portion, (9) a property of having good storability (a property of causing neither yellow coloration even over long-term storage nor bleeding of images by long-term storage (bleeding with age)), (10) a property of having high resistance to deformation and good dimensional stability (having sufficiently limited curling), and (11) a property of ensuring smooth running in apparatus.
When recording sheets are used as glazed photo paper for the purpose of obtaining photograph-like high-quality recorded matter, they are further required to have glossiness, surface smoothness and texture resembling that of photographic printing paper for silver-salt photographs in addition to the properties recited above.
For the purpose of improving these properties, inkjet recording media having porous structures in their respective ink-receiving layers have been developed and put to practical use in recent years. Such inkjet recording media can have excellent ink receptivity (quick-dry properties) and high glossiness owing to their porous structures.
For example, inkjet recording media having, on a substrate, an ink-receiving layer containing fine particles of an inorganic pigment and a water-soluble resin, and having high porosity, have been proposed (see, for example, JP-A Nos. 10-119423 and 10-217601).
Owing to their makeup, these recording media, in particular, an inkjet recording medium provided with an ink-receiving layer having a porous structure using silica as fine particles of inorganic pigment, have high ink absorbency and ink receptivity high enough to form images of high resolution, and can exhibit high glossiness.
On the other hand, among ingredients incorporated into an ink-receiving layer, cationic polymers are known as a component for improvements in prevention of bleeding (see, for example, JP-A Nos. 2006-321176 and 2006-248017).
SUMMARY OF THE INVENTION
The present invention has been made in view of the above circumstances, and provides an inkjet recording medium and a manufacturing method thereof.
A first aspect of the invention provides an inkjet recording medium comprising, on a substrate, an ink-receiving layer comprising inorganic fine particles and an organic nitrogen-containing cationic polymer, the organic nitrogen-containing cationic polymer being contained in a greater quantity in a half of the ink-receiving layer at a side nearer to the substrate (a near-substrate side) than in a half of the ink-receiving layer at a side further from the substrate (a far-substrate side) when the ink-receiving layer is divided into two equal parts by a plane parallel to the substrate
A second aspect of the invention provides a method of manufacturing an inkjet recording medium, comprising:
forming a coating layer on a substrate by applying to the substrate at least a first solution A containing inorganic fine particles and a cationic emulsion and a first solution B differing in composition from the first solution A, in order of increasing distance from the substrate, and
performing cross-linking curing of the coating layer by applying a second solution containing a basic compound at either (1) the same time as at least the first solution A and the first solution B are applied or (2) a stage during drying of the coating layer formed by applying at least the first solution A and the first solution B before the coating layer exhibits decreasing-rate drying,
an ink-receiving layer thus being formed that includes the coating layer having undergone cross-linking curing and contains an organic nitrogen-containing cationic polymer in a greater quantity in a half at a side nearer to the substrate (a near-substrate side) than in a half at a side further from the substrate (a far-substrate side) when the ink-receiving layer is divided into two equal parts by a plane parallel to the substrate.
A third aspect of the invention provides a method of manufacturing an inkjet recording medium, comprising:
forming a coating layer on a substrate by applying to the substrate at least a first solution A containing inorganic fine particles and a cationic emulsion and a first solution B differing in composition from the first solution A, in order of increasing distance from the substrate,
cooling the coating layer to a temperature at least 5° C. lower than a lower temperature of respective temperatures at which the first solution A and the first solution B are applied, and
forming an ink-receiving layer by drying the coating layer thus cooled,
the ink-receiving layer thus formed containing an organic nitrogen-containing cationic polymer in a greater quantity in a half at a side nearer to the substrate (a near-substrate side) than in a half at a side further from the substrate (a far-substrate side) when the ink-receiving layer is divided into two equal parts by a plane parallel to the substrate.


DETAILED DESCRIPTION OF THE INVENTION
According to the present invention, it is possible to provide an inkjet recording medium that allows retention of high image densities while inhibiting images recorded thereon from bleeding (bleeding with age) and that has high resistance to ozone, and to provide a method of manufacturing such an inkjet recording medium.
The invention is described below in detail.
<<Inkjet Recording Medium>>
An inkjet recording medium according to the invention has on a substrate an ink-receiving layer containing inorganic fine particles and an organic nitrogen-containing cationic polymer, and the ink-receiving layer is structured to contain the organic nitrogen-containing cationic polymer in a greater quantity in a half portion nearer the substrate (hereafter also referred to as the lower-side half of the ink-receiving layer) than in a half portion further from the substrate (hereafter also referred to as the upper-side half of the ink-receiving layer) when it is divided into two equal parts by a plane parallel to the substrate.
The presence distribution of the organic nitrogen-containing cationic polymer in the ink-receiving layer can be ascertained by elemental analysis. Specifically, the ascertainment may be made by performing mapping analysis according to the SEM-EDX method and observing the images obtained. In this case, the presence position of the ink-receiving layer as a whole is ascertained first by mapping analysis of the main component (e.g., elemental Si) of the ink-receiving layer, and then mapping analysis of elemental N is performed. From the mapping image thus obtained, it is determined which part of the ink-receiving layer, the upper-side half or the lower-side half, contains elemental N in a greater quantity.
By being so structured as described above, the present inkjet recording medium can retain high image densities while inhibiting the images recorded from bleeding (bleeding with age), and can improve resistance to ozone. When an ink-receiving layer is so structured that one half of the ink-receiving layer on the side nearer the substrate (near-substrate side) and the other half on the side further from the substrate (far-substrate side) have an equal quantity of an organic nitrogen-containing cationic polymer contained therein, or an organic nitrogen-containing cationic polymer is present in a greater quantity in the half of the ink-receiving layer at a side further from the substrate than in the half at a side nearer to the substrate, the densities of images recorded are lowered and resistance to ozone deteriorates.
The present inkjet recording medium has no particular restrictions as to its manufacturing method, but it can be manufactured suitably by methods according to the invention as described hereinafter.
In the invention, the ratio of nitrogen-containing cationic polymer content in the ink-receiving layer [content (by mass) in the upper-side half of the ink-receiving layer/content (by mass) in the lower-side half of the ink-receiving layer] is required to be smaller than 1.0.
From the viewpoint of more effectively achieving the effects of the present invention, the ratio of content is preferably from 0 to 0.8, and more preferably from 0 to 0.4.
The ink-receiving layer containing an organic nitrogen-containing cationic polymer in a content ratio as specified above can be formed, for example, by adjusting the cationic emulsion content ratio [content in a first solution B/content in a first solution A] to a range as specified hereafter in the present method of manufacturing an inkjet recording medium as described hereafter.
Further from the viewpoint of more effectively achieving the effects of the present invention, the organic nitrogen-containing cationic polymer content in the lower-side half of the ink-receiving layer is preferably from 2% to 25% by mass, more preferably from 4% to 20% by mass, and particularly preferably from 6% to 18% by mass, with respect to the total solid content in the lower-side half.
On the other hand, from the viewpoint of more effectively achieving the effects of the present invention, the organic nitrogen-containing cationic polymer content in the upper-side half of the ink-receiving layer is preferably from 1% to 20% by mass, more preferably from 2% to 15% by mass, and particularly preferably from 4% to 12% by mass, with respect to the total solid content in the upper-side half.
Furthermore from the viewpoint of more effectively achieving the effects of the present invention, the organic nitrogen-containing cationic polymer content in the whole ink-receiving layer, including both the upper-side half and the lower-side half together, is preferably from 1% to 15% by mass, more preferably from 1.5% to 12% by mass, particularly preferably from 2% to 10% by mass, with respect to the total solid content in the whole ink-receiving layer.
Additionally, the expression “total solid content in the ink-receiving layer” is intended to include all the components but water of the composition for forming the ink-receiving layer.
From the viewpoint of more effectively achieving the effects of the present invention, it is further preferred that the ratio of content of the organic nitrogen-containing cationic polymer to inorganic fine particles in the lower-side half is higher than the ratio of content of the organic nitrogen-containing cationic polymer to the inorganic fine particles in the upper-side half.
<Ink-Receiving Layer>
The ink-receiving layer in the present invention may be formed of only one layer, or it may be composed of two or more layers. When the ink-receiving layer is composed of two or more layers, when the two or more layers are regarded as one integrated ink-receiving layer and an upper-side half portion and lower-side half portion of the integrated ink-receiving layer are defined, it is required that the organic nitrogen-containing cationic polymer be contained in a greater quantity in the lower-side half of the ink-receiving layer than in the upper-side half of the ink-receiving layer.
In view of enhancing the glossiness of the ink-receiving layer, it is preferred that the present ink-receiving layer includes two or more layers in a format in which colloidal silica is contained in the uppermost layer furthest from the substrate. The uppermost layer containing colloidal silica is also referred to as “colloidal silica layer”.
In view of ensuring an absorption capacity high enough to absorb all droplets, it is preferred that the ink-receiving layer thickness is determined in conjunction with the porosity of the layer. When the ink quantity is 8 mL/mm2 and the porosity is 60%, for instance, a layer thickness of about 15 μm or more is required.
In consideration of this point, the thickness of the ink-receiving layer is preferably from 10 to 50 μm, and more preferably from 20 to 40 μm.
Further, the thickness of the colloidal silica layer, which is included in the ink-receiving layer in some cases, is preferably from 0.05 to 5 μm, and more preferably from 0.1 to 3 μm, in view of ink absorbance and glossiness.
In addition, the diameter of the pores in the ink-receiving layer is preferably from 0.005 to 0.030 μm, and more preferably from 0.01 to 0.025 μm, in terms of median diameter.
The porosity and the median diameter of pores can be measured with a mercury porosimeter (trade name: PORESIZER 9320-PC2; a product of Shimadzu Corporation).
Moreover, it is preferable that the ink-receiving layer has excellent transparency. As an index of transparency, the haze value measured when the ink-receiving layer is formed on a transparent film substrate is adopted, and is preferably 30% or less, and more preferably 20% or less.
The haze value can be measured with a haze meter (trade name: HGM-2DP; a product of SUGA TEST INSTRUMENTS).
The organic nitrogen-containing cationic polymer and inorganic fine particles, which are essential components of the present ink-receiving layer, are described below, followed by descriptions of optional components including a water-soluble resin, a sulfur compound, a magnesium salt, colloidal silica, a crosslinking agent, a water-soluble polyvalent metal salt and other ingredients.
(Organic Nitrogen-Containing Cationic Polymer)
In view of inhibiting bleeding of recorded images and dispersing silica, the ink-receiving layer of the present invention contains at least one kind of organic nitrogen-containing cationic polymer as an essential component.
The organic nitrogen-containing cationic polymer usable in the invention is not particularly limited, but polymers having primary, secondary or tertiary amino groups, or polymers having quaternary ammonium salt groups, are favorably used.
The preferred organic nitrogen-containing cationic polymers include a homopolymer of a monomer having a primary, secondary or tertiary amino group, or a salt thereof, or a monomer having a quaternary ammonium salt group (an organic nitrogen-containing cationic monomer), and a copolymer or condensate of the organic nitrogen-containing cationic monomer and another monomer. In addition, these organic nitrogen-containing cationic polymers can be used in both the form of a water-soluble polymer and the form of water-dispersible latex particles.
Examples of the organic nitrogen-containing cationic monomer include trimethyl-p-vinylbenzylammonium chloride, trimethyl-m-vinylbenzylammonium chloride, triethyl-p-vinylbenzylammonium chloride, triethyl-m-vinylbenzylammonium chloride, N,N-dimethyl-N-ethyl-N-p-vinylbenzylammonium chloride, N,N-diethyl-N-methyl-N-p-vinylbenzylammonium chloride, N,N-dimethyl-N-n-propyl-N-p-vinylbenzylammonium chloride, N,N-dimethyl-N-n-octyl-N-p-vinylbenzylammonium chloride, N,N-dimethyl-N-benzyl-N-p-vinylbenzylammonium chloride, N,N-diethyl-N-benzyl-N-p-vinylbenzylammonium chloride, N,N-dimethyl-N-(4-methyl)benzyl-N-p-vinylbenzylammonium chloride, N,N-dimethyl-N-phenyl-N-p-vinylbenzylammonium chloride, trimethyl-p-vinylbenzylammonium bromide, trimethyl-m-vinylbenzylammonium bromide, trimethyl-p-vinylbenzylammonium sulfonate, trimethyl-m-vinylbenzylammonium sulfonate, trimethyl-p-vinylbenzylammonium acetate, trimethyl-m-vinylbenzylammonium acetate, N,N,N-triethyl-N-2-(4-vinylphenyl)ethylammonium chloride, N,N,N-triethyl-N-2-(3-vinylphenyl)ethylammonium chloride, N,N-diethyl-N-methyl-N-2-(4-vinylphenyl)ethylammonium chloride, N,N-diethyl-N-methyl-N-2-(4-vinylphenyl)ethylammonium acetate, quaternarized products prepared by reacting N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, N,N-diethylaminopropyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylamide, N,N-diethylaminoethyl (meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide or N,N-diethylaminopropyl (meth)acrylamide with methyl chloride, ethyl chloride, methyl bromide, ethyl bromide, methyl iodide or ethyl iodide, and sulfonates, alkylsulfonates, acetates or alkylcarboxylates obtained by anion substitution of these quaternarized products.
Examples of such products include monomethyldiallylammonium chloride, trimethyl-2-(methacryloyloxy)ethylammonium chloride, triethyl-2-(methacryloyloxy)ethylammonium chloride, trimethyl-2-(acryloyloxy)ethylammonium chloride, triethyl-2-(acryloyloxy)ethylammonium chloride, trimethyl-3-(methacryloyloxy)propylammonium chloride, triethyl-3-(methacryloyloxy)propylammonium chloride, trimethyl-2-(methacryloylamino)ethylammonium chloride, triethyl-2-(methacryloylamino)ethylammonium chloride, trimethyl-2-(acryloylamino)ethylammonium chloride, triethyl-2-(acryloylamino)ethylammonium chloride, trimethyl-3-(methacryloylamino)propylammonium chloride, triethyl-3-(methacryloylamino)propylammonium chloride, triethyl-3-(acryloylamino)propylammonium chloride, triethyl-3-(acryloylamino)propylammonium chloride, N,N-dimethyl-N-ethyl-2-(methacryloyloxy)ethylammonium chloride, N,N-diethyl-N-methyl-2-(methacryloyloxy)ethylammonium chloride, N,N-dimethyl-N-ethyl-3-(acryloylamino)propylammonium chloride, trimethyl-2-(methacryloyloxy)ethylammonium bromide, trimethyl-3-(acryloylamino)propylammonium bromide, trimethyl-2-(methacryloyloxy)ethylammonium sulfonate and trimethyl-3-(acryloylamino)propylammonium acetate. In addition to the monomers recited above, N-vinylimidazole and N-vinyl-2-methylimidazole can be used as monomers copolymerizable with these monomers. Moreover, it is possible to utilize polymers having vinylamine units converted from their original polymerizing units, such as N-vinylacetamide and N-vinylformamide, by hydrolysis after polymerization, and the polymers having salt-form units converted from these vinylamine units.
As other monomers copolymerizable (polycondensatable) with the organic nitrogen-containing cationic monomers as recited above, monomers having neither basic nor cationic moieties, such as primary, secondary and tertiary amino groups, their salts, or quaternary ammonium bases, and showing no or substantially weak interaction with dyes in inkjet ink can be used. Examples of such comonomers include alkyl esters of (meth)acrylic acid; cycloalkyl esters of (meth)acrylic acid, such as cyclohexyl (meth)acrylate; aryl esters of (meth)acrylic acid, such as phenyl (meth)acrylate; aralkyl esters, such as benzyl (meth)acrylate; aromatic vinyl compounds, such as styrene, vinyltoluene and α-methylstyrene; vinyl esters, such as vinyl acetate, vinyl propionate and vinyl versatates; allyl esters, such as allyl acetate; halogen-containing monomers, such as vinylidene chloride and vinyl chloride; vinyl cyanides, such as (meth)acrylonitrile; and olefins, such as ethylene and propylene.
The alkyl esters of (meth)acrylic acid are preferably those containing 1 to 18 carbon atoms in their respective alkyl moieties, with examples including methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate and stearyl (meth)acrylate. Of these (meth)acrylates, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate and hydroxyethyl methacrylate are preferred over the others. The monomers other than these acrylates and methacrylates can be used alone or in combination of two or more thereof.
Of the organic nitrogen-containing cationic polymers recited above, cationic polyurethanes and the cationic polymers disclosed in JP-A No. 2004-167784 are preferred over the others in view of bleeding control, and cationic polyurethanes are even more preferable.
Examples of commercially available products of cationic polyurethanes include SUPERFLEX 650, F-8564D and F-8570D (trade names; products of DAI-ICHI KOGYO SEIYAKU CO., LTD.), and NEOFIX IJ-150 (trade name; a product of NICCA CHEMICAL CO., LTD.).
In view of dispersibility of silica, poly(diallyldimethylammonium chloride) and derivatives of poly(methacryloyloxyethyl-β-hydroxyethyldimethylammonium chloride) are preferable, and poly(diallyldimethylammonium chloride) is preferable even more. One example of a commercially available product of such polymers is CHEMISTAT 7005 (trade name; a product of Sanyo Chemical Industries, Ltd.).
In addition, it is also preferable that the organic nitrogen-containing cationic polymer used in the invention is a polymer prepared from a cationic emulsion in a first solution A described hereafter.
(Inorganic Fine Particles)
The ink-receiving layer in the present invention contains at least one kind of inorganic fine particle as an essential component.
The inorganic fine particles have a function of enhancing ink absorbency by creating a porous structure when the ink-receiving layer is formed.
It is especially favorable when the solid content of the inorganic fine particles in the ink-receiving layer is 50% or more by mass, and preferably 60% or more by mass, because it becomes possible to create a better porous structure, and to contribute to formation of an inkjet recording medium with sufficient ink absorbency. Herein, the expression “solid content” of fine particles in the ink-receiving layer refers to the content calculated on the basis of all ingredients except water in the composition for the ink-receiving layer.
Examples of inorganic fine particles for use in the invention include silica fine particles, colloidal silica, titanium dioxide, barium sulfate, calcium silicate, zeolite, kolinite, hollysite, mica, talc, calcium carbonate, magnesium carbonate, calcium sulfate, pseudo-boehmite, zinc oxide, zinc hydroxide, alumina, aluminum silicate, magnesium silicate, zirconium oxide, zirconium hydroxide, cerium oxide, lanthanum oxide and yttrium oxide. Of these substances, silica fine particles, colloidal silica, alumina fine particles and pseudo-boehmite are preferred over the others from the viewpoint of creating good porous structure. These fine particles may be used as they are primary particles, or in a state that they are formed into secondary particles. The average primary particle diameter of these fine particles is preferably 2 μm or less, and more preferably 200 nm or less.
Moreover, silica fine particles having an average primary particle diameter of 30 nm or less, colloidal silica having an average primary particle diameter of 30 nm or less, alumina fine particles having an average primary particle diameter of 20 nm or less and pseudo-boehmite having an average pore radius of 2 to 15 nm are more preferable, and silica fine particles, alumina fine particles and pseudo-boehmite in particular are favorably used.
Silica fine particles are usually roughly classified into wet method particles and dry method (vapor phase process) particles in accordance with the method of manufacturing thereof. In the mainstream of the wet method, silica fine particles are mainly produced by generating an activated silica by acid decomposition of a silicate, appropriately polymerizing the activated silica, and aggregation precipitation of the resulting polymeric silica to obtain hydrated silica. On the other hand, in the mainstream of the gas phase process, silica (anhydrous silica) particles are produced by either a method having high-temperature gas-phase hydrolysis of a silicon halide (flame hydrolysis process), or a method having reductively heating and vaporizing quartz and coke in an electric furnace, applying an arc discharge and oxidizing the vaporized silica with air (arc method). The “vapor-phase process silica” means a silica (an anhydrous silica fine particle) produced by the gas phase process. Vapor-phase process silica fine particles are particularly preferable as the silica fine particles used in the invention.
While the above vapor-phase process silica differs from hydrated silica in terms of the density of silanol groups on its surfaces, the presence or not of voids therein, and the like, and different properties are exhibited from each other, vapor-phase process silica is suitable for forming three-dimensional structures which have a high porosity. While the reason for this is not clearly understood, it can be supposed as follows. Namely, hydrated silica fine particles have a high density of silanol groups on the surface, at 5 to 8 per nm2, thus the silica fine particles tend to coagulate (aggregate) densely. In contrast, vapor-phase-process silica particles have a lower density of silanol groups on the surface, at 2 to 3 per nm2, thus vapor-phase process silica seems to form less compact, loose coagulations (flocculations), consequently leading to structures with a higher porosity.
The vapor-phase process silica has a particularly large specific surface, high ink absorbency and retention, and a low refractive index. Therefore, the vapor-phase process silica has features such that it can impart transparency to the ink-receiving layer and ensure high color densities and good color forming capabilities as long as dispersion thereof is performed until it comes to have appropriate particle diameters. It is important for the ink-receiving layer to be transparent from the viewpoint of delivering high color densities and good formed-color gloss in not only transparency-required uses, such as OHP, but also applications to recording media, such as gloss photo paper.
An average primary particle diameter of the vapor-phase process silica particles is preferably 30 nm or less, more preferably 20 nm or less, particularly preferably 10 nm or less, and the most preferably in a range of 3 to 10 nm. Since the vapor-phase process silica particles easily adhere to each other by hydrogen bonds due to the silanol groups, a structure having a high porosity can be formed thereby when the average primary particle size is 30 nm or less, whereby the ink absorption characteristic can be effectively improved.
The silica fine particles may be used in combination with other fine particles described above. When the other fine particles are used in combination with the vapor-phase silica, the amount of the vapor-phase silica relative to the total amount of fine particles is preferably 30% or more by mass, and more preferably 50% or more by mass.
Preferable examples of inorganic fine particles which can be additionally used in the invention include alumina fine particles, alumina hydrate, and mixtures or complexes thereof. Among them, alumina hydrate is further preferable, as it absorbs and holds inks well. Pseudo-boemite (Al2O3.nH2O) is particularly preferable. Alumina hydrate may be used in a variety of forms. Alumina hydrate is preferably prepared by using boehmite in the sol state as the starting material, as it easily provides smoother layers.
An average pore radius of pseudo-boemite is preferably in a range of 1 to 30 μm and more preferably in a range of 2 to 15 nm. The pore volume thereof is preferably in a range of 0.3 to 2.0 mg/g, and more preferably in a range of 0.5 to 1.5 mg/g. The average pore radius and the pore volume are determined by the nitrogen absorption-desorption method. These values may be determined, for example, by using a gas absorption-desorption analyzer (e.g., trade name: OMNISORP 369, manufactured by Beckman Coulter, Inc.).
Of the alumina fine particles, the vapor-phase process alumina fine particles are preferred because of large specific surface. The average primary particle diameter of the vapor-phase process alumina is preferably 30 nm or less, and more preferably 20 nm or less.
In application of the fine particles as recited above to an inkjet recording medium, each of the embodiments disclosed in JP-A Nos. 10-81064, 10-119423, 10-157277, 10-217601 and 11-348409, JP-A Nos. 2001-138621, 2000-43401, 2000-211235, 2000-309157, 2001-96897 and 2001-138627, JP-A Nos. 11-91242, 8-2087, 8-2090, 8-2091, 8-2093, 8-174992 and 11-192777, and JP-A No. 2001-301314 can be utilized as one embodiment of the present invention.
(Water-Soluble Resin)
The ink-receiving layer in the invention preferably contains at least one kind of water-soluble resin.
Examples of the water-soluble resin include resins having hydroxyl groups as hydrophilic structural units, such as polyvinyl alcohol resins (e.g., polyvinyl alcohol (PVA), acetoacetyl-modified polyvinyl alcohol, cation-modified polyvinyl alcohol, anion-modified polyvinyl alcohol, silanol-modified polyvinyl alcohol, polyvinyl acetal), cellulose resins (e.g., methyl cellulose (MC), ethyl cellulose (EC), hydroxyethyl cellulose (HEC), carboxymethyl cellulose (CMC), hydroxypropyl cellulose (HPC), hydroxyethylmethyl cellulose, hydroxypropylmethyl cellulose), chitins, chitosans and starch; resins having ether links (e.g., polyethylene oxide (PEO), polypropylene oxide (PPO), polyethylene glycol (PEG), polyvinyl ether (PVE)); and resins having carbamoyl groups (e.g., polyacrylamide (PAAM), polyvinyl pyrrolidone (PVP), polyacrylic acid hydrazide).
In addition, the water-soluble resins may be resins having carboxyl groups as dissociative groups, with examples including polyacrylic acid salts, maleic acid resins, alginates and gelatins.
Of these resins, at least one kind of resin selected from polyvinyl alcohol resins, cellulose resins, resin having ether links, resin having carbamoyl groups, resins having carboxyl groups or gelatins, notably polyvinyl alcohol (PVA) resins, is preferred as the water-soluble resin used in the invention.
Examples of the polyvinyl alcohol resins include the substances disclosed in JP-B Nos. 4-52786, 5-67432 and 7-29479, Japanese Patent No. 2537827, JP-B No. 7-57553, Japanese Patent Nos. 2502998 and 3053231, JP-A No. 63-176173, Japanese Patent No. 2604367, JP-A Nos. 7-276787, 9-207425, 11-58941, 2000-135858, 2001-205924, 2001-287444, 62-278080 and 9-39373, Japanese Patent No. 2750433, JP-A Nos. 2000-158801, 2001-213045, 2001-328345, 8-324105, 11-348417, 58-181687, 10-259213, 2001-72711, 2002-103805, 2000-63427, 2002-308928, 2001-205919 and 2002-264489.
In addition, examples of water-soluble resins other than the polyvinyl alcohol resins include the compounds disclosed in JP-A No. 11-165461, paragraphs [0011] and [0012], and the compounds disclosed in JP-A Nos. 2001-205919 and 2002-264489.
These water-soluble resins may be used singly or in combinations of two or more thereof. The water-soluble resin content in the invention is preferably from 9% to 40% by mass, and more preferably from 12% to 33% by mass, with respect to the total solid content in the ink-receiving layer.
In the invention, each of main components of the ink-receiving layer, namely, the water-soluble resin and the inorganic fine particles, may be a single material, or a mixture of multiple materials may be used for each main component.
Additionally, the kind of water-soluble resin used in combination with the inorganic fine particles, and silica fine particles in particular, is important from the viewpoint of transparency retention. When the vapor-phase process silica is used, the water-soluble resin used in combination is preferably a polyvinyl alcohol resin, more preferably a polyvinyl alcohol resin having a saponification degree of 70 to 100%, and particularly preferably a polyvinyl alcohol resin having a saponification degree of 80 to 99.5%.
The polyvinyl alcohol resins have hydroxyl groups in their respective structural units, and hydrogen bonds are formed between these hydroxyl groups and silanol groups present on the surfaces of silica fine particles; as a result, it becomes easy to form a three-dimensional network structure having secondary particles of silica fine particles as network chain units. It is thought that formation of such a three-dimensional network structure allows the ink-receiving layer formed to have a porous structure of a high porosity and sufficient strength.
When inkjet recording is performed, the porous ink-receiving layer formed in the foregoing manner can quickly absorb ink through capillary action and form dots of high circularity without generating ink bleeding.
The polyvinyl alcohol resin may be used in combination with other water-soluble resins. When another water-soluble resin is used in combination with the polyvinyl alcohol resin, the content of the polyvinyl alcohol resin is preferably 50% by mass or more, and more preferably 70% by mass or more relative to the total mass of water-soluble resins used in the ink-receiving layer.
Ratio of Inorganic Fine Particle Content to Water-Soluble Resin Content:
By optimization of the ratio of the inorganic fine particle content (x) by mass to the water-soluble resin content (y) by mass [PB ratio (x/y)], the film structure and film strength of the ink-receiving layer can further be enhanced.
In the invention, the ratio of mass content [PB ratio (x/y)] of the ink-receiving layer is preferably in a range of 1.5 to 10 from the viewpoints of preventing a decrease in film strength and the appearance of cracks under drying, which are caused by excessively high PB ratios, and avoiding a reduction in ink absorbability by a porosity decrease resulting from a tendency to pores being clogged by the resins, which develops when PB ratios are excessively low.
Herein, it is especially preferred that the x/y ratio in the upper-side half of the ink-receiving layer is equal to or higher than the x/y ratio in the lower-side half of the ink-receiving layer (in other words, the upper-side half and the lower-side half have the same PB ratio, or the lower-side half is rich in binder), and a case in which the PB ratios in the upper-side half and the lower-side half are the same is preferable.
At the time of passage through the feeding system of an inkjet printer, the recording medium is subjected to stress in some cases, so the ink-receiving layer is required to have sufficient film strength. In addition, from the standpoint of avoiding the occurrence of cracking and exfoliation in the ink-receiving layer when the recording medium is cut into sheets, sufficient film strength is necessary for the ink-receiving layer. In view of these cases, the mass ratio (x/y) is preferably 5 or less, while it is preferably 2 or more from the viewpoint of ensuring quick ink absorption in inkjet printer.
For example, when a coating liquid prepared by completely dispersing vapor-phase process silica fine particles having an average primary particle diameter of 20 nm or less and a water-soluble resin at a mass ratio (x/y) of 2 to 5 is applied onto a support and dried, a three-dimensional network is formed having secondary particles of the silica fine particles as network chains, whereby a translucent porous film having an average pore diameter of 30 nm or less, 50 to 80% porosity, 0.5 ml/g or more specific pore volume, and 100 m2/g or more specific surface area can be easily formed.
(Sulfur Compound)
From the viewpoint of further enhancing ozone resistance, it is preferable that the ink-receiving layer in the invention contains at least one kind of sulfur compound.
The sulfur compound contained is preferably at least one kind of sulfur compound selected from thioether compounds, thiourea compounds, disulfide compounds, sulfinic acid compounds, thiocyanic acid compounds, sulfur-containing heterocyclic compounds, or sulfoxide compounds.
Thioether Compound:
The thioether compound used for the foregoing purpose may be a water-soluble compound or an oil-soluble compound. In addition, the thioether compound may be low or high in molecular weight, but it is required to have at least one thioether group per molecule.
The number of carbon atoms in the thioether compound used is preferably 2 or more, and more preferably 4 or more.
In addition to sulfur, carbon and hydrogen atoms, it is preferable that the thioether compound used further contains an atom having lone-pair electrons (such as an oxygen, sulfur, nitrogen or phosphorus atom).
Examples of such a thioether compound include compounds represented by the following formula (1).

R1—(S—R3)m—S—R2  (1)

In formula (1), R1 and R2 each represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or an alkyl- or aryl-containing group independently. Alternatively, R1 and R2 may be the same or different, and may combine with each other to form a ring. However, at least either R1 or R2 is required to be an alkyl group substituted with an hydrophilic group, such as a hydroxyl group, a sulfo group, a carboxyl group or a (poly)ethylene oxide group, or a basic nitrogen-containing group, such as an amino group, an amido group, an ammonium group, a nitrogen-containing heterocyclic group, an aminocarbonyl group or an aminosulfonyl group, or a group containing such a substituted alkyl group (for example, this substituted alkyl group may further be bound to the thioether sulfur via a divalent linkage group, such as a carbamoyl group, a carbonyl group or a carbonyloxy group). R3 represents an alkylene group which may be substituted and which, in some cases, may have an oxygen atom. m represents an integer of 0 to 10. When m is 1 or more, at least one sulfur atom bound to R3 may be a sulfoxide group or a sulfonyl group. In addition, R1 and R2 each may be a polymer residue.
Of the compounds represented by formula (1), the compounds each containing as at least either R1 or R2 an alkyl group substituted with a hydroxyl group, a carboxyl group, an amino group or an ammonium group are especially preferred over the others. Examples of the amino group with which the alkyl group is substituted include an amino group, an monoalkylamino group (the alkyl moiety of which is preferably an alkyl group having 1 to 5 carbon atoms) and a dialkylamino group (each alkyl moiety of which is preferably an alkyl group having 1 to 5 carbon atoms), and may further include a nitrogen-containing heterocyclic group. Examples of compounds represented by formula (1) are illustrated below, but the present invention is not limited thereto.










Thiourea Compound:

The thiourea compound used may be a water-soluble compound or an oil-soluble compound. In addition, the compound may be low or high in molecular weight, but it is required of the compound to have at least one structural unit represented by >N—C(═S)—N<per molecule.
Examples of such a thiourea compound include thiourea, N-methylthiourea, N-acetylthiourea, 1,3-diphenylthiourea, tetramethylthiourea, guanylthiourea, 4-methylthiosemicarbazide, 1,3-bis(hydroxymethyl)-2(3H)-benzimidazolethione, 6-hydroxy-1-phenyl-3,4-dihydropyrimidine-2(1H)-thione, 1-allyl-2-thiourea, 1,3-dimethyl-2-thiourea, 1,3-diethyl-2-thiourea, ethylenethiourea, trimethylthiourea, 1-carboxymethyl-2-thiohydantoin, and thiosemicarbazide.
Disulfide Compound:
The disulfide compound used may be a water-soluble compound or an oil-soluble compound. In addition, the compound may be low or high in molecular weight. The compounds represented by the following formula, for example, are preferred. Of these compounds, DL-α-lipoic acid, 4,4′-dithiodimorpholine and 4,4′-dithiodibutanoic acid are especially preferable.

R1—S—S—R2 

In the above formula, R1 and R2 each represent an organic group containing the carbon or nitrogen atom bound to the disulfide sulfur. This organic group may be a group forming a substituted or unsubstituted aliphatic group, a substituted or unsubstituted aromatic group, or a substituted or unsubstituted heterocyclic group in conjunction with the carbon or nitrogen atom bound to the disulfide sulfur, or an organic group which has on the carbon or nitrogen atom bound to the disulfide sulfur a substituted or unsubstituted aliphatic, aromatic, heterocyclic or amino group and an imino group, an oxygen atom, a sulfur atom or so on. Alternatively, R1 and R2 may be the same or different, and may combine with each other to form a ring. Examples of a substituent the group represented by R1 and R2 each may have include an alkyl group, an aryl group, a heterocyclic group, an amino group, an amido group, an imino group, an ammonium group, a hydroxyl group, a sulfo group, a carboxyl group, an aminocarbonyl group, an aminosulfonyl group and a halogen atom.
Sulfinic Acid Compound:
The sulfinic acid compound used may be a water-soluble compound or an oil-soluble compound. In addition, the compound may be low or high in molecular weight, and it is essential only that the compound have at least one sulfinic acid skeleton per molecule.
The sulfinic acid compounds usable in the invention are preferably represented by the following formula.

R—SO2M

In the above formula, R represents a substituted or unsubstituted alkyl group (preferably having 6 to 30 carbon atoms), a substituted or unsubstituted aryl group (preferably having 6 to 30 carbon atoms, such as a phenyl group or a naphthyl group), or a polymer residue. M represents a hydrogen atom, an alkali metal atom or an ammonium.
Examples of a substituent which the group represented by R may have include a linear, branched or cyclic alkyl group (preferably having 1 to 20 carbon atoms), an aralkyl group (which is preferably a mono- or di-cyclic group having a 1-3C alkyl moiety), an alkoxy group (preferably having 1 to 20 carbon atoms), a mono- or di-substituted amino group (a substituent or each substituent of which is preferably a 1-20C alkyl, acyl, alkylsulfonyl or arylsulfonyl group, provided that the total number of carbon atoms in the two substituents is 20 or less), a mono- to tri-substituted or unsubstituted ureido group (preferably having 1 to 20 carbon atoms), a substituted or unsubstituted aryl group (which is preferably a 6-29C mono- or di-cyclic aryl group), a substituted or unsubstituted arylthio group (preferably having 6 to 29 carbon atoms), a substituted or unsubstituted alkylthio group (preferably having 1 to 29 carbon atoms), a substituted or unsubstituted alkylsulfoxy group (preferably having 1 to 29 carbon atoms), a substituted or unsubstituted arylsulfoxy group (preferably having a 6-29C mono- or di-cyclic aryl moiety), a substituted or unsubstituted alkylsulfonyl group (preferably having 1 to 29 carbon atoms), a substituted or unsubstituted arylsulfonyl group (preferably having a 6-29C mono- or di-cyclic aryl moiety), an aryloxy group (preferably having a 6-29C mono- or di-cyclic aryl moiety), a carbamoyl group (preferably having 1 to 29 carbon atoms), a sulfamoyl group (preferably having 1 to 29 carbon atoms), a hydroxyl group, a halogen atom (fluorine, chlorine, bromine or iodine), a sulfonic acid group and a carboxylic acid group.
Each of those substituents may further have another substituent, such as an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, a carbonamide group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, an alkylsulfoxy group, an arylsulfoxy group, an ester group, a hydroxyl group, a carboxyl group, a sulfo group or a halogen atom. Some of these groups may combine with each other to form a ring, or may form a part of homopolymer or copolymer chain.
Examples of such a sulfinic acid compound are illustrated below.




Thiocyanic Acid Compound:

Examples of a thiocyanic acid compound include methyl thiocyanate, ethyl thiocyanate, sodium thiocyanate, potassium thiocyanate and calcium thiocyanate.
Sulfur-Containing Heterocyclic Compound:
Examples of a sulfur-containing heterocyclic compound include a compound containing a sulfur atom as a constituent atom of a heterocycle, a heterocycle-substituted mercapto compound, and a heterocycle-substituted mercapto compound the mercapto hydrogen of which is substituted with an alkyl group, an aryl group, an acyl group or a sulfonyl group. Of these compounds, the compounds represented by the following formula are preferred over the others.




In the above formula, X represents a group of nonmetal atoms necessary to form a 5- to 7-membered ring. This group of nonmetal atoms may have a substituent. Examples of such a substituent include an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a hydroxyl group, an amino group, a mercapto group, a carboxyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a halogen atom, and a cyano group. These substituents may further have substituents.
M represents a hydrogen atom, an ammonium ion, or a metal atom. In addition, the group having a 5- to 7-membered ring formed in a state of containing X and another constituent may be fused together to form a condensed ring.
Examples of such heterocycle-substituted mercapto compounds include Compounds (1-1 to 1-32) disclosed in JP-A No. 2000-94829, paragraphs [0027] to [0032].
Sulfoxide Compound:
The sulfoxide compound used may be a water-soluble compound or an oil-soluble compound. In addition, the compound may be low or high in molecular weight, and it is essential only that the compound have at least one sulfoxide group per molecule.
The number of carbon atoms in the sulfoxide compound used is preferably 2 or more, more preferably 4 or more.
In addition to a sulfoxide group, carbon atoms and hydrogen atoms, it is preferable that the sulfoxide compound used further contains an atom having lone-pair electrons (such as an oxygen, sulfur, nitrogen or phosphorus atom).
Examples of such sulfoxide compounds are illustrated below.
















Examples of sulfur-containing compounds usable in the invention further include sulfone compounds, sulfonamide compounds, thioester compounds, thioamide compounds, sulfonic acid compounds, thiosulfonic acid compounds, thiosulfinic acid compounds, sulfamine compounds, thiocarbaminic acid compounds and sulfurous acid compounds.
The sulfur compound used in the invention may be a polymer.
Examples of a method for synthesizing sulfur-containing polymers usable in the invention include synthesis methods utilizing polycondensation, addition polymerization, polyaddition, addition condensation, ring-opening polymerization or polymer reaction. The polymers preferably used in the invention are polymers synthesized by addition reaction. Herein, the term “addition reaction” is intended to include nucleophilic addition to carbon-carbon double bond compounds (e.g., Michael addition), nucleophilic addition to cumulative double-bond compounds (e.g., isocyanate), ring-opening addition reaction and radical addition reaction.
Examples of a polyadduct include polyurethane [a polyadduct of an organic isocyanate compound having a divalent or higher isocyanate group (such as 2,4-tolylenediisocyanaate, 2,6-tolylenediisocyanate, m-phenylenediisocyanate, 4,4′-diphenylmethanediisocyanate, hexamethylenediisocyanate, octamethylenediisocyanate, 1,4-cyclohexylenediisocyanate, isophoronediisocyanate, 1,3-bis(isocyanatemethyl)cyclohexane, 1,5-diisocyanate-2-methylpentane, hydrogenated xylylenediisocyanate or hydrogenated 4,4′-diphenylmethanediisocyanate) and a polyol having any of an alkylthio group, an arylthio group, a thiocarbonyl group and a thiocyanate group (such as 2,2′-thiodiethanol, 3,6-dithia-1,8-octanediol, 1,4-diathine-2,5-diol, 3,3′-thiodipropanol, 3-methylthio-1,2-propanediol or 1,5,9,13-tetrathiacyclohexadecane-3,11-diol)]; polythiourethane [e.g., a polyadduct of an organic isothiocyanate compound having a divalent or higher isothiocyanate group (such as p-phenylene diisothiocyanate, 4,4′-methylenediphenyl isothiocyanate, isophthaloyl diisothiocyanate, hexamethylene diisothiocyanate or octamethylene diisothiocyanate) and a polyol (such as ethylene glycol, 1,3-propanediol, 1,2-propanediol, 2-methyl-1,3-priopanediol, neopentyl glycol, 2,2-diethyl-1,3-propanediol, 1,4-butanediol, 1,2-butanediol or 1,6-hexanediol)]; polythiourea [e.g., a polyadduct of any of the organic isothiocyanate compounds recited above and an polyamine having an active hydrogen (e.g., ethylenediamine, 1,3-diaminopropane, 1,2-diaminopropane, 1,4-diaminobutane, hexamethylenediamine or 2,2-dimethyl-1,3-propanediamine)];
polysulfide [e.g., a ring-opening polymer of a cyclic sulfide (such as ethylene sulfide, propylene sulfide, trimethylene sulfide or 3-methoxythioethane)]; polyamide sulfide [e.g., a Michael adduct of methylenebisacrylamide and a dithiol (such as 1,2-ethanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 2,3-butanedithiol, 1,6-hexanedithiol, 1,8-octanedithiol, 2,3-dimercapto-1-propanol, dithiothreitol, dithoerythritol, or 2-mercaptoethyl ether)]; polyether sulfide [e.g., a ring-opening polyadduct of a bisepoxy compound (such as ethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, polyethylene glycol, diglycidyl ether, 1,2,5,6-diepoxycyclooctane or 4-vinyl-1-cyclohexene diepoxide) and any of the dithiol compounds recited above]; and polysulfone sulfide [e.g., a polyadduct of divinylsulfone and any of the dithiol compounds recited above].
Examples of a addition polymer include homo- and co-polymers of vinyl monomers having any of alkylthio, arylthio, thiocarbonyl and thiocyanate groups (such as 2-methylthioethyl (meth)acrylate, 2-ethylthioethyl (meth)acrylate, 2-(hydroxyethylthio)ethyl (meth)acrylate, 4-vinylbenzylmethyl sulfide, 4-vinylbenzylthioacetate, 2-thiocyanatoethyl vinyl ether and vinyl thiocyanatoacetate). In addition, addition polymers can also be prepared by subjecting conjugated vinyl monomers to telomerization using as a chain transfer agent a mercapto compound (such as 2-mercaptoethanol, ethanethiol, methylthioglycolate, thioglycerol, 2-aminoethanethiol, mercaptoacetic acid, 1,2-ethanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 2,3-butanedithiol, 1,6-hexanedithiol, 1,8-octanedithiol, 2,3-dimercapto-1-propanol, dithiothreitol, dithioerythritol, 2-mercaptoethyl ether, trimethylolpropane tris(2-mercaptoacetate), or pentaerythritol tetrakis(2-mercaptoacetate)).
Furthermore, polymers usable in the invention can be synthesized by polymer reaction. Examples of polymers synthesized by polymer reaction include radical adducts of polymers having unsaturated double bonds (e.g., polybutadiene, polyisoprene) and mercapto compounds (e.g., 2-mercaptoethanol, thioglycerol, mercaptoacetic acid, mercaptopropionic acid, 2-aminoethanethiol, 2-dimethylaminoethanethiol hydrochloride, 2-diethylaminoethanethiol hydrochloride, 3-mercaptopropanesulfonic acid), and adducts of polyamines (e.g., polyallylamine, polyvinylamine, polyethyleneimine) and isothiocyanate compounds (e.g., methyl isothiocyanate, ethyl isothiocyanate, butyl isothiocyanate, allyl isothiocyanate, cyclohexyl isothiocyanate, ethoxycrbonyl isothiocyanate).
As the polymers for use in the invention, polymers having alkylthio groups are preferred, and polymers having hydrophilic groups (such as hydroxyl, carboxyl, sulfo, carbamoyl, sulfamoyl, amino, ammonio, or amidino groups) in addition to alkylthio groups are especially preferred.
As to the polymers for use in the invention, polyurethane resins having alkylthio groups are far preferred, and cationic polyurethane resins prepared by using as comonomers tertiary amine compounds having monovalent or higher hydroxyl groups at the time of polyurethane synthesis and treating the copolymerization products with quaternarization agents. Examples of such tertiary amines include N,N-dimethylethanolamine, N,N-diethylethanolamine, 3-dimethylamino-1-propanol, 1-dimethylamino-2-propanol, 2-dimethylamino-2-methyl-1-propanol, N-methyldiethanolamine, N-ethyldiethanolamine, N-butyldiethanolamine, triethanolamine, triisopropanolamine, 3-(dimethylamino)-1,2-propanediol, 2-{[2-(dimethylamino)ethyl]-methylamino}ethanol, 1,3-bis(dimethylamino)-2-propanol, and N,N,N′,N′-tetrakis(2-hydroxypropyl)-ethylenediamine. And examples of quaternarization agents usable therein include dimethyl sulfate, diethyl sulfate, methyl p-toluenesulfonate, ethyl p-toluenesulfonate, and halides (such as methyl chloride, methyl bromide, methyl iodide, benzyl chloride and benzyl bromide).
The weight-average molecular weight of those polymers usable in the invention is preferably from 1,000 to 1,000,000, and more preferably from 2,000 to 100,000. When the polymers have a weight-average molecular weight lower than 1,000, improvements in water resistance and with respect to bleeding over time cannot be obtained, while when the weight-average molecular weight is higher than 1,000,000, suitability for handling may become worse.
The preferred among those polymers usable in the invention are polymers having solubility in water or organic solvents miscible in water, or polymers stable in the form of aqueous emulsified dispersions. The expression “polymers having solubility in water” used in the invention refers to high-molecular substances having water solubility of 0.1% or more by mass at an ambient temperature of 25° C., and the water solubility is preferably 0.5% or more by mass, particularly preferably 1% or more by mass.
On the other hand, the foregoing expression of “polymers stable in the form of aqueous emulsified dispersions” refers to high-molecular substances capable of being stably emulsified and dispersed in an aqueous dispersion medium in concentrations of 0.5% or higher by mass at an ambient temperature of 25° C., and the concentrations are preferably 1% or higher by mass, and particularly preferably 3% or higher by mass.
As the sulfur-containing polymers, polymers having partial structures represented by the following formula are used to advantage.

P—Y—S—

In the above formula, P represents a polymer or oligomer residue having a repeating unit. Y represents a single bond or a divalent linkage group. Suitable examples of such a divalent linkage group include ether linkage, ester linkage, thioester linkage, carbonate linkage, a carbamoyl group, an alkylene group (such as an ethylene group, an ethyne group, a propylene group, a trimethylene group, a tetramethylene group, a hexamethylene group or an octamethylene group), an arylene group (such as a phenylene group), or groups formed by combining any of those recited above.
Of these polymers, polymers having the following structural units are preferred over the others.




In the above formula, R represents a hydrogen atom or a methyl group. J represents a single bond or a divalent linkage group (e.g., —O—, —COO—, —OCO—, —CONR′—). R1 represents an aliphatic group or an aromatic group. Such an aliphatic group is preferably an alkyl group, with examples including a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-hexyl group, a cyclohexyl group, an n-octyl group, a 2-ethylhexyl group, a decyl group and a dodecyl group. These groups each may have a substituent (such as a hydroxyl group, a carboxyl group, a sulfo group, an alkyloxycarbonyl group, a carbamoyl group, a sulfamoyl group, a cyano group, an amino group, an ammonio group or an alkoxy group). Examples of such an aromatic group include an aryl group (such as a phenyl group or a naphthyl group), an aralkyl group (such as a benzyl group) and a pyridyl group. Of these groups, the groups preferred as R1 are 1-12C alkyl groups which may be substituted, with examples including a methyl group, an ethyl group, a hydroxyethyl group, a 2,3-dihydroxypropyl group, a 2-carboxyethyl group, a 3-carboxypropyl group, a 3-sulfoxypropyl group, a 2-aminoethyl group, an N,N-dimethylaminoethyl group and a trimethylammonioethyl group. R2 represents an alkylene group which may have a substituent (such as a methylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a hexamethylene group or an octamethylene group) or an arylene group (such as a phenylene group), preferably a 1-8C (substituted) alkylene group.
In addition, it is preferable that those polymers further have hydrophilic groups. Examples of such hydrophilic groups include a hydroxyl group, a carboxyl group, a sulfo group, a carbamoyl group, a sulfamoyl group, an amino group, an ammonio group, an amidino group. Of these groups, hydroxyl, ammonio, amino and carbamoyl groups are preferred over the others. Those polymers usable in the invention are polymers having solubility in water, or polymers stable in the form of aqueous emulsified dispersions. The expression “polymers having solubility in water” used in the invention refers to high-molecular substances having water solubility of 0.1% or more by mass at an ambient temperature of 25° C., and the water solubility is preferably 0.5% or more by mass, particularly preferably 1% or more by mass.
On the other hand, the foregoing expression of “polymers stable in the form of aqueous emulsified dispersions” refers to high-molecular substances capable of being stably emulsified and dispersed in an aqueous-based dispersion medium in concentrations of 0.5% or higher by mass at an ambient temperature of 25° C., and the concentrations are preferably 1% or higher by mass, and particularly preferably 3% or higher by mass.
The weight-average molecular weight of those polymers usable in the invention is preferably from 1,000 to 1,000,000, and more preferably from 1,000 to 100,000. When the polymers have weight-average molecular weight lower than 1,000, improvement in water resistance and with respect to bleeding over time cannot be obtained, while when the weight-average molecular weight is higher than 1,000,000, suitability for handling may become worse.
Examples of a synthesis method of those polymers usable in the invention include synthesis methods utilizing polycondensation, addition polymerization, polyaddition, addition condensation, ring-opening polymerization or polymer reaction. In the invention, it is preferable to use the polymers synthesized by addition reaction. For example, the polymers obtained by addition polymerization (e.g., radical polymerization of a vinyl monomer having thioether linkage, or polymerization of a vinyl monomer with the aid of a mercapto compound as a chain transfer agent) or polymer reaction (e.g., nucleophilic or radical addition reaction to polymer side chains having reactive groups) are preferably used in the invention.
Examples of those polymers suitably used in the invention are illustrated below.
















In view of application to a substrate, polymers soluble in water or organic solvents miscible with water are preferred as polymers for use in the invention. However, polymers taking forms of water-dispersed latexes can also be used in the invention. Therefore, the polymers have no particular restriction on their solubility.
Of the sulfur compounds recited above, the thioether compounds and the sulfoxide compounds are preferred over the others.
Herein, there is no particular restrictions as to a mode of incorporation of such a sulfur compound as recited above into the ink-receiving layer. From the viewpoint of keeping density of recorded images higher, however, it is preferable to adopt such a mode of incorporation that the ink-receiving layer has a higher content of sulfur compound in the lower-side half thereof than in the upper-side half thereof.
In other words, the content ratio as to the sulfur compound incorporated into the ink-receiving layer [content in the upper-side half of the ink-receiving layer/content in the lower-side half of the ink-receiving layer] is preferably lower than 1.0, more preferably from 0 to 0.6, particularly preferably 0 (which means a mode that no sulfur compound is present in the upper-side half of the ink-receiving layer).
In the invention, the presence distribution of sulfur compound in the ink-receiving layer can be ascertained by elemental analysis. Specifically, the ascertainment may be made by performing mapping analysis according to the SEM-EDX method and observing the images obtained. In this case, the presence position of the ink-receiving layer as a whole is ascertained first by mapping analysis of the main component (e.g., elemental Si) of the ink-receiving layer, and then the mapping analysis of elemental S is performed. By the mapping image thus obtained, which part of the ink-receiving layer, the upper-side half or the lower-side half, contains elemental S in greater quantity is judged.
From the viewpoints of further enhancing ozone resistance and keeping image densities higher, the sulfur compound content in the lower-side half of the ink-receiving layer is preferably from 1% to 20% by mass, more preferably from 3% to 15% by mass, particularly preferably from 4% to 10% by mass, based on the total solids in the lower-side half.
On the other hand, the sulfur compound content in the upper-side half of the ink-receiving layer in view of keeping the recorded-image densities higher is preferably from 0 to 5% by mass, more preferably from 0 to 3% by mass, particularly preferably 0% by mass (namely, a state of being free of sulfur compound in the upper-side half), based on the total solids in the upper-side half.
In addition, from the viewpoints of further enhancing ozone resistance and keeping image densities higher, the sulfur compound content in the whole ink-receiving layer into which the upper-side half and the lower-side half are united is preferably from 0.5% to 5% by mass, more preferably 1% to 4% by mass, particularly preferably from 1.5% to 3% by mass, based on the total solids in the whole ink-receiving layer.
(Magnesium Salt)
From the viewpoint of further enhancing ozone resistance, it is preferable that the ink-receiving layer in the invention further contains at least one kind of magnesium salt.
Examples of such a magnesium salt include magnesium acetate, magnesium oxalate, magnesium sulfate, magnesium chloride hexahydrate, and magnesium citrate nanohydrate. Of these salts, magnesium chloride hexahydrate is preferred over the others.
Examples of a commercially available magnesium salt include WHITE NIGARI NS and ENKA MAG (TOKUGO) NS (trade names, products of Naikai Salt Industries Co., Ltd.).
From the viewpoint of more effectively achieving effects of the invention, the magnesium-salt content in the ink-receiving layer is preferably from 0.05% to 5% by mass, more preferably from 0.1% to 3% by mass, particularly preferably from 0.2% to 2% by mass.
(Colloidal Silica)
When the ink-receiving layer in the invention has a colloidal silica layer as the uppermost layer, the average primary particle diameter of colloidal silica used is preferably from 10 nm to 200 nm, more preferably from 50 nm to 150 nm.
The colloidal silica preferably used in the invention is either anionic or nonionic. And anionic colloidal silica in particular is preferable. The colloidal silica content is preferably from 0.01 g/m2 to 5 g/m2, particularly preferably from 0.05 g/m2 to 2 g/m2.
(Crosslinking Agent)
In point of crosslinking the water-soluble resin, it is preferable that the ink-receiving layer in the invention contains at least one kind of crosslinking agent.
Adoption of the ink-receiving layer in a mode of porous layer formed by using the foregoing combination of inorganic fine particles and water-soluble resin in particular and hardening the water-soluble resin by crosslinking reaction with a crosslinking agent is one embodiment of the invention.
For crosslinking of the water-soluble resins, notably polyvinyl alcohol, boron compounds are suitably used.
Examples of such boron compounds include borax, boric acid, borates (such as orthoborate, InBO3, ScBO3, YBO3, LaBO3, Mg3(BO3)2 and CO3(BO3)2), diborates (such as Mg2B2O5 and CO2B2O5), metaborates (such as LiBO2, Ca(BO2)2, NaBO2 and KBO2), tetraborates (such as Na2B4O7.10H2O), and pentaborates (such as KB5O8.4H2O, Ca2B6O11.7H2O and CsB5O5). Of these boron compounds, borax, boric acid and borates, especially boric acid, are used to advantage in point of quick induction of crosslinking reaction.
As crosslinking agents for the water-soluble resins, the following compounds other than the boron compounds can also be used.
For example, the compounds usable as the crosslinking agents include aldehyde compounds, such as formaldehyde, glyoxal and gurtaraldehyde; ketone compounds, such as diacetyl and cyclopentanedione; active halogen compounds, such as bis(2-chloroethylurea)-2-hydroxy-4,6-dichloro-1,3,5-triazine and sodium 2,4-dichloro-6-s-triazine); active vinyl compounds, such as divinylsulfonic acid, 1,3-vinylsulfonyl-2-propanol, N,N′-ethylenebis(vinylsulfonylacetamide) and 1,3,5-triacryloyl-hexahydro-s-triazine; N-methylol compounds, such as dimethylolurea and methyloldimethylhydantoin; melamine resins, such as methylolmelamine and alkylated methylolmelamine; epoxy resins;
isocyanate compounds, such as 1,6-hexamethylene diisocyanate; the aziridine compounds disclosed in U.S. Pat. Nos. 3,017,280 and 2,983,611; the carboxylmide compounds disclosed in U.S. Pat. No. 3,100,704; epoxy compounds, such as glycerol triglycidyl ether; ethyleneimino compounds, such as 1,6-hexamethylene-N,N′-bisethyleneurea; halogenated carboxyaldehyde compounds, such as mucochloric acid and mucophenoxychloric acid; dioxane compounds, such as 2,3-dihydroxydioxane; metal-containing compounds, such as titanium lactate, aluminum sulfate, chrome alum, potassium alum, zirconyl acetate and chromium acetate; polyamine compounds, such as tetraethylenepentamine; hydrazide compounds, such as adipic dihydrazide; and low-molecular and polymer compounds each having at least two oxazoline groups.
The crosslinking agents as recited above can be used alone or as combinations of any two or more thereof.
The amount of crosslinking agent(s) used is preferably from 1% to 50% by mass, more preferably from 5% to 40% by mass, based on the water-soluble resin.
(Water-Soluble Polyvalent Metal Salt)
In addition of the magnesium salt as recited above, the ink-receiving layer in the invention preferably contains at least one kind of water-soluble polyvalent metal compound as a mordant.
As water-soluble polyvalent metal compounds, trivalent or higher metal compounds are preferably used in the invention. Further, the polyvalent metal compounds may be water-soluble salts of metals chosen from calcium, barium, manganese, copper, cobalt, nickel, aluminum, iron, zinc, zirconium, chromium, tungsten or molybdenum.
Examples of such metal compounds include calcium acetate, calcium chloride, calcium formate, calcium sulfate, calcium butyrate, barium acetate, barium sulfate, barium phosphate, barium oxalate, barium naphtoresorcincarboxylate, barium butyrate, manganese chloride, manganese acetate, manganese formate dihydrate, ammonium manganese sulfate hexahydrate, cupric chloride, ammonium copper(II) chloride dihydrate, copper sulfate, copper(II) butyrate, copper oxalate, copper phthalate, copper citrate, copper gluconate, copper naphthenate, cobalt chloride, cobalt thiocyanate, cobalt sulfate, cobalt(II) acetate, cobalt naphthenate, nickel sulfate hexahydrate, nickel chloride hexahydrate, nickel acetate tetrahydrate, ammonium nickel sulfate hexahydrate, nickel amidosulfate tetrahydrate, nickel sulfaminate, nickel 2-hexylhexanoate, aluminum sulfate, aluminum sulfite, aluminum thiosulfate, polyaluninum chloride, aluminum nitrate nanohydrate, aluminum chloride hexahydrate, aluminum acetate, aluminum lactate, basic aluminum thioglycolate, ferrous bromide, ferrous chloride, ferric chloride, ferrous sulfate, ferric sulfate, iron(III) citrate, iron(III) lactate trihydrate, triammonium iron(III) trioxalate trihydrate, zinc bromide, zinc chloride, zinc nitrate hexahydrate, zinc sulfate, zinc acetate, zinc lactate, zirconium acetate, zirconium tetrachloride, zirconium chloride, zirconium oxychloride octahydrate, zirconium hydroxychloride, chromium acetate, chromium sulfate, sodium phosphotungstate, sodium tungsten citrate, phospho-12-tungstic acid n-hydrate, 12-silicotungstic acid hexacosahydrate, molybdenum chloride, phospho-12-molybdic acid n-hydrate, aluminum alum, basic polyaluminum hydroxide, zinc phenolsulfonate, ammonium zinc acetate, and ammonium zinc carbonate. These water-soluble polyvalent metal compounds may be used as combinations of any two or more thereof. The expression “water-soluble” in the term water-soluble polyvalent metal compound means that the polyvalent metal compound can be dissolved in 20° C. water in a concentration of 1% or more by mass.
Of those water-soluble polyvalent metal compounds, aluminum compounds or compounds containing the group IV A metals in the periodic table (e.g., zirconium, titanium) are preferred over the others, and aluminum compounds are far preferred. Water-soluble aluminum compounds in particular are preferable. Among water-soluble aluminum compounds, inorganic salts, such as aluminum chloride or hydrates thereof, aluminum sulfate or hydrates thereof, and aluminum alum, are known. In addition to these salts, basic polyaluminum hydroxide compounds as inorganic aluminum-containing cationic polymers (hereafter referred to as basic polyaluminum chloride or polyaluminum chloride too) are also known, and can be used to advantage.
The term “basic polyaluminum hydroxide compounds” described above refers to water-soluble polyaluminum hydroxides whose main components are represented by the following formula 1, 2 or 3, and stably containing basic polymeric polynuclear condensed ions, such as [Al6(OH)15]3+, [Al8(OH)20]4+, [Al13(OH)34]5+ and [Al21(OH)60]3+.

    Formula 1: [Al2(OH)nCl6-n]m 
    Formula 2: [Al(OH)3]nAlCl3 
    Formula 3: Aln(OH)mCl(3n-m), 0≦m≦3n


Such basic polyaluminum hydroxide compounds are available from TAKI CHEMICAL CO., LTD. as a water treatment chemical under the trade name of Polyaluminum Chloride (PAC), Asada Chemical Industry Co., Ltd. under the trade name of Polyaluminum Hydroxide (Paho), rikengreen Co., Ltd. under the trade name of HAP-25, TAIMEI Chemicals Co., Ltd. under the trade name of ALFINE 83, or other makers as products developed with intentions similar to the above, and they are easy to get various grades of products for.
As the water-soluble compounds containing elements of the group IV A in the periodic table, titanium- and zirconium-containing water-soluble compounds are preferred. Examples of a titanium-containing water-soluble compound include titanium chloride, titanium sulfate, titanium tetrachloride, tetraisopropyl titanate, titanium acetylacetonate, and titanium lactate. Examples of zirconium-containing water-soluble compound include zirconium acetate, zirconium chloride, zirconium hydroxychloride, zirconium nitrate, basic zirconium carbonate, zirconium hydroxide, zirconium lactate, ammonium zirconium carbonate, potassium zirconium carbonate, zirconium sulfate, and zirconium fluoride compounds.
The proportion of water-soluble polyvalent metal compounds added is preferably from 0.1 to 10% by mass, more preferably from 0.5 to 8% by mass, based on the inorganic fine particles.
(Other Ingredients)
In addition to the organic nitrogen-containing cationic polymers, the magnesium salts and the water-soluble polyvalent metal salts as recited above, the ink-receiving layer in the invention may contain a mordant, various kinds of surfactants and other ingredients.
As the other ingredients, those chosen appropriately from the ingredients disclosed in JP-A No. 2005-14593, paragraphs [0088] to [0117], and JP-A No. 2006-321176, paragraphs [0138] to [0155], can be used.
<Substrate>
As the substrate in the invention, both a transparent substrate made from a transparent material such as plastic and an opaque substrate made from an opaque material such as paper can be used. In order to capitalize on the transparency of the ink-receiving layer, it is preferable to use a transparent substrate or a high-gloss opaque substrate. Alternatively, the substrate used may be a read-only optical disc, such as CD-ROM or DVD-ROM, a write-once optical disc, such as CD-R or DVD-R, or a rewritable optical disc, and on the label side of such a disc the ink-receiving layer can be provided.
A transparent material resistant to radiant heat applied thereto when the medium is used on an OHP or back light display is preferable as the material for the transparent substrate. Examples of the material include polyesters such as polyethylene terephthalate (PET), polysulfone, polyphenylene oxide, polyimide, polycarbonate, polyamide and the like. Among them, polyesters are preferable, and polyethylene terephthalate is particularly preferable.
The thickness of the transparent substrate has no particular limits, but it is preferably from 50 to 200 μm in point of easy handling.
The high-gloss opaque substrate preferably has a glossiness of 40% or more on the surface where the ink-receiving layer is formed. The glossiness is a value determined by a known method taught by ISO 8254-1, i.e., Paper and board-Measurement of specular gloss-Part 1: 75 degree gloss with a converging beam. Specific examples of the substrates include the following:
Specific examples of the high-gloss opaque substrate include: high-gloss paper substrates such as art paper, coated paper, cast-coated paper, baryta paper commonly used as a silver salt photographic substrate and the like; high-gloss films opacified by adding a white pigment or the like to any one of plastic films such as polyesters such as polyethylene terephthalate (PET), nitrocellulose, cellulose acetate, cellulose esters such as cellulose acetate butylate, polysulfone, polyphenylene oxide, polyimide, polycarbonate, polyamide or the like (which may be additionally surface calendered); substrates having a polyolefin coating layer containing or not containing a white pigment formed on the surface of these various paper and transparent substrates or the high-gloss films containing a white pigment; or the like.
Foamed polyester films containing a white pigment (e.g., a foamed polyester formed by expanding a polyolefin microparticle-containing PET film so as to forming voids therein) are favorable and also included as examples. In addition, resin coated papers commonly used as photographic papers for silver salt photographs are also preferable.
While the thickness of the opaque substrate is not particularly limited, it is preferably in a range of 50 to 300 μm from the viewpoint of ease of handling.
The surface of substrate may be subjected to corona discharge treatment, glow discharge treatment, flame treatment, ultraviolet ray irradiation treatment or the like for improvement in wetting property and adhesiveness.
Then, base paper used in the resin-coated papers is described in detail.
The base paper is made from wood pulp as a principal material and, if needed, synthetic pulp made from, e.g., polypropylene, or synthetic fiber, such as nylon fiber or polyester fiber, as an additional material. As the wood pulp, any of LBKP, LBSP, NBKP, NBSP, LDP, NDP, LUKP and NUKP can be used. It is advantageous to use wood pulp with a high content of short fibers, such as LBKP, NBSP, LBSP, NDP and LDP.
However, the proportion of LBSP and/or LDP is preferably from 10% to 70% by mass.
Chemical pulps (such as sulfate salt pulp or sulfite pulp) containing a smaller amount of impurities are preferably used as the pulp used in the invention. Bleached pulps which are improved in whiteness are also useful.
Various additives including a sizing agent such as higher fatty acid or alkylketene dimer, a white pigment such as calcium carbonate, talc or titanium oxide, a paper-strength additive such as starch, polyacrylamide or polyvinyl alcohol, a fluorescent whitening agent, a moisturizing agent such as polyethylene glycols, a dispersing agent, a softener such as quaternary ammonium, and the like may be added to the base paper in accordance with necessity.
The freeness of the pulp for use in sheeting is preferably 200 to 500 ml as per CSF (Canadian Standard Freeness) regulations In regard to the fiber length after beating, the pulps remaining on 24- and 42-mesh screens is preferably 30 to 70% by mass, as determined by the known method taught by ISO 534, i.e., Paper and board-Determination of thickness and density. Further, the pulp remaining on 4-mesh screen is preferably 20% by mass or less.
The basis weight of base paper is preferably from 30 to 250 g/m2, particularly preferably from 50 to 200 g/m2. The thickness of base paper is preferably from 40 to 250 μm. It is also possible to impart high smoothness to base paper by performing calender treatment during a papermaking stage or after the papermaking has finished. The base paper density is generally from 0.7 to 1.2 g/m3 (JIS P-8118).
Furthermore, the stiffness of base paper is preferably from 20 to 200 g under conditions defined by JIS P-8143.
The base paper surface may be coated with a surface sizing agent, and the same sizing agent as added for internal sizing of base paper can also be used as the surface sizing agent.
The pH of base paper is preferably from 5 to 9 as measured according to the hydrothermal extraction method defined by JIS P-8113.
The polyethylene covering the front and rear surfaces of the base paper is mainly a low-density polyethylene (LDPE) and/or a high-density polyethylene (HDPE), but other LLDPE, polypropylene, or the like may also be used partially.
In particular, the polyethylene layer on which the ink-receiving layer is provided is preferably formed of polyethylenes containing rutile-titanium oxide, anatase-titanium oxide, a fluorescent whitening agent, and/or ultramarine that are improved in opacity, whiteness and hue, which are commonly used in photographic papers. The content of the titanium oxide is preferably in a range of about 3 to 20% and more preferably in a range of 4 to 13% by mass with respect to the polyethylene. The thickness of the polyethylene layer, either front or rear, is not particularly limited, but is favorably in a range of 10 to 50 μm. In addition, an undercoat layer may be formed on the polyethylene layer for increasing the adhesiveness thereof to an ink-receiving layer. Hydrophilic polyester, gelatin, and PVA are preferable for the undercoat layer. The thickness of the undercoat layer is preferably in a range of 0.01 to 5 μm.
The polyethylene-coated paper may be used as a glossy paper.
The polyethylene layer coated on the surface of the base paper by melt-extrusion may be further subjected to a surface modification treatment such as embossing so that it has a mat or silky surface similar to that of common photographic printing papers.
The substrate can be provided with a backcoating layer. To the backcoating layer, white pigment, aqueous binder and other ingredients can be added.
Examples of white pigment which can be incorporated into the backcoating layer include inorganic white pigments, such as precipitated calcium carbonate, ground calcium carbonate, kaolin, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulfide, zinc carbonate, satin white, aluminum silicate, diatomaceous earth, calcium silicate, magnesium silicate, synthetic amorphous silica, colloidal silica, colloidal alumina, pseudo-boehmite, aluminum hydroxide, alumina, lithopone, zeolite, hydrous halloysite, magnesium carbonate and magnesium hydroxide; and organic pigments, such as styrene-base plastic pigment, acrylic plastic pigment, polyethylene, microcapsules, urea resin and melamine resin.
Examples of the aqueous binders for use in the backcoat layer include water-soluble polymers such as styrene/maleic acid salt copolymers, styrene/acrylic salt copolymers, polyvinyl alcohol, silanol-modified polyvinyl alcohols, starch, cationic starch, casein, gelatin, carboxymethylcellulose, hydroxyethylcellulose, or polyvinylpyrrolidone; water-dispersible polymers such as styrene butadiene latexes or acryl emulsions; and the like.
The other components contained in the backcoat layer include defoaming agent, antifoaming agent, dye, fluorescent whitening agent, antiseptic, water-resistance imparting agent, and the like.
<Others>
In addition to the ink-receiving layer, the present inkjet recording medium may further have an ink-solvent absorption layer, an interlayer and a protective layer. Furthermore, a subbing layer may also be provided on the substrate for the purposes of enhancing adhesion between the substrate and the ink-receiving layer and adjusting the electric resistance as appropriate.
To constituent layers (e.g., the ink-receiving layer and the backcoating layer) of the present inkjet recording medium, a polymer fine-particle dispersion may be added. This polymer fine-particle dispersion is used for the purpose of improving film properties, such as film's dimensional stability and anti-curling, anti-sticking and anti-cracking properties. Descriptions of the polymer fine-particle dispersion can be found, e.g., in JP-A Nos. 62-245258 and 10-228076 each. Additionally, when a dispersion of polymer fine particles with a low glass transition temperature (40° C. or below) is added to a layer containing a mordant as recited above, the layer can escape being cracked and curled. Alternatively, curling can be prevented also by adding a dispersion of polymer fine particles with a high glass transition temperature to the backing layer.
Additionally, the ink-receiving layer, though may be provided on only one side of the substrate, may also be provided on both sides of the substrate with the intention of preventing deformation, such as curling. When the ink-receiving layer is on only one side of the substrate in preparing a recording medium for use in OHP or the like, an antireflection coating can also be provided on the opposite side or both sides of the substrate for the purpose of heightening optical transparency.
Further, it is also possible to apply boric acid or a boron compound to the substrate surface on the side where the ink-receiving layer is to be provided and then form thereon the ink-receiving layer, which can ensure glossiness and surface smoothness for the ink-receiving layer and allows inhibition of printed-image bleeding with age in high-temperature and high-humidity environments.
<<Method of Manufacturing Inkjet Recording Medium>>
A first aspect of a method of manufacturing the present inkjet recording medium is an aspect that the method includes a process of forming a coating layer by applying a first solution A containing at least inorganic fine particle and cationic emulsion and a first solution B differing from the first solution A in composition in order of increasing distance from the substrate, and a process of performing cross-link hardening of the coating layer by applying a second solution containing a basic compound at either (1) the same time as at least the first solution A and the first solution B are applied or (2) a stage in the course of drying of the coating layer formed by applying at least the first solution A and the first solution B, and that before the coating layer shows decreasing-rate drying, whereby forming an ink-receiving layer that includes the coating layer having undergone cross-link hardening and contains an organic nitrogen-containing cationic polymer in a greater quantity in half at a side nearer to the substrate than in half on the far-substrate side when the ink-receiving layer is divided into two equal parts by a plane parallel to the substrate.
And a second aspect of a method of manufacturing the present inkjet recording medium is an aspect that the method includes a process of forming a coating layer on a substrate by applying to the substrate at least a first solution A containing inorganic fine particles and a cationic emulsion and a first solution B differing from the first solution A in composition in order of increasing distance from the substrate, a process of cooling the coating layer to a temperature at least 5° C. lower than lower one of temperatures at which the first solution A and the first solution B are applied, respectively, and a process of forming an ink-receiving layer by drying the coating layer cooled, whereby forming an ink-receiving layer that contains an organic nitrogen-containing cationic polymer in a greater quantity in half at a side nearer to the substrate than in half at a side further from the substrate when the ink-receiving layer is divided into two equal parts by a plane parallel to the substrate.
By configuring a method of manufacturing the present inkjet recording medium to have the first aspect or the second aspect, the ink-receiving layer can be formed so as to contain the organic nitrogen-containing cationic polymer in a greater quantity in its lower half than in its upper half. As a result, it becomes possible to manufacture the inkjet recording medium which can keep high image density while inhibiting the images recorded thereon from bleeding (bleeding with age) and also has high resistance to ozone.
In each of the first and second aspects, though the ink-receiving layer is formed by multilayer coating of plural coating solutions, the ink-receiving layer formed may have a multilayer structure which allows recognition of interfaces between the plural coating solutions, or a single-layer structure in which neither of interfaces between the plural coating solutions can be recognized.
<Process of Forming Coating Layer>
Each of the first and second aspects has a process of forming a coating layer by applying a first solution A containing at least inorganic fine particles and a cationic emulsion and a first solution B differing from the first solution A in composition in order of increasing distance from the substrate (Hereinafter, this process is also referred to as the coating-layer formation process.)
In the coating-layer formation process, though it is required to apply to the substrate a plurality of solutions including at least the first solution A and the first solution B in the order of mention, a first solution C and other solutions may further be applied to the first solution B, if needed. In addition, a solution for barrier layer (interlayer solution) may be laid between any adjacent two of the solutions applied.
The first solutions A and B (and besides, the first solution C and others as required) have no particular restriction as to the mode of their applications. In other words, those solutions may be formed into a coating layer in accordance with a simultaneous multilayer coating method hitherto known, or they may be formed into a coating layer on a one-by-one basis (by sequential application) in accordance with a heretofore-known method.
The simultaneous multilayer coating can be performed with known coating apparatus, such as an extrusion die coater and a curtain flow coater.
And the sequential coating can be performed with known coating apparatus, such as an extrusion die coater, an air doctor coater, a blade coater, a rod coater, a knife coater, a squeegee coater, a reverse roll coater and a bar coater.
Herein, the suitable quantity of each coating solution applied is described.
The application quantity of the first solution A on a wet basis is preferably from 50 to 200 ml/m2, more preferably from 75 to 150 ml/m2, while the application quantity of the first solution A on a solids basis is preferably from 5 to 25 g/m2, more preferably from 10 to 18 g/m2.
The application quantity of the first solution B on a wet basis is preferably from 50 to 200 ml/m2, more preferably from 75 to 150 ml/m2, while the application quantity of the first solution B on a solids basis is preferably from 5 to 25 g/m2, more preferably from 10 to 18 g/m2.
When the first solution C containing colloidal silica is used, the application quantity of the first solution C on a wet basis is preferably from 10 to 150 ml/m2, more preferably from 20 to 100 ml/m2, while the application quantity of the first solution C on a solids basis is preferably from 0.01 to 10 g/m2, more preferably from 0.05 to 5 g/m2.
The first solution A, the first solution B, and the first solution C used as required are described below.
(First Solution A)
The first solution A contains at least one kind of inorganic fine particles and at least one kind of cationic emulsions.
Cationic Emulsion:
Herein, cationic emulsions usable in the invention are described.
The term cationic emulsion as used in the invention is intended to include cationic aqueous emulsions and aqueous emulsions modified by cationization. Examples of such aqueous emulsions include emulsions of conjugated diene copolymers, such as styrene-butadiene copolymer and methyl methacrylate-butadiene copolymer; emulsions of acrylic polymers, such as homo- or co-polymers of acrylates or methacrylates, and a homo- or co-polymer of acrylic acid or methacrylic acid; emulsions of styrene-acrylic copolymers, such as styrene-acrylate copolymers and styrene-methacrylate copolymers; emulsions of vinyl polymers, such as ethylene-vinyl acetate copolymer; and urethane emulsions which have urethane linkage and are cationized with a cationic groups, emulsions whose surfaces are cationized with cationic surfactants, and emulsions which are polymerized in the presence of cationic polyvinyl alcohol and have surfaces on which the polyvinyl alcohol is spread. Of these cationic emulsions, cationic emulsions predominantly composed of urethane emulsions are preferred over the others.
Additionally, such a cationic emulsion can constitute the organic nitrogen-containing cationic polymer for use in the invention when the ink-receiving layer is formed. The organic nitrogen-containing cationic polymer is the same as described in the foregoing section on the ink-receiving layer, and the preferable range thereof is also the same.
From the standpoint of achieving effects of the invention with greater efficiency, it is appropriate that the cationic emulsion content in the first solution A be from 1 to 20% by mass, preferably from 2 to 15% by mass, particularly preferably from 4 to 12% by mass, based on the total solids in the first solution A.
Additionally, the expression “the total solids in the first solution A” used in the invention refers to all ingredients but water in the first solution A. The meaning of the term “total solids” is substantially similar for other solutions.
In view of enhancement of ozone resistance, it is preferable that the first solution A further contains a sulfur compound.
In this case, from the standpoint of achieving effects of the invention more effectively, it is appropriate that the sulfur compound content in the first solution A be from 1 to 20% by mass, preferably from 3 to 15% by mass, particularly preferably from 4 to 10% by mass, based on the total solids in the first solution A.
In addition, the first solution A may further contain a water-soluble resin, a crosslinking agent, a mordant, a dispersant, a surfactant, and other ingredients.
When the first solution A is applied, it is also preferable that the first solution A is subjected to in-line mixing with a solution containing the water-soluble polyvalent metal salt as recited above (preferably a basic polyaluminum chloride), and then applied.
Details of various ingredients including the inorganic fine particles, the sulfur compound, the water-soluble resin, the crosslinking agent, the mordant and the water-soluble polyvalent metal compound are the same as described in the section <Ink-Receiving Layer>, and preferred forms of those ingredients are also the same as specified in that section. Dispersants which may be contained therein are described hereinafter.
The first solution A is preferably acidic, and the pH thereof is preferably 5.0 or below, more preferably 4.5 or below, further preferably 4.0 or below.
The first solution A can be adjusted to such a pH range by appropriately choosing the kind and amount of the cationic polymer added. Alternatively, the pH adjustment may be made by addition of an organic or inorganic acid. When the pH of the first solution A is 5.0 or below, crosslinking reaction of the water-soluble resin with a crosslinking agent (a boron compound in particular) in the first solution A can be adequately inhibited.
Preparation Method of First Solution A:
In the invention, the first solution A containing at least inorganic fine particles and a cationic emulsion can be prepared, e.g., as follows.
Specifically, vapor-phase process silica fine particles and a dispersant are added to water (so that the silica fine particles added has a content of, e.g., 10 to 20% by mass in water), subjected to a dispersing operation using a rapidly rotating wet colloidal mill (e.g., CLEARMIX, trade name, made by M TECHNIQUE) under conditions that the dispersion time is, e.g., 20 minutes (preferably from 10 to 30 minutes) and the revs are, e.g., as high as 10,000 rpm (preferably from 5,000 to 20,000 rpm). To the resulting dispersion, a crosslinking agent (e.g., boric acid), an aqueous polyvinyl alcohol (PVA) solution (in such an amount that the PVA content becomes about one-third of the vapor-phase process silica content) and a cationic emulsion are added, and further the water-soluble polyvalent metal salt (e.g., basic polyaluminum hydroxide) is added, and then subjected to the dispersion operation under the same rotational conditions as mentioned above, thereby preparing the first solution A.
The water-soluble polyvalent metal salt may be added by in-line mixing just before application.
As an alternative machine for the dispersing operations, a liquid-liquid collision dispersing machine (e.g., ULTIMIZER, trade name, made by Sugino Machine Ltd.) can also be used.
The coating solution obtained is in a homogeneous sol state, and this solution is applied to a substrate in accordance with the following application method, and then dried. Thus, a porous ink-receiving layer having a three-dimensional network structure can be formed.
The aqueous dispersion containing the vapor-phase process silica and the dispersant may be prepared by preparing in advance an aqueous dispersion of the vapor-phase process silica and then adding the aqueous dispersion to an aqueous dispersant solution or adding an aqueous dispersant solution to the aqueous dispersion of the vapor-phase process silica, or mixing them simultaneously. Alternatively, vapor-phase process silica powder, not the aqueous dispersion of vapor-phase process silica, may be directly added to the aqueous dispersant solution.
After mixing the vapor-phase process silica and the dispersant, the resulting mixture is subjected to fining of particles by use of a dispersing machine, and thereby an aqueous dispersion having an average particle size of 50 to 300 nm can be obtained. Examples of a dispersing machine usable for obtaining such an aqueous dispersion include various dispersing machines hitherto known, such as a rapidly rotating dispersing machine, a medium agitation-type dispersing machine (such as a ball mill or a sand mill), a ultrasonic dispersing machine, a colloid mill dispersing machine and a high-pressure dispersing machine. Of these dispersing machines, an agitation-type dispersing machine, a colloid mill dispersing machine and a high-pressure dispersing machine are preferred over the others from the viewpoint of effectively dispersing clotted fine grains.
In each of the foregoing steps, water, an organic solvent or a mixture thereof can be used as solvent. Examples of an organic solvent usable in the application include alcohol compounds such as methanol, ethanol, n-propanol, isopropanol and methoxypropanol, ketones such as acetone and methyl ethyl ketone, tetrahydrofuran, acetonitrile, ethyl acetate and toluene.
The dispersant used in the foregoing preparation is a cationic polymer. Examples of such a cationic polymer include the mordants disclosed in JP-A No. 2006-321176, paragraphs [0138] to [0148]. Alternatively, the use of a silane coupling agent as the dispersant is also advantageous.
The amount of the dispersant added is preferably from 0.1% to 30%, more preferably from 1% to 10%, based on the fine particles.
(First Solution B)
The first solution B is a solution differing from the first solution A in composition.
From the viewpoint of forming an ink-receiving layer so that the organic nitrogen-containing cationic polymer, for example, is contained in a greater quantity in the lower half than in the upper half of the ink-receiving layer formed, it is preferable that the cationic emulsion content in the first solution B is made lower than the cationic emulsion content in the first solution A.
In other words, it is required that the content ratio of the cationic emulsion [content (by mass) in the first solution B/content (by mass) in the first solution A] be lower than 1.0.
From the viewpoint of achieving effects of the invention with higher efficiency, the content ratio is preferably from 0 to 0.8, more preferably from 0 to 0.4, particularly preferably 0 (which indicates a state in which the coating solution B contains no cationic emulsion).
In view of further efficient attainment of the effects of the invention, the cationic emulsion content in the first solution B is preferably from 0 to 8% by mass, more preferably from 0 to 4% by mass, particularly preferably 0% by mass (which indicate a state in which the coating solution B contains no cationic emulsion), based on the total solids in the first solution B.
In addition, the first solution B may contain a sulfur compound, but from the viewpoint of keeping the densities of recorded images higher, the sulfur compound content in the first solution B is preferably made lower than the sulfur compound content in the first solution A.
In other words, it is required that the content ratio of the sulfur compound [content in the first solution B/content in the first solution A] be lower than 1.0.
In this case, the content ratio of the sulfur compound [content in the first solution B/content in the first solution A] is preferably from 0 to 0.6, more preferably from 0 to 0.3, particularly preferably 0 (which indicates a state in which the coating solution B contains no sulfur compound).
In view of further efficient attainment of the effects of the invention, the sulfur compound content in the first solution B is preferably from 0 to 5% by mass, more preferably from 0 to 3% by mass, particularly preferably 0% by mass (which indicate a state in which the coating solution B contains no sulfur compound), based on the total solids in the first solution B.
Moreover, the first solution B may contain inorganic fine particles, a water-soluble resin, a dispersant, a crosslinking agent, a mordant, a surfactant, and other ingredients.
When the first solution B is applied, it is also preferable that the first solution B is subjected to in-line mixing with a solution containing the water-soluble polyvalent metal salt as recited above (preferably a basic polyaluminum chloride), and then applied.
Details of various ingredients including the inorganic fine particles, the sulfur compound, the water-soluble resin, the crosslinking agent, the mordant, the surfactant and the water-soluble polyvalent metal salt are the same as described in the section <Ink-Receiving Layer>, and preferred forms of those ingredients are also the same as specified in that section. Details of the dispersant are the same as mentioned in the description of the first solution A, and a preferred range of the dispersant is also the same.
In addition, the first solution B can be prepared in the same manner as the first solution A.
The first solution B is preferably acidic similarly to the first solution A, and the pH thereof is preferably 5.0 or below, more preferably 4.5 or below, further preferably 4.0 or below. The pH adjustment to such a range can be made by appropriately choosing the kind and amount of the cationic resin added. Alternatively, the adjustment may be made by addition of an organic or inorganic acid. When the pH of the first solution B is 5.0 or below, crosslinking reaction of the water-soluble resin with a crosslinking agent (a boron compound in particular) in the first solution B can be inhibited satisfactorily.
(First Solution C)
The first solution C, which is used as required, is described below.
The first solution C preferably contains colloidal silica. By further applying the first solution C containing colloidal silica to the first solution B, the colloidal silica layer can be formed as the uppermost layer of the ink-receiving layer. As a result, the glossiness of the ink-receiving layer formed can be enhanced.
The colloidal silica is the same as described in the foregoing section <Ink-Receiving Layer>, and the preferred range thereof is also the same.
The first solution C can be prepared by adding colloidal silica to ion exchange water, and mixing them with stirring.
<Hardening Process>
The first aspect has a process of performing cross-link hardening of the coating layer formed in the coating-layer formation process by application of a basic compound-containing second solution at either (1) the same time as at least the first solution A and the first solution B are applied or (2) a stage in the course of drying of the coating layer formed by applying at least the first solution A and the first solution B, and that before the coating layer shows decreasing-rate drying. Hereafter, this process is referred to as the hardening process too.
As a method of applying the second coating solution “(1) at the same time as at least the first solution A and the first solution B are applied”, the mode of simultaneous coating (multilayer coating) in which the first solution A, the first solution B, the first solution C as required, and the second solution are applied simultaneously in the order of mention, the nearest the substrate first, is suitable. Alternatively, it may adopt a mode that the first solution A is applied, and then to the first solution A applied, the coating solution for the uppermost layer (the first solution B or the first solution C) and the second solution are applied simultaneously (which is also referred to as multilayer coating or simultaneous multilayer coating).
The simultaneous coating (multilayer coating) can be performed with known coating apparatus, such as an extrusion die coater or a curtain flow coater.
A method of applying the second solution “(2) at a stage in the course of drying of the coating layer formed by applying at least the first solution A and the first solution B, and that before the coating layer shows decreasing-rate drying” is the method referred to as “Wet-On-Wet method” or “WOW method”. Details of “Wet-On-Wet method” are described, e.g., in JP-A No. 2005-14593, paragraphs [0016] to [0037].
In the invention, application of the second solution can be carried out as follows: After a coating layer is formed by performing simultaneous coating (multilayer coating) or sequential coating of the first solution A and the first solution B (and further the first solution C as required) so that these solutions are applied in the order of mention from the substrate side, the second solution is applied at a stage in the course of drying of the coating layer formed, and that before the coating layer shows decreasing-rate drying, according to (i) a method of further applying the second solution to the coating layer formed, (ii) a method of spraying the second solution on the coating layer formed, or (iii) a method of immersing the coating layer-provided substrate in the second solution.
Method available for applying the second layer coating liquid in the method (i) include methods known in the art such as using a curtain flow coater, extrusion die coater, air doctor coater, blade coater, rod coater, knife coater, squeeze coater, reverse roll coater and bar coater. The methods of using a extrusion die coater, curtain flow coater or bar coater are preferable, since these methods are able to apply the coat without making direct contact with the already formed first coated layer.
The expression “before the coating layer exhibits decreasing-rate drying” in the cross-link hardening process usually refers to a period of several minutes from immediately after the application of coating solutions for the ink-receiving layer (which include the first solution A and the first solution B (and further the first solution C as required) in the invention), and in this course the coating layer applied exhibits the phenomenon of “constant-rate drying” in which the solvent (dispersion medium) content in the coating layer applied decreases in proportion to a lapse of time. On the time for such “constant-rate drying”, there are descriptions in, e.g., Kagaku Kogaku Binran (Handbook of Chemical Technology), pp. 707-712, MARUZEN Co., Ltd. (Oct. 25, 1980).
As to conditions for drying the coating layer until it comes to show decreasing-rate drying, they are generally chosen from the drying temperature range of 40° to 180° C. and the drying time range of 0.5 to 10 minutes (preferably 0.5 to 5 minutes). Although it is natural that the drying time varies according to the application quantity, the range specified above is usually appropriate.
(Second Solution)
Hereafter, the second solution for use in the cross-link hardening process is described.
Basic Compound:
The second solution for use in the invention contains at least one kind of basic compound. Examples of such a basic compound include ammonium salts of weak acids, alkali metal salts of weak acids (such as lithium carbonate, sodium carbonate, potassium carbonate, lithium acetate, sodium acetate and potassium acetate), alkaline earth metal salts of weak acids (such as magnesium carbonate, barium carbonate, magnesium acetate and barium acetate), ammonium hydroxide, primary to tertiary amines (such as triethylamine, tripropylamine, tributylamine, trihexylamine, dibutylamine and butylamine), primary to tertiary anilines (such as diethylaniline, dibutylaniline, ethylaniline and aniline) and pyridines which may have substituents (such as 2-aminopyridine, 3-aminopyridine, 4-aminopyridine and 4-(2-hydroxyethyl)-aminopyridine).
In addition to the basic compounds recited above, combinations of those basic compounds with other basic substances and/or salts thereof can also be used. Examples of the other basic substances include ammonia, primary amines such as ethylamine and polyallylamine, secondary amines such as dimethylamine, tertiary amines such as N-ethyl-N-methylbutylamine, and hydroxides of alkali metals and alkaline earth metals.
Of the basic compounds recited above, ammonium salts of weak acids are preferred over the others. The term “weak acids” refers to the acids having pKa of 2 or more among inorganic and organic acids described, e.g., in Kagaku Binran Kisohen II (Handbook of Chemistry Basic Edition II), published by MARUZEN Co., Ltd. Examples of the ammonium salts of weak acids include ammonium carbonate, ammonium hydrogen carbonate, ammonium borate, ammonium acetate and ammonium carbamate, but they are not limited to these salts. Of these salts, ammonium carbonate, ammonium hydrogen carbonate and ammonium carbamate are used to particular advantage in point of reduction in ink bleed, because they don't remain in the layer after drying.
Additionally, the basic compounds can also be used as combinations of two or more thereof.
The content of the basic compound (especially an ammonium salt of weak acid) in the second solution is preferably from 0.5% to 10% by mass, more preferably from 1% to 5% by mass, based on all the ingredients (including the solvent) of the second solution. By adjusting the content of basic compounds (especially ammonium salts of weak acids) to the foregoing range in particular, a sufficient degree of hardening can be attained and impairment of a working environment due to too high an ammonia concentration can be avoided.
Metal Compound:
The second solution for use in the invention preferably contains at least one kind of metal compound.
As to the metal compound to be incorporated in the second solution, any compounds are usable as long as they are stable under basic conditions. Specifically, any of the water-soluble polyvalent metal salts as recited above, metal complex compounds, inorganic oligomers and inorganic polymers may be used. More specifically, zirconium compounds and the compounds recited as inorganic mordants in JP-A No. 2005-14593, paragraphs [0100] and [0101], are used to advantage. And examples of usable metal complex compounds include the metal complexes described in Kagaku Sosetsu (Review of Chemistry), No. 32 (1981), edited by The Chemical Society of Japan, and the transition metal complexes containing transition metals including ruthenium as described in Coordination Chemistry Review, vol. 84, pp. 85-277 (1988), and JP-A No. 2-182701.
Of the compounds recited above, zirconium compounds and zinc compound, especially zirconium compounds, are preferred over the others. Examples of such zirconium compounds include ammonium zirconium carbonate, ammonium zirconium nitrate, potassium zirconium carbonate, ammonium zirconium citrate, zirconium stearate, zirconium octylate, zirconyl nitrate, zirconium oxychloride and zirconium hydroxychloride. Of these zirconium compounds, ammonium zirconium carbonate is used to particular advantage. In the second solution, two or more metal compounds (preferably including a zirconium compound) may also be used in combination.
The content of a metal compound (a zirconium compound in particular) in the second solution is preferably from 0.05% to 5% by mass, more preferably from 0.1% to 2% by mass, based on all the ingredients (including the solvent) of the second solution. By adjusting the content of a metal compound (a zirconium compound in particular) to the foregoing range, not only the hardening of the coating layer can be fully achieved, but also insufficient print density and beading due to reduction in mordanting capability can be avoided, and besides, no deterioration of a working environment due to too high a concentration of basic compound, such as ammonia, is caused. Additionally, two or more kinds of metal compounds may be used in combination. When a metal compound is used in combination with a mordant other than metal compounds among the mordant components described hereafter, the mordant can be used in such an amount that the total content of the metal compound and the mordant falls within the range specified above and there occurs no impairment of effects of the invention.
In terms of image density and ozone resistance, it is also preferable that the second solution contains as a metal compound any of the magnesium salts recited above. As the magnesium salt contained, magnesium chloride is particularly suitable.
In this case, the amount of the magnesium salt added is preferably from 0.1% to 1% by mass, more preferably from 0.15% to 0.5% by mass, based on all the ingredients of the second solution.
The second solution can contain a crosslinking agent and other mordant components as required.
The second solution can speed up hardening when used in a state of alkaline solution, so the pH thereof is adjusted preferably to 7.1 or higher, more preferably to 8.0 or higher, particularly preferably to 9.0 or higher. When the pH is 7.1 or higher, the crosslinking reaction of the water-soluble resin which may be contained in the first solution A and/or the first solution B can be further promoted, and bronzing and cracking in the ink-receiving layer can be prevented more effectively.
The second solution can be prepared by adding to, for example, ion exchange water a metal compound (such as a zirconium compound at, for example, a concentration of 1 to 5%) and a basic compound (such as ammonium carbonate at, for example, 1 to 5%), and further paratoluenesulfonic acid (at, for example, 0.5 to 3%) as required, and then thoroughly stirring them. Additionally, “%” for each ingredient represents % by mass of solid content.
As to the solvent for preparation of the second solution, water, an organic solvent or a mixture thereof is usable. Examples of an organic solvent which can be used for application include alcohol compounds such as methanol, ethanol, n-propanol, isopropanol and methoxypropanol, ketones such as acetone and methyl ethyl ketone, tetrahydrofuran, acetonitrile, ethyl acetate and toluene.
<Cooling Process and Drying Process>
The second aspect has a process of cooling the coating layer formed in the coating layer formation process to a temperature at least 5° C. lower than lower one of temperatures at which the first solution A and the first solution B are applied, respectively (hereinafter referred to as “a cooling process” too), and a process of forming an ink-receiving layer by drying the coating layer cooled (hereinafter referred to as “a drying process” too).
As a method of cooling the coating layer in the cooling process, it is preferable to adopt a method of cooling the substrate, on which the coating layer is formed, in a cooling zone kept at temperatures ranging from 0° to 20° C. The method of cooling for 5 to 30 seconds in a cooling zone kept at temperatures ranging from 0° to 10° C. is far preferred.
The temperature of the cooling zone is preferably from 110° C. to 20° C. Herein, the temperature of the coating layer can be determined by temperature measurement made on the coating surface.
<Other Processes>
In the first aspect and the second aspect, the surface smoothness, glossiness, transparency and strength of coated layer may be improved by applying calender treatment by heating and passing the sheet through roll nips under pressure, using a super calender or gloss calender machine after forming the ink receiving layer is formed on the substrate. However, since in some cases the calender treatment may cause a decrease of the porosity (resulting in a decrease in ink absorbing property), conditions that give a small decrease of the porosity should be employed.
The roll temperature in the case of performing calender treatment is preferably from 30° to 150° C., more preferably from 40° to 100° C.
And the linear pressure between rolls at the time of calender treatment is preferably from 50 to 400 kg/cm, more preferably from 100 to 200 kg/cm.
<<Inkjet Recording Method>>
As to the inkjet recording method for recording images on the present inkjet recording medium, there is no particular restriction, and various known methods can be adopted which include a charge control method in which jets of ink are discharged by utilizing electrostatic attraction, a drop-on-demand method (a pressure pulse method) which utilizes vibration pressure of a piezo device, an acoustic inkjet method in which ink is irradiated with acoustic beams converted from electric signals and the radiation pressure created thereby is utilized for ink jetting, and a thermal inkjet method in which bubbles are formed by heating of ink and the pressure generated thereby is utilized. In addition, a method in which small volumes of great many droplets of low-density ink referred to as photo ink are made to jet out, a method of improving image quality by using plural kinds of ink having substantially the same color hue but differing in density, and a method of using colorless, transparent ink are included in the foregoing inkjet recording methods.
EXAMPLES
The present invention will now be illustrated in more detail by reference to the following examples, but the invention should not be construed as being limited by these examples. Additionally, all “parts” and all “%” in the examples are by mass unless otherwise noted.
Example 1
<<Production of Inkjet Recording Medium>>
<Making of Substrate>
Wood pulp constituted of 100 parts of LBKP was beaten to a Canadian freeness of 300 ml by means of a double disk refiner, and thereto 0.5 parts of epoxidized behenic acid amide, 1.0 parts of anionic polyacrylamide, 0.1 parts of polyamidepolyamine epichlorohydrin and 0.5 parts of cationic polyacrylamide were added in bone dry mass ratio to the pulp. The resulting pulp was made into raw paper with a basis weight of 170 g/m2 by means of a Fourdrinier paper machine.
In order to adjust a surface size of the raw paper made, the raw paper was impregnated with a 4% aqueous polyvinyl alcohol solution to which 0.04% of a fluorescent whitening agent (Whitex BB, trade name, manufactured by Sumitomo Chemical Co., Ltd.) was added so as to form a 0.5 g/m2 of coating on a bone dry weight basis, dried and then subjected to calender treatment, thereby preparing base paper adjusted to a density of 1.05.
The base paper obtained was given corona discharge treatment on the wire side (the back), and then coated with high-density polyethylene by use of a melt extrusion machine under a condition that the film thickness became 19 μm, thereby forming a resin layer having a matte surface (hereinafter, this resin layer side was referred to as “the back”). This resin layer on the back was further given corona discharge treatment, and thereto a dispersion prepared by dispersing into water an antistatic agent containing aluminum oxide (ALUMINA SOL 100, trade name, manufactured by Nissan Chemical Industries, Ltd.) and silicon dioxide (SNOWTEX O, trade name, manufactured by Nissan Chemical Industries, Ltd.) at a ratio of 1:2 by mass was applied so as to have a dry weight of 0.2 g/m2.
Further, the base paper was given corona discharge treatment on the felt side (top side) where the resin layer was not provided, and then coated with low-density polyethylene which had an MFR (melt flow rate) of 3.8 and contained 10% of anatase-type titanium dioxide, a very small amount of ultramarine blue and 0.01% of a fluorescent whitening agent (based on the polyethylene) by use of a melt extrusion machine under a condition that the film thickness became 29 μm, thereby forming a high-gloss thermoplastic resin layer on the top side of the base paper (hereinafter, this high-gloss surface is referred to as “the front surface”). The thus treated base paper was used as substrate in the present example.
<Preparation of First Solution B (for Upper Layer)>
As shown in the following composition, (1) vapor-phase process silica fine particles, (2) ion exchange water, (3) SHALLOL DC-902P and (4) ZA-30 were mixed, and dispersed with a liquid-liquid collision dispersing machine (ULTIMIZER, trade name, made by Sugino Machine Ltd.). Then, the dispersion obtained was heated up to 45° C. and kept for 20 hours as it was. Thereafter, (5) a polyvinyl alcohol-dissolved liquor was added to the dispersion at a temperature of 30° C., thereby preparing a first solution B (for the upper layer).
The mass ratio of the silica fine particles to the water-soluble resin (PB ratio=(1):(5)) was 4.0:1, and the first solution B was acidic and the pH thereof was 3.4.














Composition of First Solution B (for Upper Layer):




(1) Vapor-phase process silica fine particles
8.9
parts


(inorganic fine particles, AEROSIL 300SF75, trade name,


manufactured by NIPPON AEROSIL CO., LTD.)


(2) Ion exchange water
1.0
parts


(3) SHALLOL DC-902P (51.5% aqueous solution, trade
0.78
parts


name, a dispersant manufactured by DAI-ICHI KOGYO


SEIYAKU CO., LTD.)


(4) ZA-30 (trade name, zirconium acetate manufactured by
0.48
parts


DAIICHI KIGENSO KAGAKU KOGYO CO., LTD.)


(5) Polyvinyl alcohol (water-soluble resin) dissolved liquor
31.2
parts


Composition of Dissolved Liquor:


PVA235 (trade name, saponification degree: 88%,
2.2
parts


polymerization degree: 3500, manufactured by


KURARAY CO., LTD.)


Ion exchange water
28.2
parts


Diethylene glycol monobutyl ether (Butycenol 20P, trade
0.7
parts


name, manufactured by Kyowa Hakko Chemicals Co., Ltd.)


EMULGEN 109P (surfactant, manufactured by Kao
0.1
parts


Corporation)









<Preparation of First Solution A (for Lower layer)>

As shown in the following composition, (1) vapor-phase process silica fine particles, (2) ion exchange water, (3) SHALLOL DC-902P, (4) ZA-30 and (5) 30% methionine sulfoxide were mixed, and dispersed with a liquid-liquid collision dispersing machine (ULTIMIZER, trade name, made by Sugino Machine Ltd.). Then, the dispersion obtained was heated up to 45° C. and kept for 20 hours as it was. Thereafter, (6) boric acid, (7) a polyvinyl alcohol-dissolved liquor and (8) SUPERFLEX 650 (25% by mass aqueous solution) were added to the dispersion at a temperature of 30° C., thereby preparing a first solution A (for the lower layer).
The mass ratio of the silica fine particles to the water-soluble resin (PB ratio=(1):(7)) was 4.0:1, and the first solution A (for lower layer) was acidic and the pH thereof was 3.8.














Composition of First Solution A (for Lower Layer):




(1) Vapor-phase process silica fine particles
8.9
parts


(inorganic fine particles, AEROSIL 300SF75, trade name,


manufactured by NIPPON AEROSIL CO., LTD.)


(2) Ion exchange water
1.0
parts


(3) SHALLOL DC-902P (51.5% aqueous solution, trade
0.78
parts


name, a dispersant manufactured by DAI-ICHI KOGYO


SEIYAKU CO., LTD.)


(4) ZA-30 (trade name, zirconium acetate manufactured by
0.24
parts


DAIICHI KIGENSO KAGAKU KOGYO CO., LTD.)


(5) 30% Methionine sulfoxide (sulfur compound)
1.76
parts


(6) Boric acid (crossliniking agent)
0.4
parts


(7) Polyvinyl alcohol (water-soluble resin) - dissolved
31.2
parts


liquor


Composition of Dissolved Liquor


PVA235 (trade name, saponification degree: 88%,
2.2
parts


polymerization degree: 3500, manufactured by


KURARAY CO., LTD.)


Ion exchange water
28.2
parts


Diethylene glycol monobutyl ether (Butycenol 20P, trade
0.7
parts


name, manufactured by Kyowa Hakko Chemicals Co., Ltd.)


EMULGEN 109P (surfactant, manufactured by Kao
0.1
parts


Corporation)


(8) SUPERFLEX 650 (25 mass % aqueous solution,
3.1
parts


cationic emulsion, manufactured by DAI-ICHI


KOGYO SEIYAKU CO., LTD.)









<Preparation of First Solution C (for Uppermost Layer)>

A first solution C (for the uppermost layer) was prepared by mixing and stirring the following ingredients in amounts shown below.










Composition of First Solution C (for Uppermost Layer):
















(1) PL-3L (trade name, colloidal silica manufactured by
 2.5 parts


FUSO CHEMICAL CO., LTD., average


primary grain size: 32 nm)


(2) Ion exchange water
97.5 parts









<Formation of Ink-Receiving Layer>

After corona discharge treatment was given to the front surface of the substrate, the first solution A (for the lower layer), the first solution B (for the upper layer) and the first solution C (for the uppermost layer) were applied to the front surface by means of an extrusion die coater according to a simultaneous multilayer coating method, thereby forming a coating layer.
Specifically, the following procedure was carried out in the simultaneous multilayer coating: The first solution A (for the lower layer) and the following in-line solution was subjected to in-line mixing at rates of 96 ml/m2 and 6.0 ml/m2, respectively, and the resulting mixture was applied as the lower layer; the first solution B (for the upper layer) and the following in-line solution were subjected to in-line mixing at rates of 91 ml/m2 and 6.0 ml/m2, respectively, and the resulting mixture was applied as the upper layer; and the first solution C (for the uppermost layer) was applied at a rate of 0.1 ml/m2 as the uppermost layer. The layer structure thus formed was first solution C (for the uppermost layer)/first solution B (for the upper layer)/first solution A (for the lower layer)/substrate.










Composition of In-Line Solution:
















(1) ALFINE 83 (trade name, manufactured by
2.0 parts


TAIMEI Chemicals Co., Ltd.)


(2) Ion exchange water
7.8 parts


(3) HYMAX SC-505E (trade name, 60 mass % aqueous
0.2 parts


solution of dimethylamine-epichlorohydrin


polycondensate, manufactured by HYMO Co., Ltd.)









The coating layer formed by the simultaneous multilayer coating method was dried at 80° C. with a hot-air dryer (air velocity: 3 to 8 m/sec) until the solids concentration therein reached 24%. During this period, the coating layer showed a constant-rate drying speed. Immediately thereafter, the coating layer was immersed for 3 seconds in a second solution having the following composition, and thereby 13 g/m2 of the second solution was deposited on the coating layer surface, and further 10-minute drying at 72° C. was carried out (drying process). Thus, an ink-receiving layer was formed on the substrate.










Composition of Second Solution:
















(1) Boric acid
1.3 parts


(2) Ammonium carbonate (first grade, manufactured by
5.0 parts


KANTO CHEMICAL CO., INC.)


(3) Zircosol AC-7 (trade name, animonium zirconyl
2.5 parts


carbonate manufactured by DAIICHI KIGENSO KAGAKU


KOGYO CO., LTD.)


(4) Ion exchange water
85.2 parts 


(5) Polyoxyethylene lauryl ether (surfactant, EMULGEN
6.0 parts


109P, trade name, manufactured by Kao Corporation, 


10% aqueous solution, HLB value: 13.6)









In the foregoing manner, an inkjet recording medium according to the invention, which had on the substrate the ink-receiving layer having a dry thickness of 35 μm, was produced.
<<Evaluation>>
The following evaluations were made on the inkjet recording medium thus produced. Evaluation results are shown in Table 1.
<Evaluation of Ozone Resistance>
Ozone resistance of magenta and cyan were evaluated as follows.
By use of an inkjet printer (the model PMA-820 from EPSON) loaded with a manufacturer-authorized ink set including magenta ink and cyan ink, a solid magenta image was printed on a recording medium sample, and stored for 72 hours in an atmosphere having a temperature of 23° C., a relative humidity of 60% and an ozone concentration of 10 ppm. The residual ratio of magenta density (ratio of the magenta image density after storage to the magenta image density before storage) was determined and ozone resistance of magenta was evaluated on the following criteria.
Likewise, a solid cyan image was printed and ozone resistance of cyan was evaluated.
Evaluation Criteria:
A: Residual rate is 75% or more.
B: Residual rate is between 60% and 75%.
C: Residual rate is 60% or less.
<Measurement of Print Density>
Printing of a solid black image was done with the inkjet printer PMA-820, and the density of the black portion obtained was measured with a reflection densitometer (the model Xrite 938 from Xrite, Incorporated).
<Bleeding>
By use of an inkjet printer (PIXUS MP950, trade name, made by Canon Inc.), a grid pattern formed with adjacent magenta and black inks (line width: 0.28 μm) was printed on an inkjet recording medium sample, and stored for 14 days in a chamber kept at a constant temperature of 23° C. and a constant relative humidity of 90%, and bleeding (bleeding with age) was evaluated on the following criteria.
Evaluation Criteria:
A: No appreciable change is observed.
B: A slight change is observed.
C: A great change is observed.
<Glossiness>
Glossiness of the ink-receiving layer surface of the inkjet recording medium before printing was measured at a measurement angle of 60 degrees by use of a digital variable gloss meter (UGV-50DP, trade name, made by SUGA TEST INSTRUMENTS CO., LTD.).
<Ascertainment of Presence Distribution of Organic Nitrogen-Containing Cationic Polymer>
A cross section of the inkjet recording medium obtained is cut away with a microtome, and mapping analyses of elemental Si and N were carried out with SEM-EDX (a combination of S-2150 from Hitachi Ltd. with EDX apparatus). By the mapping image of elemental Si, the presence position of the ink-receiving layer was ascertained, and the mapping image of elemental N was observed in a state of being juxtaposed with the mapping image of elemental Si.
Evaluation Criteria:
a: Quantity of elemental N present in the lower half of ink-receiving layer>quantity of elemental N present in the upper half of ink-receiving layer
b: Quantity of elemental N present in the lower half of ink-receiving layer≦quantity of elemental N present in the upper half of ink-receiving layer
<Ascertainment of Presence Distribution of Sulfur Compound>
A cross section of the inkjet recording medium obtained is cut away with a microtome, and mapping analyses of elemental Si and S were carried out with SEM-EDX (a combination of S-2150 from Hitachi Ltd. with EDX apparatus). By the mapping image of elemental Si, the presence position of the ink-receiving layer was ascertained, and the mapping image of elemental S was observed in a state of being juxtaposed with the mapping image of elemental Si.
Evaluation Criteria:
a: Quantity of elemental S present in the lower half of ink-receiving layer>quantity of elemental N present in the upper half of ink-receiving layer
b: Quantity of elemental S present in the lower half of ink-receiving layer≦quantity of elemental S present in upper half of ink-receiving layer
Example 2
An inkjet recording medium was produced in the same manner as in Example 1, except that the first solution C (for the uppermost layer) was not applied, and evaluations thereof were made according to the same methods as in Example 1. Evaluation results obtained are also shown in Table 1.
Example 3
An inkjet recording medium was produced in the same manner as in Example 2, except that the composition of the second solution was changed to the following composition, and evaluations thereof were made according to the same methods as in Example 1. Evaluation results obtained are also shown in Table 1.










Composition of Second Solution:
















(1) Boric acid
1.3 parts


(2) Ammonium carbonate (first grade, manufactured by
5.0 parts


KANTO CHEMICAL CO., INC.)


(3) Magnesium chloride (White Nigari NS, trade name,
2.5 parts


manufactured by Naikai Salt Industries Co., Ltd.)


(4) Ion exchange water
87.7 parts 


(5) Polyoxyethylene lauryl ether (surfactant, EMULGEN
6.0 parts


109P, trade name, manufactured by Kao Corporation,


10% aqueous solution, HLB value: 13.6)









Example 4
After corona discharge treatment was given to the front surface of the substrate made in Example 1, high-frequency corona discharge treatment was further given to the surface of the polyolefin resin-coated paper, and the resulting front surface was coated with a subbing layer having the following composition so as to have a gelatin coverage of 50 mg/m2, and dried. Thus, a substrate to be used in this example was prepared (sometimes the subbing layer surface is referred to as the front surface of the substrate hereafter). Additionally, the term “parts” represents parts by mass on a solids basis.










Composition of Subbing Layer:



















Lime-processed gelatin
100
parts



2-Ethylhexyl sulfosuccinate
2
parts



Chrome alum
10
parts










To the front surface, the first solution A (for the lower layer), the first solution B (for the upper layer) and the first solution C (for the uppermost layer) were applied with an extrusion die coater in accordance with a simultaneous multilayer coating method, thereby forming a coating layer. Herein, the compositions of the first solution A (for the lower layer), the first solution B (for the upper layer) and the first solution C (for the uppermost layer) were the same as the first solution A (for the lower layer), the first solution B (for the upper layer) and the first solution C (for the uppermost layer) in Example 1, respectively.
Specifically, the following procedure was carried out in the simultaneous multilayer coating: The first solution A (for the lower layer) and the foregoing in-line solution were subjected to in-line mixing at rates of 96 ml/m2 and 2.0 ml/m2, respectively, and the resulting mixture was applied as the lower layer; the first solution B (for the upper layer) and the foregoing in-line solution were subjected to in-line mixing at rates of 91 ml/m2 and 2.0 ml/m2, respectively, and the resulting mixture was applied as the upper layer; and the first solution C (for the uppermost layer) was applied at a rate of 0.1 ml/m2 as the uppermost layer. The layer structure thus formed was first solution C (for the uppermost layer)/first solution B (for the upper layer)/first solution A (for the lower layer)/substrate.
In addition, the temperature of each solution at the time of application was checked with a film-surface thermometer, and it was found that the temperatures of the first solutions A (for the lower layer), B (for the upper layer) and C (for the uppermost layer) were all 30° C.
The substrate on which the coating layer was formed by the simultaneous multilayer coating was cooled for 20 seconds in a cooling zone kept at 0° C. By this cooling, the temperature of the coating layer was lowered to 15° C. from 30° C. which was the temperature of the first solutions A to C before cooling. After the cooling, the coating layer was dried at 80° C. by means of a hot-air dryer (air velocity: 3 to 8 m/sec). Thus, an ink-receiving layer was formed on the substrate, and an inkjet recording medium was obtained.
On the thus obtained inkjet recording medium, evaluations was made according to the same methods as in Example 1. Evaluation results obtained are also shown in Table 1.
Example 5
An inkjet recording medium was produced in the same manner as in Example 2, except that, in preparing the first solution B (for the upper layer) in Example 2, 0.59 parts of 30% methionine sulfoxide was further added to the composition of the first solution B (for the upper layer), while the 30% methionine sulfoxide in the first solution A (for the lower layer) was reduced to 2.07 parts. On the thus obtained inkjet recording medium, evaluations were made according to the same methods as in Example 1. Evaluation results obtained are also shown in Table 1.
Example 6
An inkjet recording medium was produced in the same manner as in Example 2, except that, in preparing the first solution B (for the upper layer) in Example 2, 1.03 parts of SUPERFLEX 650 (a 25 mass % of aqueous solution) (trade name, a cationic emulsion manufactured by DAI-ICHI KOGYO SEIYAKU CO., LTD.) was further added to the composition of the first solution B (for the upper layer), while the SUPERFLEX 650 in the first solution A (for the lower layer) was reduced to 2.07 parts. On the thus obtained inkjet recording medium, evaluations were made according to the same methods as in Example 1. Evaluation results obtained are also shown in Table 1.
Comparative Example 1
An inkjet recording medium was produced in the same manner as in Example 2, except that the first solution B (for the upper layer) was applied as the lower layer and the first solution A (for the lower layer) was applied as the upper layer, and evaluated in accordance with the same methods as in Example 1. Evaluation results obtained are also shown in Table 1.
Comparative Example 2
An inkjet recording medium was produced in the same manner as in Example 2, except that, instead of the simultaneous multilayer coating of the first solution A (for the lower layer) and the first solution B (for the upper layer), the first solution A (for the lower layer) and the foregoing in-line solution were subjected to in-line mixing at rates of 187 ml/m2 and 24.2 ml/m2, respectively, and then the resulting mixture was applied into a single layer. On the thus produced inkjet recording medium, evaluations were made in accordance with the same methods as in Example 1. Evaluation results obtained are also shown in Table 1.
Comparative Example 3
An inkjet recording medium was produced in the same manner as in Example 2, except that the compositions of the first solution A (for the lower layer) and the first solution B (for the upper layer) in Example 2 were changed to the following compositions, respectively, and evaluated according to the same methods as in Example 1. Evaluation results obtained are also shown in Table 1.














Composition of First Solution B (for Upper Layer):




(1) Vapor-phase process silica fine particles (inorganic
8.9
parts


fine particles, AEROSIL 300SF75, trade


name, manufactured by NIPPON AEROSIL CO., LTD.)


(2) Ion exchange water
1.0
parts


(3) SHALLOL DC-902P (51.5% aqueous solution,
0.78
parts


trade name, a dispersant manufactured by


DAI-ICHI KOGYO SEIYAKU CO., LTD.)


(4) ZA-30 (trade name, zirconium acetate manufactured by
0.48
parts


DAIICHI KIGENSO KAGAKU KOGYO CO., LTD.)


(5) Polyvinyl alcohol (water-soluble resin)-dissolved liquor
31.2
parts


Composition of Dissolved Liquor


PVA235 (trade name, saponification degree: 88%,
2.2
parts


polymerization degree: 3500, manufactured by


KURARAY CO., LTD.)


Ion exchange water
28.2
parts


Diethylene glycol monobutyl ether (Butycenol 20P, trade
0.7
parts


name, manufactured by Kyowa Hakko Chemicals Co., Ltd.)


EMULGEN 109P (surfactant, manufactured by
0.1
parts


Kao Corporation)


(6) Boric acid (crosslinking agent)
0.4
parts


(7) Thioether compound illustrated below
1.5
parts


 








 


Composition of First Solution A (for Lower Layer):


(1) Vapor-phase process silica fine particles (inorganic fine
8.9
parts


particles, AEROSIL 300SF75, trade name, manufactured


by NIPPON AEROSIL CO., LTD.)


(2) Ion exchange water
1.0
parts


(3) SHALLOL DC-902P (51.5% aqueous solution,
0.78
parts


trade name, a dispersant manufactured by


DAI-ICHI KOGYO SEIYAKU CO., LTD.)


(4) ZA-30 (trade name, zirconium acetate manufactured by
0.48
parts


DAIICHI KIGENSO KAGAKU KOGYO CO., LTD.)


(5) Polyvinyl alcohol (water-soluble resin)-dissolved liquor
31.2
parts


Composition of Dissolved Liquor


PVA235 (trade name, saponification degree: 88%,
2.2
parts


polymerization degree: 3500, manufactured by


KURARAY CO., LTD.)


Ion exchange water
28.2
parts


Diethylene glycol monobutyl ether (Butycenol 20P,
0.7
parts


trade name, manufactured by Kyowa Hakko


Chemicals Co., Ltd.)


EMULGEN 109P (surfactant, manufactured by
0.1
parts


Kao Corporation)


(6) Boric acid (crosslinking agent)
0.4
parts


















TABLE 1









Evaluation Results











Ink-Receiving Layer

Pre-



















Upper-




Pre-
sence





most




sence
distribu-




Content
layer




distri-
tion of



Content
ratio of
(col-

Im-
Ozone

bution
the



ratio of
sulfur
loidal

age
resistance
Gloss-
of the
sulfur




















Half on far
Half on near
cationic
com-
silica
Bleed-
den-

ma-
iness
cationic
com-



substrate side
substrate side
polymer
pound
layer)
ing
sity
cyan
genta
(%)
polymer
pound























Example 1
SHALLOL DC-902P
SHALLOL DC-902P
0.4
0
present
A
2.40
B
A
50
a
a




SUPERFLEX 650




Sulfur compound


Example 2
SHALLOL DC-902P
SHALLOL DC-902P
0.4
0
absent
A
2.45
B
A
45
a
a




SUPERFLEX 650




Sulfur compound


Example 3
SHALLOL DC-902P
SHALLOL DC-902P
0.4
0
absent
A
2.40
A
A
45
a
a



Magnesium
SUPERFLEX 650



chloride
Sulfur compound


Example 4
SHALLOL DC-902P
SHALLOL DC-902P
0.4
0
present
A
2.43
B
A
52
a
a




SUPERFLEX 650




Sulfur compound


Example 5
SHALLOL DC-902P
SHALLOL DC-902P
0.4
0.5
absent
A
2.35
B
A
42
a
a



Sulfur compound
SUPERFLEX 650




Sulfur compound


Example 6
SHALLOL DC-902P
SHALLOL DC-902P
0.7
0
absent
A
2.34
B
B
45
a
a



SUPERFLEX 650
SUPERFLEX 650




Sulfur compound


Comparative
SHALLOL DC-902P
SHALLOL DC-902P
2.7
1.0<<
absent
A
2.10
B
B
44
b
b


Example 1
SUPERFLEX 650



Sulfur compound


Comparative
SHALLOL DC-902P
SHALLOL DC-902P
1.0
1.0
absent
A
2.10
B
B
43
b
b


Example 2
SUPERFLEX 650
SUPERFLEX 650



Sulfur compound
Sulfur compound


Comparative
SHALLOL DC-902P
SHALLOL DC-902P
1.0
1.0<<
absent
C
2.40
B
A
42
b
b


Example 3
Sulfur compound









The term “cationic polymer” used in Table 1 refers to the organic nitrogen-containing cationic polymer for use in the invention, specifically SUPERFLEX 650, SHALLOL DC-902P or HYMAX SC-505E.
In addition, the “Half on far substrate side” and “Half on near substrate side” columns in Table 1 indicate which position each ingredient, namely the organic nitrogen-containing cationic polymer (SUPERFLEX 650, SHALLOL DC-902P or HYMAX SC-505E), the sulfur compound or magnesium chloride, was incorporated in.
Further, the “Content ratio of cationic polymer” and “Content ratio of sulfur compound” columns indicate the content ratio of the organic nitrogen-containing cationic polymer and the content ratio of the sulfur compound, respectively, in the ink-receiving layer [content in the upper half the ink-receiving layer/content in the lower half the ink-receiving layer].
As can be seen from Table 1, the images recorded on the inkjet recording media produced in Examples 1 to 6 were inhibited from bleeding, had high image densities and offered high ozone resistance.
On the other hand, the inkjet recording medium of Comparative Example 1 wherein the organic nitrogen-containing cationic polymer was incorporated in only the upper half of the ink-receiving layer, and the inkjet recording medium of Comparative Example 2 wherein the content ratio [content in the upper half of the ink-receiving layer/content in the lower half of the ink-receiving layer] was 1.0 suffered reduction in image density and deterioration in ozone resistance. And the inkjet recording medium of Comparative Example 3 which was free of the organic nitrogen-containing cationic polymer caused bad bleeding.
Preferred embodiments of the present invention are described below, but the invention should not be construed as being limited to these embodiments.
<1> An inkjet recording medium comprising, on a substrate, an ink-receiving layer comprising inorganic fine particles and an organic nitrogen-containing cationic polymer, the organic nitrogen-containing cationic polymer being contained in a greater quantity in a half of the ink-receiving layer at a side nearer to the substrate (a near-substrate side) than in a half of the ink-receiving layer at a side further from the substrate (a far-substrate side) when the ink-receiving layer is divided into two equal parts by a plane parallel to the substrate.
<2> The inkjet recording medium of <1>, wherein the ratio of the content by mass of the organic nitrogen-containing cationic polymer in the far-substrate side half of the ink-receiving layer to that of the organic nitrogen-containing cationic polymer in the near-substrate side half of the ink-receiving layer is from 0 to 0.4.
<3> The inkjet recording medium of <1>, wherein the organic nitrogen-containing cationic polymer is a polymer selected from polymers having primary amino groups, polymers having secondary amino groups, polymers having tertiary amino groups and polymers having quaternary ammonium salt groups.
<4> The inkjet recording medium of <1>, wherein the organic nitrogen-containing cationic polymer is a polymer selected from cationic polyurethanes.
<5> The inkjet recording medium of <1>, wherein the ink-receiving layer further comprises a sulfur compound.
<6> The inkjet recording medium of <5>, wherein the ink-receiving layer has a higher sulfur compound content in the half at the near-substrate side than in the half at the far-substrate side.
<7> The inkjet recording medium of <1>, wherein the ink-receiving layer further comprises a magnesium salt.
<8> The inkjet recording medium of <1>, wherein the ink-receiving layer has two or more constituent layers and an uppermost constituent layer lying furthest from the substrate contains colloidal silica.
<9> The inkjet recording medium of <1>, wherein the inorganic fine particles are silica particles synthesized by a vapor-phase process.
<10> The inkjet recording medium of <1>, wherein the ink-receiving layer further comprises a water-soluble resin.
<11> The inkjet recording medium of <10>, wherein the water-soluble resin is polyvinyl alcohol.
<12> The inkjet recording medium of <1>, wherein the ink-receiving layer further comprises a crosslinking agent.
<13> The inkjet recording medium of <12>, wherein the crosslinking agent is boric acid.
<14> A method of manufacturing an inkjet recording medium, comprising:
forming a coating layer on a substrate by applying to the substrate at least a first solution A containing inorganic fine particles and a cationic emulsion and a first solution B differing in composition from the first solution A, in order of increasing distance from the substrate, and
performing cross-linking curing of the coating layer by applying a second solution containing a basic compound at either (1) the same time as at least the first solution A and the first solution B are applied or (2) a stage during drying of the coating layer formed by applying at least the first solution A and the first solution B before the coating layer exhibits decreasing-rate drying,
an ink-receiving layer thus being formed that includes the coating layer having undergone cross-linking curing and contains an organic nitrogen-containing cationic polymer in a greater quantity in a half at a side nearer to the substrate (a near-substrate side) than in a half at a side further from the substrate (a far-substrate side) when the ink-receiving layer is divided into two equal parts by a plane parallel to the substrate.
<15> A method of manufacturing an inkjet recording medium, comprising:
forming a coating layer on a substrate by applying to the substrate at least a first solution A containing inorganic fine particles and a cationic emulsion and a first solution B differing in composition from the first solution A, in order of increasing distance from the substrate,
cooling the coating layer to a temperature at least 5° C. lower than a lower temperature of respective temperatures at which the first solution A and the first solution B are applied, and
forming an ink-receiving layer by drying the coating layer thus cooled,
the ink-receiving layer thus formed containing an organic nitrogen-containing cationic polymer in a greater quantity in a half at a side nearer to the substrate (a near-substrate side) than in a half at a side further from the substrate (a far-substrate side) when the ink-receiving layer is divided into two equal parts by a plane parallel to the substrate.
All publications, patent applications, and technical standards mentioned in this specification are herein incorporated by reference to the same extent as if each individual publication, patent applications, and technical standards was specifically and individually indicated to be incorporated by reference.

## Claims

1. An inkjet recording medium comprising, on a substrate, an ink-receiving layer comprising inorganic fine particles and an organic nitrogen-containing cationic polyurethane, the organic nitrogen-containing cationic polyurethane being contained in a greater quantity in a half of the ink-receiving layer at a side nearer to the substrate (a near-substrate side) than in a half of the ink-receiving layer at a side further from the substrate (a far-substrate side) when the ink-receiving layer is divided into two equal parts by a plane parallel to the substrate,
wherein the ink-receiving layer has two or more constituent layers and an uppermost constituent layer lying furthest from the substrate has a thickness of from 0.05 μm to 5 μm and contains colloidal silica,
wherein the ink-receiving layer further comprises a sulfur compound selected from the group consisting of a thioether compound, a thiourea compound, a disulfide compound, a sulfinic acid compound, a thiocyanic acid compound, a sulfur-containing heterocyclic compound, and a sulfoxide compound,
the thioether compound being a compound represented by the following formula (1):


R1—(S—R3)m—S—R2  (1)


wherein, in formula (1), R1 and R2 each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or an alkyl- or aryl-containing group, R1 and R2 may combine with each other to form a ring, provided that at least either R1 or R2 represents an alkyl group substituted with an hydrophilic group or a basic nitrogen-containing group; R3 represents an alkylene group which may be substituted and which may have an oxygen atom; m represents an integer of 0 to 10, and when m is 1 or more, at least one sulfur atom bound to R3 may be a sulfoxide group or a sulfonyl group;
the thiourea compound being a compound having at least one structural unit represented by >N—C(═S)—N< per molecule;
the disulfide compound being a compound represented by the following formula:


R1—S—S—R2 


wherein, in the formula, R1 and R2 each independently represents an organic group containing a carbon or nitrogen atom bound to the disulfide sulfur;
the sulfinic acid compound being a compound represented by the following formula:


R—SO2M


wherein, in the formula, R represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a polymer residue; and M represents a hydrogen atom, an alkali metal atom or an ammonium.

2. The inkjet recording medium of claim 1, wherein the ratio of the content by mass of the organic nitrogen-containing cationic polyurethane in the far-substrate side half of the ink-receiving layer to that of the organic nitrogen-containing cationic polyurethane in the near-substrate side half of the ink-receiving layer is from 0 to 0.4.

3. The inkjet recording medium of claim 1, wherein the organic nitrogen-containing cationic polyurethane is a polyurethane selected from polyurethanes having primary amino groups, polyurethanes having secondary amino groups, polyurethanes having tertiary amino groups and polyurethanes having quaternary ammonium salt groups.

4. The inkjet recording medium of claim 1, wherein the ink-receiving layer has a higher sulfur compound content in the half at the near-substrate side than in the half at the far-substrate side.

5. The inkjet recording medium of claim 1, wherein the ink-receiving layer further comprises a magnesium salt.

6. The inkjet recording medium of claim 1, wherein the inorganic fine particles are silica particles synthesized by a vapor-phase process.

7. The inkjet recording medium of claim 1, wherein the ink-receiving layer further comprises a water-soluble resin.

8. The inkjet recording medium of claim 7, wherein the water-soluble resin is polyvinyl alcohol.

9. The inkjet recording medium of claim 1, wherein the ink-receiving layer further comprises a crosslinking agent.

10. The inkjet recording medium of claim 9, wherein the crosslinking agent is boric acid.