JP2003305944A - Ink jet recording sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ink jet recording sheet generating no crack or the like, having strength and good ink absorbility, excellent in image density, having light fastness, water resistance and gas resistance in an image part and generating no blur with the elapse of time when preserved for a long time under a high temperature and high humidity environment. <P>SOLUTION: In the ink jet recording sheet wherein a colorant receiving layer is provided on a support, the colorant receiving layer contains at least inorganic fine particles, a surface treatment agent (a) with a molecular weight of <1,000 for modifying inorganic fine particles and a polymer (b) with a weight average molecular weight of 1,000-500,000 having a group capable of forming a bond with respect to inorganic fine particles by chemical reaction. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid ink such as a water-based ink (using a dye or a pigment as a coloring material) and an oil-based ink, or a solid ink which is solid at room temperature and is melted and liquefied for printing. The present invention relates to a recording material supplied for ink jet recording using ink or the like, and more particularly to an ink jet recording sheet excellent in print density and image storage stability.

[0002]

2. Description of the Related Art In recent years, with the rapid development of the information technology industry, various information processing systems have been developed, and a recording method and a recording apparatus suitable for the information processing system have also been developed.
Each has been put to practical use. Among these recording methods, the inkjet recording method is not limited to offices, because it is capable of recording on various types of recording materials, has a relatively inexpensive hardware (device) and is compact, and has excellent quietness. , Has also been widely used in so-called home use.

Further, with the recent increase in resolution of ink jet printers, it has become possible to obtain so-called photograph-like high quality recorded matter. With the progress of such hardware (apparatus), ink jet recording has become possible. Various recording sheets have been developed. The properties required for the recording sheet for inkjet recording are generally (1) quick-drying property (high ink absorption speed), and (2) proper and uniform ink dot diameter. (No bleeding), (3) good graininess, (4) high dot roundness, (5) high color density, (6) high saturation (dullness (7) Good water resistance, light resistance, and gas resistance (ozone resistance) of the printed area, (8) High whiteness of the recording sheet, (9) Storage stability of the recording sheet Is good (no yellowing coloring occurs even after long-term storage, the image does not bleed after long-term storage), (10) is resistant to deformation and has good dimensional stability (curl is sufficiently small), (11) )
It can be mentioned that the hard running property is good. Furthermore,
In the application of photo glossy paper used for the purpose of obtaining so-called photographic-like high quality recorded matter, in addition to the above characteristics, glossiness, surface smoothness, photographic paper-like texture similar to silver halide photography are also required. To be done.

In order to improve the above-mentioned various properties, an inkjet recording sheet having a porous structure in the colorant receiving layer has been developed and put into practical use in recent years. Since such an inkjet recording sheet has a porous structure, it has excellent ink receptivity (quick drying) and high gloss.

For example, in JP-A-10-119423 and JP-A-10-217601, a coloring material receiving layer containing fine inorganic pigment particles and a water-soluble resin and having a high porosity is provided on a support. Ink jet recording sheets have been proposed. These ink jet recording sheets, particularly ink jet recording sheets provided with a coloring material receiving layer having a porous structure using silica as inorganic fine particles, have excellent ink absorbability due to the constitution and form a high resolution image. It has a high ink receiving performance to be obtained and can exhibit high gloss.

However, since it is a porous film, it has a high oxygen permeability, which may accelerate the deterioration of the components contained in the colorant receiving layer. Further, image bleeding over time (hereinafter referred to as "time bleeding") may occur due to water adsorption on the silica surface.

JP-A-62-178384 and JP-B-3-24905 disclose an ink jet recording sheet having a colorant receiving layer containing silica particles surface-treated with a silane coupling agent. .. However, these are for the purpose of improving the adhesiveness with the support and reducing the blurring immediately after printing, or improving the light resistance by reducing the surface activity of the silica particles. It does not prevent bleeding or improve gas resistance. Furthermore, in the coating liquid for the colorant receiving layer using the surface-treated silica fine particles, agglomeration occurs when mixed with a water-soluble resin such as PVA, and the particle size of the silica particles in the coating liquid increases. Therefore, the gloss coating film strength, the ink absorption speed, the water resistance, and the print density are adversely affected.

[0008]

SUMMARY OF THE INVENTION It is an object of the present invention to solve the above-mentioned problems of the prior art and achieve the following objects. That is, the object of the present invention is capable of forming a high-resolution and high-density image, excellent light resistance, water resistance, gas resistance of the image area, even after printing for a long time under high temperature and high humidity environment. An object of the present invention is to provide an ink jet recording sheet that stably holds an image without causing blurring over time and has excellent manufacturing suitability.

[0009]

[Means for Solving the Problems] Means for solving the above problems are as follows. That is, <1> In an inkjet recording sheet having a colorant-receiving layer on a support, the colorant-receiving layer modifies at least inorganic fine particles and has a molecular weight of 1
Inkjet recording comprising a surface treatment agent (a) of less than 000 and a polymer (b) having a group capable of forming a bond with inorganic fine particles by a chemical reaction and having a weight average molecular weight of 1,000 to 500,000. It is a sheet for.

<2> The ink jet recording sheet according to <1>, wherein the inorganic fine particles are inorganic fine particles modified with a surface treatment agent (a). <3> The surface treatment agent (a) contains Si, T in the molecule.
<1 which is a compound having at least one selected from the group consisting of i, Al, and Zr
> Or <2>, the inkjet recording sheet. <4> The polymer (b) is a polymer type silane coupling agent, <1> to <3>
The inkjet recording sheet according to any one of 1. <5> The inkjet recording sheet according to any one of <1> to <4>, wherein the polymer (b) is represented by the following general formula (1).

[0011]

[Chemical 3] [In the general formula (1), R ¹ , R ² , and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms which may include a saturated or unsaturated cyclic structure, and a carbon number 1 To 8 represent an alkoxy group or an aryloxy group, R
^At least one of ¹ , R ² and R ³ is an alkoxy group or an aryloxy group, and Q represents a divalent linking group having a total of 1 to 18 carbon atoms, which may have a heteroatom, and is substituted. It may have a group. A is a repeating unit provided from a cationic monomer, and B is a repeating unit provided from a nonionic monomer. m and n respectively represent the mol% of the A component and the B component, and m and n are each independently 0 to 100 mol%. ]

<6> The inkjet recording sheet according to any one of <1> to <4>, wherein the polymer (b) is at least a polymer represented by the following general formula (2).

[0013]

[Chemical 4] [In the general formula (2), R ⁴ , R ⁵ , and R ⁶ are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms which may contain a saturated or unsaturated cyclic structure, and a carbon number 1 To 8 represent an alkoxy group or an aryloxy group, R
^At least one of ⁴ , R ⁵ and R ⁶ is an alkoxy group or an aryloxy group, and J represents a divalent linking group having 1 to 18 total carbon atoms which may pass through a hetero atom, and a substituent May have. X represents a repeating unit provided from a cationic monomer, and Y represents a repeating unit provided from a nonionic monomer. r, p, and q represent mol% of each repeating unit, and r is 1 to 50.
Mol%, p and q are each independently 0 to 99 mol%. ]

<7> Any of <1> to <6>, wherein the inorganic fine particles are at least one selected from the group consisting of silica fine particles, colloidal silica, alumina fine particles, and pseudo-boehmite. The inkjet recording sheet described in Crab. <8> The inkjet recording sheet according to any one of <1> to <7>, wherein the color material receiving layer further contains a water-soluble resin. <9> The water-soluble resin is at least one selected from the group consisting of polyvinyl alcohol resin, cellulose resin, resin having ether bond, resin having carbamoyl group, resin having carboxyl group, and gelatins. The inkjet recording sheet according to <8>, wherein the sheet is for inkjet recording. <10> The color material receiving layer further contains a crosslinking agent capable of crosslinking the water-soluble resin, <8>
Alternatively, it is the inkjet recording sheet according to <9>. <11> The inkjet recording sheet according to <10>, wherein the crosslinking agent is a boron compound. <12> The above-mentioned <1>, wherein the coloring material receiving layer further contains a mordant capable of fixing an anionic dye.
To <11>, the inkjet recording sheet. <13> The above-mentioned <1>, wherein the mordant is at least one selected from polyallylamine or a derivative thereof, polyvinylamine or a derivative thereof.
2> The inkjet recording sheet described in 2>. <14> The coloring material receiving layer applies a first coating liquid containing at least inorganic fine particles, the surface treatment agent (a), the polymer (b), and a water-soluble resin to the surface of the support. , (1) at the same time as the coating, (2) during the drying of the coating layer formed by the coating and before the coating layer shows a rate-of-decrease drying rate, or (3) coating the coating layer by drying. After forming the film, a second coating liquid having a pH of 8 or more is applied to any of the above, and the crosslinking agent is added to the first coating liquid and the second coating liquid, or the first coating liquid and the first coating liquid. The ink jet recording sheet according to any one of claims 1 to 13, which is obtained by adding and applying it to at least one of the third coating liquids different from the second coating liquid. is there.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION In the ink jet recording sheet of the present invention, the coloring material receiving layer comprises inorganic fine particles, a surface treating agent (a) having a molecular weight of less than 1000, which modifies the inorganic pigment, and the inorganic pigment. Having a group capable of forming a bond by a chemical reaction with the bond and having a weight average molecular weight of 1,000 to 500,000
The polymer (b) of the above is included.

<Surface treatment agent (a)> The surface treatment agent for the inorganic fine particles in the present invention has a molecular weight of less than 1,000,
It is preferably 100 to 800 and is not particularly limited as long as it is a compound capable of chemically reacting with a functional group on the surface of the inorganic fine particles to form a bond. As such a compound, a coupling agent or an organic compound having a reactive group may be used. As the reactive group, a trialkoxysilyl group, a trichlorosilyl group, an isocyanate group, an isothiocyanate group, an acyl halide group, an epoxy group, a thiirane group,
Non-hydroxyl group, N-methylol group, lactam group, lactone group and the like can be mentioned. Of these, a coupling agent is preferable, and a coupling agent containing at least one selected from the group consisting of Si, Ti, Al, and Zr in the molecule is particularly preferable. Examples of these are given below.

(Surface-treating agent containing Si) As a surface-treating agent having Si, a silane coupling agent can be mentioned, and specific examples thereof are given below.

[0018]

[Chemical 5]

[0019]

[Chemical 6]

(Ti-Containing Surface Treatment Agent) Examples of the Ti-containing surface treatment agent include titanate coupling agents such as titanium acylate and titanium alcoholate, and specific examples thereof include tetramethyl titanate, tetraethyl titanate and tetra-titanate. Isopropyl titanate,
Tetrabutyl titanate, tetra (2-ethylhexyl) titanate, titanium octylene glycolate, titanium lactate, titanium lactate ammonium salt, titanium lactate ethyl ester, titanium stearate, titanium triethanolaminate, butyl titanate dimer, polytitanium acetylacetonate. , Polyhydroxytitanium stearate, and the like.

(Surface-treating agent containing Al) Examples of the surface-treating agent containing Al include aluminum coupling agents such as aluminum acylate and aluminum alcoholate. Specific examples thereof include aluminum lactate and aluminum isopropoxide. , Acetoalkoxy aluminum diisopropylate and the like. Further, a basic polynuclear complex containing aluminum may be used, and specific examples thereof include polyaluminum chloride represented by [Al ₂ (OH) _n Cl _6-n ] _m and polyaluminum silicate sulfate.

(Zr-Containing Surface Treatment Agent) Zr-containing surface treatment agents include zirconium-based coupling agents such as zirconium acylate and zirconium alcoholate. Specific examples thereof include zirconium propionate and zirconium isopropylate. Onate, zirconium butyrate, zirconium lactate, zirconium acetylacetonate, zirconium butyrate stearate, acetylacetone zirconium butyrate, tetra (triethanolamine) zirconate
Etc. Further, a zircoaluminate coupling agent represented by the following formula can be given.

[0023]

[Chemical 7]

Even if the surface treatment agents are used alone,
Mixtures of two or more may be used. The total content of the above-mentioned treatment agents contained in the color material receiving layer is preferably 0.001 to 20% by mass of the inorganic fine particles, and more preferably 0.05 to 10% by mass. When the total content is within this range, the ink receptivity, light resistance and gas resistance of the inkjet recording sheet are further improved.

When the surface treatment agent is contained in the color material receiving layer, it is added to the coating solution for the color material receiving layer in the form of an aqueous solution. Alternatively, a water-soluble organic solvent such as an alcohol compound (methanol, ethanol, isopropyl alcohol,
Ethylene glycol, diethylene glycol, diethylene glycol monobutyl ether, polyethylene glycol, polypropylene glycol, glycerin, diglycerin, trimethylolpropane, trimethylolbutane, etc.), ether compounds (tetrahydrofuran, dioxane, etc.), amide compounds (dimethylformamide,
Dimethylacetamide, N-methylpyrrolidone, etc.),
A ketone compound (acetone or the like) may be mixed and added to the coating material for the colorant-receptive layer in a state where the affinity for water is increased.

When the surface treatment agent does not have sufficient water solubility, a hydrophobic organic solvent such as an ester compound (ethyl acid acid salt, dioctyl adipate, butyl phthalate, methyl stearate, tricresyl phosphate, etc.) is used. ), Ether compounds (anisole, hydroxyethoxybenzene, hydroquinone dibutyl ether, etc.),
Hydrocarbon compounds (toluene, xylene, diisopropylnaphthalene, etc.), amide compounds (N-butylbenzenesulfonamide, stearic acid amide, etc.), alcohol compounds (2-ethylhexyl alcohol, benzyl alcohol, phenethyl alcohol, etc.), ketone compounds (hydroxy Acetophenone, benzophenone, cyclohexane, etc.), or the water-soluble organic solvent described above may be mixed and added. The form of addition may be oil drops, latex, solid dispersion, polymer dispersion, or the like.

<Polymer (b)> The polymer (b) in the present invention has a weight average molecular weight of 1,000 to 500,000 and has a group capable of forming a bond by a chemical reaction with the surface functional group of the inorganic fine particles. The combination is not particularly limited. As a group capable of forming a bond by a chemical reaction with the surface functional group of the inorganic pigment, a trialkoxysilyl group, a halogenated silyl group, an isocyanate group, an isothiocyanate group,
Examples thereof include an acyl halide group, an epoxy ring, a thiirane ring, a non-hydroxyl group, an N-methylol group, a lactam ring and a lactone ring. Of these, trialkoxysilyl groups,
Halogenated silyl groups are particularly preferred.

The polymer (b) has a weight average molecular weight of preferably 1,000 to 200,000,
More preferably, it is 1000 to 100,000. When the molecular weight is less than 1,000 or more than 500,000, not only the handling suitability is deteriorated but also the inorganic fine particles are aggregated.

The polymer (b) is preferably soluble in water or an organic solvent miscible with water, but it can be used in the form of a water-dispersible latex. Further, the total content in the inkjet recording sheet of the polymer (b), preferably from 0.1 to 10 g / m ^2, more preferably 0.2-5 g / m ^2. If the total content is less than 0.1 g / m ² or more than 10 g / m ² ,
It may cause aggregation of the inorganic fine particles.

Further, the polymer (b) is preferably a polymer represented by the following general formula (1).

[0031]

[Chemical 8] [In the general formula (1), R ¹ , R ² , and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms which may include a saturated or unsaturated cyclic structure, or a carbon number 1 to 8 represents an alkoxy group or an aryloxy group, at least one of R ¹ , R ² and R ³ is an alkoxy group or an aryloxy group, and Q is the total number of carbon atoms which may be passed through a hetero atom. It represents a divalent linking group of 1 to 18 and may have a substituent. A is a repeating unit provided from a cationic monomer, and B is a repeating unit provided from a nonionic monomer. m,
n represents the mol% of A component and B component, respectively, and m and n are 0-100 mol% each independently. ]

The alkyl group represented by R ¹ , R ² and R ³ has 1 to 18 carbon atoms, preferably 1 to 8 carbon atoms.
When the carbon number is 1 to 8, it is possible to sufficiently secure the reactivity with the inorganic fine particles. Examples of the alkyl group include, for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group,
A tetradecyl group and an octadecyl group are mentioned, and a methyl group, an ethyl group, a propyl group and a butyl group are preferable.

The alkoxy group represented by R ¹ , R ² and R ³ has 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms.
When the carbon number is 1 to 8, it is possible to sufficiently secure the reactivity with the inorganic fine particles. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a hexyloxy group and an octyloxy group, and a methoxy group, an ethoxy group and a propoxy group are preferable.

In the general formula (1), Q represents a divalent linking group having a total of 1 to 18 carbon atoms, which may have a heteroatom,
It may have a substituent. The total number of carbon atoms in Q is preferably 2-8. Since the carbon number is 1 to 18, water,
The solubility in alcoholic solvents is sufficient and sufficient performance can be secured. Examples of the substituent include a halogen atom, a hydroxyl group, an amino group, an ester group, an ether group, an amide group and the like. The hetero atom, an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom,
Examples thereof include phosphorus atom, and oxygen atom, nitrogen atom, and sulfur atom are preferable.

Specific preferred examples of the divalent linking group include methylene group, ethylene group, propylene group, tetramethylene group, hexamethylene group, xylylene group and the like.

In the general formula (1), A is at least one repeating unit provided from a cationic monomer. Specific examples of the cationic monomer include trimethyl-
p-vinylbenzylammonium chloride, trimethyl-m-vinylbenzylammonium chloride, triethyl-p-vinylbenzylammonium chloride,
Triethyl-m-vinylbenzylammonium chloride, N, N-dimethyl-N-ethyl-Np-vinylbenzylammonium chloride, N, N-diethyl-N
-Methyl-Np-vinylbenzylammonium chloride, N, N-dimethyl-Nn-propyl-Np-
Vinylbenzylammonium chloride, N, N-dimethyl-Nn-octyl-Np-vinylbenzylammonium chloride, N, N-dimethyl-N-benzyl-Np-vinylbenzylammonium chloride,
N, N-diethyl-N-benzyl-N-p-vinylbenzylammonium chloride, N, N-dimethyl-N-
(4-Methyl) benzyl-Np-vinylbenzylammonium chloride, N, N-dimethyl-N-phenyl-N-p-vinylbenzylammonium chloride, trimethyl-p-vinylbenzylammonium bromide, trimethyl-m-vinylbenzyl. Ammonium bromide, trimethyl-p-vinylbenzyl ammonium sulfonate, trimethyl-m-vinyl benzyl ammonium sulfonate, trimethyl-p-vinyl benzyl ammonium acetate, trimethyl-m-vinyl benzyl ammonium 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, 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, methyl chloride, ethyl chloride, methyl bromide, ethyl bromide of N, N-diethylaminopropyl (meth) acrylamide, Me Quaternized products by Ruaiodaido or ethyl iodide, or sulfonate substituted their anions, alkyl sulfonate, acetate or alkyl carboxylate and the like.

Further, in the general formula (1), B is at least one repeating unit provided from a nonionic monomer. Specific examples of the nonionic monomer include, for example,
(Meth) acrylic acid alkyl ester [for example, 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, stearyl (meth) acrylate and the like, alkyl (meth) acrylate having 1 to 18 carbon atoms. Ester, etc.], (meth) acrylic acid cycloalkyl ester [cyclohexyl (meth) acrylate, etc.],
(Meth) acrylic acid aryl ester [phenyl (meth) acrylate, etc.], aralkyl ester [benzyl (meth) acrylate, etc.], substituted (meth) acrylic acid alkyl ester [eg, 2-hydroxyethyl (meth) acrylate, etc. ], (Meth) acrylamides [eg,
(Meth) acrylamide, dimethyl (meth) acrylamide, etc.], aromatic vinyls [styrene, vinyltoluene, α-methylstyrene, etc.], vinyl esters [vinyl acetate, vinyl propionate, vinyl versatate, etc.], allyl esters Examples include [allyl acetate and the like], halogen-containing monomers [vinylidene chloride, vinyl chloride and the like], vinyl cyanide [(meth) acrylonitrile and the like], olefins [ethylene, propylene and the like] and the like.

In the general formula (1), the units represented by A and B may be one kind or a combination of two or more kinds of copolymerizable components.

Further, as the polymer (b), a polymer represented by the following general formula (2) can also be preferably used.

[0040]

[Chemical 9]

[In the general formula (2), R^Four, R^Five, And R
⁶Are each independently a hydrogen atom, saturated or unsaturated
Alky having 1 to 18 carbon atoms which may contain a cyclic structure
Group, an alkoxy group having 1 to 8 carbon atoms, or an ant
Represents an alkyloxy group, R^Four, R^Five, R ⁶At least of
One is an alkoxy group or an aryloxy group,
J is 1 to 1 in total carbon number which may be through a hetero atom.
8 represents a divalent linking group and may have a substituent.
X is a repeating unit provided from a cationic monomer
And Y is a repeating unit provided by a nonionic monomer
Represents r, p, and q are mol% of each repeating unit
Where r is 1 to 50 mol%, p and q are each independently.
It is 0 to 99 mol%. ]

The alkyl group represented by R ⁴ , R ⁵ and R ⁶ has 1 to 18 carbon atoms, preferably 1 to 8 carbon atoms.
When the carbon number is 1 to 8, it is possible to sufficiently secure the reactivity with the inorganic fine particles. Examples of the alkyl group include, for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group,
A tetradecyl group and an octadecyl group are mentioned, and a methyl group, an ethyl group, a propyl group and a butyl group are preferable.

The alkoxy group represented by R ⁴ , R ⁵ and R ⁶ has 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms.
When the carbon number is 1 to 8, it is possible to sufficiently secure the reactivity with the inorganic fine particles. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a hexyloxy group and an octyloxy group, and a methoxy group, an ethoxy group and a propoxy group are preferable.

J is a divalent linking group, an alkylene group,
Arylene group, aralkylene group, -O-, -COO-,
It may be -OCO-, -CONH-, -CONR'-, or a combination thereof. Here, R'represents any of an alkyl group, an aryl group, and an aralkyl group.

In the general formula (2), specific examples of the monomer having a unit having a silyl group include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (2-methoxyethoxy) silane, vinyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane,
Examples thereof include 3- (meth) acryloxypropyltriethoxysilane and 3- (meth) acryloxypropyldimethoxymethylsilane.

In the general formula (2), X and Y are respectively
It has the same meaning as A and B in the general formula (1), and the same specific examples can be given.

(Inorganic Fine Particles) In the ink jet recording sheet of the present invention, the coloring material receiving layer contains inorganic fine particles together with the surface treatment agent and the polymer. When the colorant receiving layer contains the inorganic fine particles, a porous structure is obtained, which improves the ink absorbing performance. Particularly, when the solid content of the inorganic fine particles in the coloring material receiving layer is 50% by mass or more, more preferably more than 60% by mass,
This is preferable because it becomes possible to form a more favorable porous structure, and an inkjet recording sheet having sufficient ink absorbency can be obtained. Here, the solid content of the inorganic fine particles in the color material receiving layer is a content calculated based on components other than water in the composition constituting the color material receiving layer.

Examples of the above-mentioned inorganic fine particles include silica fine particles, colloidal silica, titanium dioxide, barium sulfate, calcium silicate, zeolite, kaolinite, halloysite, mica, talc, calcium carbonate, magnesium carbonate, calcium sulfate, pseudoboehmite, and oxidation. Examples thereof include zinc, zinc hydroxide, alumina, aluminum silicate, calcium silicate, magnesium silicate, zirconium oxide, zirconium hydroxide, cerium oxide, lanthanum oxide and yttrium oxide. Among these, silica fine particles, colloidal silica, alumina fine particles or pseudo-boehmite are preferable from the viewpoint of forming a good porous structure. The inorganic fine particles may be used as the primary particles as they are, or may be used in the state where the secondary particles are formed. The average primary particle size of these inorganic fine particles is preferably 2 μm or less, more preferably 200 nm or less. Further, silica fine particles having an average primary particle diameter of 20 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, or pseudoboehmite having an average pore radius of 2 to 15 nm is more preferable. Especially, silica fine particles, alumina fine particles, and pseudo-boehmite are preferable.

Silica fine particles are generally roughly classified into wet method particles and dry method (gas phase method) particles according to the production method. In the above-mentioned wet method, a method in which activated silica is generated by acid decomposition of a silicate, and the activated silica is appropriately polymerized and coagulated and precipitated to obtain hydrous silica is the mainstream. On the other hand, the vapor phase method is a method by high temperature vapor phase hydrolysis of silicon halide (flame hydrolysis method),
The mainstream method is to obtain anhydrous silica by a method in which silica sand and coke are heated and reduced and vaporized by an arc in an electric furnace, and this is oxidized by air (arc method). It means anhydrous silica fine particles obtained by the method. As the silica fine particles used in the present invention, vapor phase method silica fine particles are particularly preferable.

The above vapor phase silica has different properties from the hydrous silica such as the density of silanol groups on the surface and the presence / absence of pores, and shows different properties, but is suitable for forming a three-dimensional structure having a high porosity. ing. Although the reason for this is not clear, in the case of hydrous silica, the density of silanol groups on the surface of the fine particles is as high as 5 to 8 / nm ² , and the silica fine particles are likely to be densely aggregated (aggregate). In the case of the method silica, since the density of silanol groups on the surface of the fine particles is as few as 2-3 / nm ^2, it is assumed that sparse soft agglomeration (flocculate) occurs, resulting in a structure with a high porosity. To be done.

Since the vapor phase silica has a particularly large specific surface area, it has high ink absorption and retention efficiency, and has a low refractive index. Is provided, and high color density and good color developability are obtained. The transparency of the receiving layer is not only for applications requiring transparency such as OHP, but also for obtaining high color density and good color forming gloss even when applied to recording sheets such as photo glossy paper. is important.

The average primary particle diameter of the vapor phase method silica is preferably 30 nm or less, more preferably 20 nm or less, particularly preferably 10 nm or less, most preferably 3 to 10 nm. In the vapor phase silica, particles are easily attached to each other by hydrogen bonds due to silanol groups, so that a structure having a large porosity can be formed when the average primary particle diameter is 30 nm or less, and the ink absorption characteristics are effectively improved. Can be improved.

The silica fine particles may be used in combination with the above-mentioned other fine particles. When the other fine particles are used in combination with the vapor phase silica, the content of the vapor phase silica in all the fine particles is preferably 30% by mass or more, and more preferably 50% by mass or more.

In the present invention, the inorganic fine particles are also preferably alumina fine particles, alumina hydrate, or a mixture or composite thereof. Of these, alumina hydrate is preferable because it absorbs ink well and fixes it, and pseudo-boehmite (Al ₂ O ₃ .nH ₂ O) is particularly preferable. Alumina hydrate can be used in various forms,
It is preferable to use sol-like boehmite as a raw material because a smooth layer can be easily obtained.

Regarding the pore structure of pseudo-boehmite, its average pore radius is preferably 1 to 30 nm, and 2 to 15 nm.
Is more preferable. The pore volume is 0.3 to 2.0.
ml / g is preferable, and 0.5 to 1.5 ml / g is more preferable. Here, the measurement of the pore radius and the pore volume,
It is measured by a nitrogen adsorption / desorption method and can be measured by, for example, a gas adsorption / desorption analyzer (for example, trade name "Omnisorb 369" manufactured by Coulter, Inc.). Among the alumina fine particles, vapor phase method alumina fine particles are preferable because of their large specific surface area. The average primary particle diameter of the vapor grown alumina is preferably 30 nm or less, more preferably 20 nm or less.

When the above-mentioned inorganic fine particles are used for an ink jet recording sheet, for example, JP-A-10-8106 is used.
No. 4, No. 10-119423, No. 10-157277.
No. 10-217601 and No. 11-348409.
No. 2001-138621 and 2000-43.
401, 2000-212135, 2000-
309157, 2001-96897, 200
1-138627, JP-A-11-91242 and 8
-2087, 8-2090, 8-2091,
8-2093, 8-174992, 11-1
It can be preferably used also in the modes disclosed in the respective publications such as No. 92777 and JP 2001-301314 A.

(Water-Soluble Resin) In the ink jet recording sheet of the present invention, it is preferable that the coloring material receiving layer further contains a water-soluble resin.

The water-soluble resin is, for example, a polyvinyl alcohol resin [polyvinyl alcohol (PV
A), acetoacetyl-modified polyvinyl alcohol, cation-modified polyvinyl alcohol, anion-modified polyvinyl alcohol, silanol-modified polyvinyl alcohol,
Polyvinyl acetal, etc.], cellulosic resin [methyl cellulose (MC), ethyl cellulose (EC), hydroxyethyl cellulose (HEC), carboxymethyl cellulose (CMC), hydroxypropyl cellulose (HPC), hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, etc.], chitins , Chitosans, starch, resins having an ether bond [polyethylene oxide (PEO), polypropylene oxide (PPO), polyethylene glycol (PEG), polyvinyl ether (PVE), etc.], resins having a carbamoyl group [polyacrylamide (PAAM), Polyvinylpyrrolidone (PVP), polyacrylic acid hydrazide, etc.] and the like. Further, polyacrylic acid salts having a carboxyl group as a dissociative group, maleic acid resins, alginates, gelatins and the like can also be mentioned.

Among the above, polyvinyl alcohol resin is particularly preferable. Examples of the polyvinyl alcohol include Japanese Patent Publication No. 4-52786, Japanese Patent Publication No. 5-67432.
No. 7-29479, Japanese Patent No. 2537827
No. 7, Japanese Patent Publication No. 7-75553, and Japanese Patent No. 2502998.
No. 3,053,231, JP-A-63-17617
No. 3, Japanese Patent No. 2604367, and Japanese Patent Laid-Open No. 7-27678.
7, JP-A-9-207425, JP-A-11-589.
41, JP-A-2000-135858, JP-A-2001
-205924, JP 2001-287444 A, JP 62-278080 A, JP 9-39373 A,
Japanese Patent No. 2750433, Japanese Patent Laid-Open No. 2000-158801
No. 2001-213045, 2001-3
28345, JP-A-8-324105, JP-A-11
Examples thereof include those described in each publication such as -348417. Further, examples of the water-soluble resin other than the polyvinyl alcohol-based resin include the compounds described in paragraph Nos. 0011 to 0014 of JP-A No. 11-165461. These water-soluble resins may be used alone or in combination of two or more.

In the present invention, the content of the water-soluble resin is preferably 9 to 40% by mass, and more preferably 12 to 33% by mass, based on the total mass of the solid content of the colorant receiving layer.

In the present invention, the above-mentioned water-soluble resin and the above-mentioned inorganic fine particles, which mainly constitute the colorant receiving layer, may be a single material, or may be a mixed system of a plurality of materials. Good. From the viewpoint of maintaining transparency, the type of water-soluble resin combined with fine particles, especially silica fine particles, is important. When using the vapor phase silica,
The water-soluble resin is preferably a polyvinyl alcohol-based resin, more preferably a polyvinyl alcohol-based resin having a saponification degree of 70 to 100%, and a saponification degree of 80 to 9
A 9.5% polyvinyl alcohol resin is particularly preferred.

The polyvinyl alcohol-based resin has a hydroxyl group in its structural unit. Since the hydroxyl group and the surface silanol group of the silica fine particles form a hydrogen bond, the secondary particles of the silica fine particles are used as a network chain unit. It becomes easy to form a three-dimensional network structure. It is considered that the formation of this three-dimensional network structure forms a colorant receiving layer having a porous structure with high porosity and sufficient strength. In ink jet recording, the porous coloring material-receiving layer obtained as described above rapidly absorbs ink by a capillary phenomenon,
It is possible to form dots having good circularity without causing ink bleeding.

The polyvinyl alcohol resin may be used in combination with the other water-soluble resin. When the other water-soluble resin and the polyvinyl alcohol-based resin are used in combination, the content of the polyvinyl alcohol-based resin in the total water-soluble resin is preferably 50% by mass or more, and more preferably 70% by mass or more.

(Content Ratio of Inorganic Fine Particles to Water-Soluble Resin) Mass ratio of inorganic fine particles (x) to water-soluble resin (y) [P
The B ratio (x / y)] also greatly affects the film structure and film strength of the colorant receiving layer. That is, when the mass content ratio [PB ratio] increases, the porosity, pore volume, and surface area (per unit mass) increase, but the density and strength tend to decrease.

In the present invention, the coloring material-receptive layer has a decrease in film strength and a crack during drying due to the PB ratio being too large as the above-mentioned mass content ratio [PB ratio (x / y)]. To prevent and the PB ratio is too small,
From the viewpoint of preventing the ink absorptivity from being lowered due to the fact that the voids are easily filled with the resin and the void ratio is reduced, 1.5: 1 to 10: 1 is preferable.

Since the recording sheet may be stressed when passing through the transport system of the ink jet printer, the coloring material receiving layer must have sufficient film strength. Further, in the case of cutting into a sheet shape, it is necessary that the coloring material receiving layer has sufficient film strength in order to prevent cracking or peeling of the coloring material receiving layer. Considering these cases, the mass ratio (x / y) is 5: 1.
The following is more preferable, and from the viewpoint of ensuring high-speed ink absorbency in an inkjet printer, it is more preferably 2: 1 or more.

For example, gas phase method silica fine particles having an average primary particle diameter of 20 nm or less and a water-soluble resin are mixed in a mass ratio (x /
y) A three-dimensional network structure having secondary particles of silica fine particles as a network chain when a coating solution which is completely dispersed in an aqueous solution at 2: 1 to 5: 1 is coated on a support and the coating layer is dried. Are formed, the average pore diameter is 30 nm or less, and the porosity is 50 to
It is possible to easily form a light-transmitting porous film having a pore volume of 80%, a specific pore volume of 0.5 ml / g or more, and a specific surface area of 100 m ² / g or more.

(Crosslinking Agent) In the coloring material receiving layer of the ink jet recording sheet of the present invention, the coating layer containing the inorganic fine particles and the water-soluble resin further contains a crosslinking agent capable of crosslinking the water-soluble resin. A preferred embodiment is a porous layer cured by a cross-linking reaction between a water-soluble resin and

The above water-soluble resins, especially polyvinyl alcohol
Boron compounds are preferred for crosslinking the polyol. The boration
Examples of the compound include borax, boric acid, borate (for example,
For example, orthoborate, InBO₃, ScBO₃, YB
O₃, LaBO₃, Mg₃(BO₃) ₂, Co₃(BO₃)₂,
Diborate (eg Mg₂B₂O_Five, Co₂B₂O_Five),
Taborate (eg LiBO₂, Ca (BO₂)₂, N
aBO₂, KBO₂), Tetraborate (eg Na₂B_FourO
₇・ 10H₂O), pentaborate (eg KB_FiveO₈・ 4H
₂O, Ca₂B₆O₁₁・ 7H₂O, CsB_FiveO_Five) Etc.
be able to. Above all, the crosslinking reaction should occur promptly.
Borax, boric acid, and borate are preferable in that
Boric acid is preferred.

As the crosslinking agent for the water-soluble resin, the following compounds other than the boron compound can be used. For example, aldehyde compounds such as formaldehyde, glyoxal, and glutaraldehyde; ketone compounds such as diacetyl and cyclopentanedione; bis (2-chloroethylurea) -2-hydroxy-4,6-dichloro-
1,3,5-triazine, 2,4-dichloro-6-S-
Active halogen compounds such as triazine / sodium salt; divinylsulfonic acid, 1,3-vinylsulfonyl-2-propanol, N, N'-ethylenebis (vinylsulfonylacetamide), 1,3,5-triacryloyl-hexahydro Active vinyl compounds such as -S-triazine; N such as dimethylolurea and methyloldimethylhydantoin
A methylol compound; a melamine resin (eg methylol melamine, alkylated methylol melamine); an epoxy resin;

Isocyanate compounds such as 1,6-hexamethylene diisocyanate; US Pat. No. 301
Nos. 7280 and 2983611; aziridine compounds; carboximide compounds described in U.S. Pat. No. 3,100,704; epoxy compounds such as glycerol triglycidyl ether; 1,6-hexamethylene-N, N '. -Ethyleneimino compounds such as bisethyleneurea; halogenated carboxaldehyde compounds such as mucochloric acid and mucophenoxycyclolic acid; dioxane compounds such as 2,3-dihydroxydioxane; titanium lactate, aluminum sulfate, chromium alum, potassium Examples thereof include metal-containing compounds such as alum, zirconyl acetate and chromium acetate, polyamine compounds such as tetraethylenepentamine, hydrazide compounds such as adipic acid dihydrazide, and low molecular weight compounds or polymers containing two or more oxazoline groups. The above-mentioned crosslinking agents may be used alone or in combination of two or more.

The above-mentioned cross-linking agent is preferably applied as follows when a boron compound is used as an example. That is, the coloring material receiving layer is cross-linked with the coating liquid containing inorganic fine particles, a water-soluble resin containing polyvinyl alcohol, and a boron compound (hereinafter sometimes referred to as “first coating liquid”). It is a cured layer, and the cross-linking curing is (1) at the same time when the coating liquid is applied, and (2) during the dry coating of the coating layer formed by applying the coating liquid, the coating layer is reduced. At any time before showing rate dryness
It is carried out by applying a basic solution of 8 or more (hereinafter, sometimes referred to as "second coating solution") to the coating layer or coating film. The amount of cross-linking agent used is based on the water-soluble resin.
1 to 50 mass% is preferable, and 5 to 40 mass% is more preferable.

(Mordant) In the present invention, a mordant is preferably contained in the colorant-receiving layer in order to improve the water resistance and bleeding resistance of the formed image. As the mordant, a cationic polymer (cationic mordant) as an organic mordant, or an inorganic mordant is preferable, and by allowing the mordant to be present in the colorant-receptive layer, a liquid ink having an anionic dye as a colorant is formed. Can interact with each other to stabilize the coloring material and improve water resistance and bleeding resistance over time. The organic mordant and the inorganic mordant may be used alone, respectively, or the organic mordant and the inorganic mordant may be used in combination.

The mordant is added to the coating liquid containing the inorganic fine particles and the water-soluble resin (first coating liquid), or is contained in the second coating liquid if there is a risk of aggregation with the inorganic fine particles. A coating method can be used.

As the cationic mordant, a polymer mordant having a primary to tertiary amino group or a quaternary ammonium group as a cationic group is preferably used, but a cationic non-polymer mordant is also used. can do. As the polymer mordant, a homopolymer of a monomer having a primary to tertiary amino group and a salt thereof, or a quaternary ammonium salt group (mordant monomer), or the mordant monomer and other monomer (hereinafter, Those obtained as a copolymer or a polycondensation polymer with "non-mordanting monomer") are preferable. Further, these polymer mordants can be used in any form of water-soluble polymer or water-dispersible latex particles.

Examples of the above-mentioned monomer (mordanting 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-Nn
-Propyl-N-p-vinylbenzyl ammonium chloride, N, N-dimethyl-Nn-octyl-N-p
-Vinylbenzylammonium chloride, N, N-dimethyl-N-benzyl-Np-vinylbenzylammonium chloride, N, N-diethyl-N-benzyl-
N-p-vinylbenzylammonium chloride, N,
N-dimethyl-N- (4-methyl) benzyl-Np-
Vinylbenzylammonium chloride, N, N-dimethyl-N-phenyl-Np-vinylbenzylammonium chloride;

Trimethyl-p-vinylbenzylammonium bromide, trimethyl-m-vinylbenzylammonium bromide, trimethyl-p-vinylbenzylammonium sulfonate, trimethyl-m-vinylbenzylammonium sulfonate, trimethyl-p-vinylbenzylammonium acetate, trimethyl- m
-Vinylbenzyl ammonium 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;

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, N, Methyl chloride of N-diethylaminopropyl (meth) acrylamide,
Examples thereof include ethyl chloride, methyl bromide, ethyl bromide, quaternary compounds of methyl iodide or ethyl iodide, and sulfonates, alkylsulfonates, acetates or alkylcarboxylates of which anions are substituted.

Specifically, for example, 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- (methacryloyl) Amino) ethylammonium chloride, trimethyl-
2- (acryloylamino) ethylammonium chloride, triethyl-2- (acryloylamino) ethylammonium chloride, trimethyl-3- (methacryloylamino) propylammonium chloride, triethyl-3- (methacryloylamino) propylammonium chloride, trimethyl-3- (Acryloylamino) propyl ammonium chloride, triethyl-
3- (acryloylamino) propyl ammonium 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, trimethyl-
3- (acryloylamino) propyl ammonium acetate etc. can be mentioned. In addition, as the copolymerizable monomer, N-vinylimidazole, N-vinyl-2-methylimidazole and the like can also be mentioned.

Further, allylamine, diallylamine, derivatives thereof, salts and the like can be used. Examples of such compounds include allylamine, allylamine hydrochloride, allylamine acetate, allylamine sulfate, diallylamine, diallylamine hydrochloride, diallylamine acetate, diallylamine sulfate, diallylmethylamine and salts thereof (as the salt, for example, Hydrochloride, acetate, sulfate, etc.),
Examples thereof include diallylethylamine and salts thereof (for example, hydrochlorides, acetates, sulfates and the like), diallyldimethylammonium salts (for counter anions of the salts chloride, acetate ion sulfates and the like). Since these allylamine and diallylamine derivatives have poor polymerizability in the form of amine, it is common to polymerize in the form of a salt and desalt as necessary. Further, it is also possible to use a unit such as N-vinylacetamide or N-vinylformamide, which is converted into a vinylamine unit by hydrolysis after polymerization, or a salt thereof.

The non-mordant monomer does not contain a basic or cationic moiety such as a primary to tertiary amino group and its salt, or a quaternary ammonium salt group, and interacts with the dye in the inkjet ink. A monomer that does not show or has a substantially small interaction. Examples of the non-mordanting monomer include (meth) acrylic acid alkyl ester; (meth) acrylic acid cycloalkyl ester such as (meth) acrylic acid cyclohexyl; (meth) acrylic acid aryl ester such as (meth) acrylic acid phenyl; Aralkyl esters such as benzyl (meth) acrylate; aromatic vinyls such as styrene, vinyltoluene, α-methylstyrene; vinyl acetate, vinyl propionate,
Vinyl esters such as vinyl versatate; allyl esters such as allyl acetate; halogen-containing monomers such as vinylidene chloride and vinyl chloride; vinyl cyanide such as (meth) acrylonitrile; olefins such as ethylene and propylene. Can be mentioned.

The above-mentioned (meth) acrylic acid alkyl ester has a (meth) alkyl group having 1 to 18 carbon atoms.
Acrylic acid alkyl esters are preferable, for example, methyl (meth) acrylate, ethyl (meth) acrylate,
Propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate,
Examples include hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, and stearyl (meth) acrylate. Among them, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate and hydroxyethyl methacrylate are preferable. The above non-mordanting monomers can also be used alone or in combination of two or more.

Further, as the polymer mordant, polydiallyldimethylammonium chloride, polymethacryloyloxyethyl-β-hydroxyethyldimethylammonium chloride, polyethyleneimine, polyallylamine and its derivatives, polyamide-polyamine resin, cationized starch, dicyandiamide formalin condensation. , Dimethyl-2-hydroxypropylammonium salt polymer, polyamidine, polyvinylamine, dicyan-based cation resin represented by dicyandiamide-formalin polycondensate, polyamine-based cation resin represented by dicyanamide-diethylenetriamine polycondensate, epichlorohydrin- dimethylamine addition polymer, dimethyldiallylammonium phosphorus chloride -SO ₂ copolymers, diallylamine salt -SO Preferable ones are ₂ copolymers, (meth) acrylate-containing polymers having a quaternary ammonium salt group-substituted alkyl group in the ester moiety, and styryl type polymers having a quaternary ammonium salt group-substituted alkyl group.

As the polymer mordant, specifically,
JP-A-48-28325, JP-A-54-74430, JP-A-54-124726, JP-A-55-22766, and JP-A-55.
-142339, 60-2850, 60-2
No. 3851, No. 60-23852, No. 60-2385
No. 3, No. 60-57836, No. 60-60643,
No. 60-118834, No. 60-122940, No. 60-122941, No. 60-122942, No. 6
0-235134, JP-A-1-161236, U.S. Pat.
No. 24, No. 4124386, No. 4193800, No. 4273853, No. 4282305, No. 44502.
24, JP-A-1-161236, 10-8106.
No. 4, No. 10-119423, No. 10-157277.
No. 10-217601 and No. 11-348409.
No. 2001-138621 and 2000-43.
401, 2000-212135, 2000-
309157, 2001-96897, 200
1-138627, JP-A-11-91242 and 8
-2087, 8-2090, 8-2091,
8-2093, 8-174992, 11-1
92777, JP 2001-301314 A, JP-B 5-35162, 5-35163 and 5-351.
No. 64, No. 5-88846, JP-A-7-118333.
No. 2000-344990 and Japanese Patent No. 26488.
No. 47, No. 2661677, etc. are mentioned. Among them, polyallylamine and its derivatives are particularly preferable.

The organic mordant used in the present invention has a weight average molecular weight of 1,000, especially from the viewpoint of preventing bleeding over time.
A polyallylamine of 00 or less and its derivatives are preferable.

In the present invention, various known allylamine polymers and their derivatives can be used as the polyallylamine or its derivative. Such derivatives include:
Salt of polyallylamine and acid (as acid, hydrochloric acid, sulfuric acid,
Inorganic acids such as phosphoric acid and nitric acid, methanesulfonic acid, toluenesulfonic acid, acetic acid, propionic acid, cinnamic acid, (meth)
Organic acids such as acrylic acid, or combinations thereof, or salts obtained by partially salting allylamine), derivatives of polyallylamine by polymer reaction, copolymers of polyallylamine and other copolymerizable monomers (such as Specific examples of the monomer include (meth) acrylic acid esters,
Styrenes, (meth) acrylamides, acrylonitrile, vinyl esters and the like).

Specific examples of polyallylamine and its derivatives include JP-B-62-31722 and JP-B-2-1.
No. 4364, Japanese Patent Publication No. 63-43402, No. 63-434
03, 63-45721, 63-29881,
Japanese Patent Publication No. 1-263632, No. 2-56365, No. 2-5
7084, 4-41686, 6-2780, 6-45649, 6-15592, 4-6862.
No. 2, Patent No. 3199227, No. 30083369,
JP-A-10-330427, JP-A-11-21321,
JP-A-2000-281728, 2001-1067
36, JP-A-62-256801, JP-A-7-17
No. 3286, No. 7-213897, No. 9-23531
No. 8, No. 9-302026, No. 11-21321,
Examples thereof include compounds described in WO99 / 21901, WO99 / 19372, JP-A-5-140213, and JP-A-11-506488.

In the present invention, an inorganic mordant may be used as the mordant, and examples thereof include polyvalent water-soluble metal salts and hydrophobic metal salt compounds. Specific examples of the inorganic mordant include, for example, magnesium, aluminum, calcium, scandium, titanium, vanadium, manganese,
Iron, nickel, copper, zinc, gallium, germanium, strontium, yttrium, zirconium, molybdenum, indium, barium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, dysprosium, erbium, ytterbium, hafnium, tungsten, Mention may be made of salts or complexes of metals selected from bismuth.

Specifically, for example, calcium acetate, calcium chloride, calcium formate, calcium sulfate, barium acetate, barium sulfate, barium phosphate, manganese chloride, manganese acetate, manganese formate dihydrate, manganese ammonium sulfate hexahydrate. Substance, cupric chloride, copper (II) chloride dihydrate, copper sulfate, cobalt chloride, cobalt thiocyanate, cobalt sulfate, nickel sulfate hexahydrate,
Nickel chloride hexahydrate, nickel acetate tetrahydrate, nickel ammonium sulfate hexahydrate, nickel amidosulfate tetrahydrate, aluminum sulfate, aluminum alum, basic polyaluminum hydroxide, aluminum sulfite, aluminum thiosulfate, Polyaluminum chloride, aluminum nitrate nonahydrate, aluminum chloride hexahydrate, ferrous bromide, ferrous chloride, ferric chloride, ferrous sulfate, ferric sulfate, zinc phenolsulfonate, odor Zinc oxide, zinc chloride,
Zinc nitrate hexahydrate, zinc sulfate, titanium tetrachloride, tetraisopropyl titanate, titanium acetylacetonate,
Titanium lactate, zirconium acetylacetonate, zirconyl acetate, zirconyl sulfate, ammonium zirconium carbonate, zirconyl stearate, zirconyl octylate, zirconyl nitrate, zirconium oxychloride, zirconium hydroxychloride, chromium acetate, chromium sulfate, magnesium sulfate, magnesium chloride hexahydrate Hydrate, magnesium citrate nonahydrate, sodium phosphotungstate,
Sodium tungsten citrate, 12 tungstophosphoric acid n hydrate, 12 tungstosilicic acid 26 hydrate, molybdenum chloride, 12 molybdophosphoric acid n hydrate, gallium nitrate, germanium nitrate, strontium nitrate, yttrium acetate, yttrium chloride, Yttrium nitrate, indium nitrate, lanthanum nitrate, lanthanum chloride, lanthanum acetate, lanthanum benzoate, cerium chloride, cerium sulfate,
Examples thereof include cerium octylate, praseodymium nitrate, neodymium nitrate, samarium nitrate, europium nitrate, gadolinium nitrate, dysprosium nitrate, erbium nitrate, ytterbium nitrate, hafnium chloride and bismuth nitrate.

In the present invention, the inorganic mordant is preferably an aluminum-containing compound such as basic polyaluminum hydroxide, a titanium-containing compound, a zirconium-containing compound, or a metal compound (salt or complex) of Group IIIB series of the Periodic Table of Elements. . Mordant amount contained in the colorant receiving layer in the present ^{invention, 0.01g / m 2 ~5g / m} 2 are preferred,
0.1g / m ² ~3g / m ² is more preferable.

(Other Components) The ink jet recording sheet of the present invention may further contain various known additives such as acids, ultraviolet absorbers, antioxidants, fluorescent brighteners, monomers and polymerization initiators, if necessary. Agent, polymerization inhibitor, anti-bleeding agent,
An antiseptic, a viscosity stabilizer, a defoaming agent, a surfactant, an antistatic agent, a matting agent, an anti-curl agent, a water resistant agent and the like can be contained.

In the present invention, the coloring material receiving layer may contain an acid. By adding an acid, the surface pH of the colorant receiving layer is adjusted to 3 to 8, preferably 5 to 7.5. This is preferable because the yellowing resistance of the white background portion is improved. The surface pH is measured by the Japan Pulp and Paper Technology Association (J. TAPP
In the measurement of the surface pH defined in I), the measurement is performed by the method A (coating method). For example, the measurement can be carried out using a paper surface pH measuring set “type MPC” manufactured by Kyoritsu Rikagaku Kenkyusho Co., Ltd. corresponding to the method A.

Specific examples of acids include formic acid, acetic acid, glycolic acid, oxalic acid, propionic acid, malonic acid, succinic acid, adipic acid, maleic acid, malic acid, tartaric acid, citric acid, benzoic acid and phthalic acid. , Isophthalic acid, glutaric acid, gluconic acid, lactic acid, aspartic acid, glutamic acid, salicylic acid, salicylic acid metal salt (Zn, Al, C
a, salts such as Mg), methanesulfonic acid, itaconic acid, benzenesulfonic acid, toluenesulfonic acid, trifluoromethanesulfonic acid, styrenesulfonic acid, trifluoroacetic acid, barbituric acid, acrylic acid, methacrylic acid, cinnamic acid, 4 -Hydroxybenzoic acid, aminobenzoic acid, naphthalenedisulfonic acid, hydroxybenzenesulfonic acid,
Toluenesulfinic acid, benzenesulfinic acid, sulfanilic acid, sulfamic acid, α-resorcinic acid, β-resorcinic acid, γ-resorcinic acid, gallic acid, phloroglysin, sulfosalicylic acid, ascorbic acid, erythorbic acid, bisphenolic acid, hydrochloric acid, nitric acid , Sulfuric acid, phosphoric acid,
Examples thereof include polyphosphoric acid, boric acid, and boronic acid. The addition amount of these acids may be determined so that the surface pH of the colorant receiving layer becomes 3 to 8.

The above-mentioned acids are metal salts (for example, salts of sodium, potassium, calcium, cesium, zinc, copper, iron, aluminum, zirconium, lanthanum, yttrium, magnesium, strontium, cerium, etc.) or amine salts (for example, ammonia, Triethylamine, tributylamine, piperazine, 2-methylpiperazine, polyallylamine, etc.).

In the present invention, the colorant receiving layer preferably contains a preservative improving agent such as an ultraviolet absorber, an antioxidant and a bleeding inhibitor. These UV absorbers, antioxidants,
Examples of the anti-bleeding agent include alkylated phenol compounds (including hindered phenol compounds), alkylthiomethylphenol compounds, hydroquinone compounds, alkylated hydroquinone compounds, tocopherol compounds, thiodiphenyl ether compounds, compounds having two or more thioether bonds, and bisphenol. Compounds, O-, N- and S-benzyl compounds, hydroxybenzyl compounds, triazine compounds, phosphonate compounds, acylaminophenol compounds, ester compounds, amide compounds, ascorbic acid, amine antioxidants, 2- (2-hydroxyphenyl) ) Benzotriazole compounds, 2-hydroxybenzophenone compounds, acrylates, water-soluble or hydrophobic metal salts, organometallic compounds, metal complexes, hindered amine compounds (TEM (Including O compound), 2- (2-hydroxyphenyl) 1,3,5-triazine compound, metal deactivator, phosphite compound, phosphonite compound, hydroxyamine compound, nitrone compound, peroxide scavenger, polyamide Stabilizer, polyether compound, basic co-stabilizer, nucleating agent, benzofuranone compound, indolinone compound, phosphine compound, polyamine compound, thiourea compound, urea compound, hydrazito compound, amidine compound, sugar compound, hydroxybenzoic acid compound, dihydroxy Examples thereof include benzoic acid compounds and trihydroxybenzoic acid compounds.

Among these, alkylated phenol compounds, compounds having two or more thioether bonds, bisphenol compounds, ascorbic acid, amine antioxidants, water-soluble or hydrophobic metal salts, organometallic compounds, metal complexes, Preferred are hindered amine compounds, hydroxyamine compounds, polyamine compounds, thiourea compounds, hydrazide compounds, hydroxybenzoic acid compounds, dihydroxybenzoic acid compounds, trihydroxybenzoic acid compounds and the like.

Specific examples of the compounds are described in Japanese Patent Application No. 2002-13.
005, JP-A-10-182621, and JP-A-2001.
-260519, Japanese Patent Publication No. 4-34953, Japanese Patent Publication 4
-34513, JP-A-11-170686, JP-B-4-34512, EP1138509, JP-A-60.
-67190, JP-A-7-276808, JP-A-20
01-94829, JP-A-47-10537, and JP-A-5-10537.
8-111942, 58-212844, 59
-19945, 59-46646, 59-10.
No. 9055, No. 63-53544, Japanese Patent Publication No. 36-10
No. 466, No. 42-26187, No. 48-30492.
No. 48-31255, No. 48-41572, No. 48-54965, No. 50-10726, U.S. Patent Nos. 2,719,086, 3,707,375, and 3,754,919. No. 4,220,711,

Japanese Examined Patent Publication Nos. 45-4699 and 54-532
No. 4, European Published Patent Nos. 223739, 309.
No. 401, No. 309402, No. 310551, No. 310552, No. 459416, German Published Patent No. 3435443, JP-A-54-48535, No. 6
0-107384, 60-107383, 60
-125470, 60-125471, 60-
125472, 60-287485, 60-2
87486, 60-287487, 60-28
7488, 61-160287, 61-185.
No. 483, No. 61-211079, No. 62-1466.
No. 78, No. 62-146680, No. 62-14667.
No. 9, No. 62-282885, No. 62-262047.
No. 63-051174, No. 63-89877,
63-88380, 66-88381, 63
-113536,

63-163351 and 63-203.
372, 63-224989, 63-2512
No. 82, No. 63-267594, No. 63-18248.
4, JP-A-1-239382, and JP-A-2-2626.
No. 54, No. 2-71262, No. 3-121449,
No. 4-291685, No. 4-291688, No. 5-
61166, 5-1149449, 5-1886
No. 87, No. 5-188686, No. 5-110490
No. 5-1108437, No. 5-170361,
Examples thereof include those described in JP-B-48-43295, JP-A-48-33212, US Pat. Nos. 4,814,262, and 4,980,275.

The other components may be used alone or in combination of two or more. These other components may be added after being made water-soluble, dispersed, polymer-dispersed, emulsified, oil-dropped, or encapsulated in microcapsules. In the inkjet recording sheet of the present invention,
The addition amount of the above-mentioned other components is 0.01 to 10 g.
/ M ² is preferred.

In the present invention, the coating liquid for the color material receiving layer preferably contains a surfactant. As the surfactant, any of cationic, anionic, nonionic, amphoteric, fluorine-based, and silicon-based surfactants can be used. Examples of the nonionic surfactants include polyoxyalkylene alkyl ethers and polyoxyalkylene alkylphenyl ethers (for example, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxy). Ethylene nonyl phenyl ether, etc.), oxyethylene / oxypropylene block copolymer, sorbitan fatty acid esters (eg, sorbitan monolaurate, sorbitan monooleate, sorbitan trioleate, etc.), polyoxyethylene sorbitan fatty acid esters (eg, polyoxyethylene) Sorbitan monolaurate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan Lyoleate), polyoxyethylene sorbitol fatty acid esters (eg, tetraoleic acid polyoxyethylene sorbit), glycerin fatty acid esters (eg, glycerol monooleate), polyoxyethylene glycerin fatty acid esters (monostearic acid polyoxyethylene) Ethylene glycerin, polyoxyethylene glycerin monooleate, etc.), polyoxyethylene fatty acid esters (polyethylene glycol monolaurate, polyethylene glycol monooleate, etc.), polyoxyethylene alkylamines, acetylene glycols (eg 2, 4, 7 , 9
-Tetramethyl-5-decyne-4,7-diol, and ethylene oxide adducts and propylene oxide adducts of the diols) and the like, and polyoxyalkylene alkyl ethers are preferable. The nonionic surfactant can be used in the first coating liquid and the second coating liquid. Further, the nonionic surfactants may be used alone or in combination of two or more kinds.

Examples of the amphoteric surfactant include amino acid type, carboxyammonium betaine type, sulfolammonium betaine type, ammonium sulfate ester betaine type, imidazolium betaine type and the like. For example, US Pat. No. 3,843,368. Specification, JP-A-5
9-49535, 63-236546,
What is described in Unexamined-Japanese-Patent No. 5-303205, 8-262742, 10-282619 etc. can be used conveniently. As the amphoteric surfactant,
Amino acid type amphoteric surfactants are preferable, and as the amino acid type amphoteric surfactants, as described in JP-A-5-303205, for example, derivatized from an amino acid (glycine, glutamic acid, histidine acid, etc.) Examples thereof include N-aminoacylic acid having a long-chain acyl group introduced and salts thereof. The amphoteric surfactants may be used alone or in combination of two or more.

Examples of the anionic surfactants include fatty acid salts (eg sodium stearate, potassium oleate),
Alkyl sulfate ester salts (eg sodium lauryl sulfate, triethanolamine lauryl sulfate), sulfonates (eg sodium dodecylbenzenesulfonate),
Examples thereof include alkyl sulfosuccinates (for example, sodium dioctyl sulfosuccinate), alkyl diphenyl ether disulfonates, alkyl phosphates and the like. Examples of the cationic surfactant include alkylamine salts,
Examples thereof include primary ammonium salts, pyridinium salts and imidazolium salts.

Examples of the above-mentioned fluorine-containing surfactant include compounds derived from an intermediate having a perfluoroalkyl group by a method such as electrolytic fluorination, telomerization and oligomerization. Examples thereof include perfluoroalkyl sulfonates, perfluoroalkyl carboxylates, perfluoroalkyl ethylene oxide adducts, perfluoroalkyl trialkyl ammonium salts, perfluoroalkyl group-containing oligomers, perfluoroalkyl phosphates and the like.

As the silicone-based surfactant, silicone oil modified with an organic group is preferable, and a structure in which a side chain of a siloxane structure is modified with an organic group, a structure in which both ends are modified, or a structure in which one end is modified is adopted. obtain. Examples of the organic group modification include amino modification, polyether modification, epoxy modification, carboxyl modification, carbinol modification, alkyl modification, aralkyl modification, phenol modification, and fluorine modification.

In the present invention, the content of the surfactant is 0.001 to 2.0 with respect to the coating liquid for the colorant receiving layer.
% Is preferable, and 0.01 to 1.0% is more preferable. When two or more coating liquids for the color material receiving layer are used for coating, it is preferable to add a surfactant to each coating liquid.

In the present invention, the colorant receiving layer preferably contains a high boiling organic solvent for preventing curling. The high-boiling point organic solvent is an organic compound having a boiling point of 150 ° C. or higher under normal pressure and is a water-soluble or hydrophobic compound. These may be liquid or solid at room temperature, and may be low molecular weight or high molecular weight.
Specifically, aromatic carboxylic acid esters (eg, dibutyl phthalate, diphenyl phthalate, phenyl benzoate, etc.), aliphatic carboxylic acid esters (eg, dioctyl adipate, dibutyl sebacate, methyl stearate, dibutyl maleate) , Dibutyl fumarate, acetyl triethyl citrate, etc.), phosphates (eg trioctyl phosphate, tricresyl phosphate etc.), epoxies (eg epoxidized soybean oil, epoxidized fatty acid methyl etc.), alcohols (eg stearyl) Alcohol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, glycerin, diethylene glycol monobutyl ether (DE
GMBE), triethylene glycol monobutyl ether, glycerin monomethyl ether, 1,2,3-butanetriol, 1,2,4-butanetriol, 1,
2,4-pentanetriol, 1,2,6-hexanetriol, thiodiglycol, triethanolamine,
Polyethylene glycol etc.), vegetable oil (eg soybean oil, sunflower oil etc.) and higher aliphatic carboxylic acid (eg linoleic acid, oleic acid etc.) and the like.

(Support) In the present invention, the support may be either a transparent support made of a transparent material such as plastic or an opaque support made of an opaque material such as paper. In order to make the most of the transparency of the colorant receiving layer, it is preferable to use a transparent support or a highly glossy opaque support.

As a material usable for the transparent support, a material which is transparent and has a property of withstanding radiant heat when used in an OHP or a backlight display is preferable. Examples of the material include polyesters such as polyethylene terephthalate (PET); polysulfone,
Examples thereof include polyphenylene oxide, polyimide, polycarbonate and polyamide. Among them, polyesters are preferable, and polyethylene terephthalate is particularly preferable. The thickness of the transparent support is not particularly limited, but is preferably 50 to 200 μm from the viewpoint of easy handling.

As the highly glossy opaque support, one having a glossiness of 40% or more on the surface on which the colorant receiving layer is provided is preferable. The glossiness is JIS P-814.
It is a value obtained according to the method described in 2 (75-degree specular gloss test method for paper and paperboard). Specific examples include the following supports.

For example, high gloss paper supports such as art paper, coated paper, cast coated paper, baryta paper used for silver salt photographic supports, polyesters such as polyethylene terephthalate (PET), nitrocellulose. Cellulose esters such as cellulose acetate and cellulose acetate butyrate, and plastic films such as polysulfone, polyphenylene oxide, polyimide, polycarbonate and polyamide are made opaque by containing a white pigment and the like (may be subjected to surface calendering treatment). High-gloss film; or a high-gloss film containing the above various paper supports, the above-mentioned transparent supports or white pigments, etc., provided with a polyolefin coating layer containing or not containing a white pigment. And a support or the like. A white pigment-containing expanded polyester film (for example, expanded PET in which polyolefin fine particles are contained and voids are formed by stretching) can also be preferably mentioned. Further, resin coated paper used for silver salt photographic printing paper is also suitable.

The thickness of the opaque support is not particularly limited, but is preferably 50 to 300 μm from the viewpoint of handleability.

The surface of the support may be subjected to a corona discharge treatment, a glow discharge treatment, a flame treatment, an ultraviolet irradiation treatment or the like in order to improve the wetting property and the adhesiveness.

Next, the base paper used for the resin coated paper will be described in detail. The base paper is made from wood pulp as a main raw material, and if necessary, synthetic paper such as polypropylene, or synthetic fiber such as nylon or polyester is used in addition to wood pulp. Examples of the wood pulp include LBKP, LBSP, NBKP, NBS
Any of P, LDP, NDP, LUKP and NUKP can be used, but LBKP and NBS with a large amount of short fibers
It is preferable to use more P, LBSP, NDP, and LDP. However, the ratio of LBSP and / or LDP is preferably 10% by mass or more and 70% by mass or less.

As the above pulp, a chemical pulp containing few impurities (sulfate pulp or sulfite pulp) is preferably used,
Pulp that has been bleached to improve its whiteness is also useful.

In the base paper, sizing agents such as higher fatty acids and alkyl ketene dimers, white pigments such as calcium carbonate, talc and titanium oxide, paper strengthening agents such as starch, polyacrylamide and polyvinyl alcohol, fluorescent whitening agents, A water retention agent such as polyethylene glycol, a dispersant, and a softening agent such as quaternary ammonium can be appropriately added.

The freeness of the pulp used for papermaking is as follows.
According to CSF regulations, 200 to 500 ml is preferable, and
The fiber length after beating is preferably 30 to 70% of the sum of the 24% mesh residual mass% and the 42 mesh residual mass% defined by JIS P-8207. The mass% of the 4-mesh residue is preferably 20 mass% or less.

The basis weight of the base paper is preferably 30 to 250 g, particularly preferably 50 to 200 g. The thickness of the base paper is preferably 40 to 250 μm. The base paper can be given a high smoothness by calendering at the papermaking stage or after the papermaking. The base paper density is 0.7 to 1.2 g / m ² (J
ISP-8118) is common. Furthermore, the stiffness of the base paper is 2 under the conditions specified in JIS P-8143.
0 to 200 g is preferable.

A surface sizing agent may be applied to the surface of the base paper, and as the surface sizing agent, the same sizing agent as that which can be added to the base paper can be used. The pH of the base paper is JI
It is preferably 5 to 9 when measured by the hot water extraction method specified in SP-8113.

The polyethylene for covering the front surface and the back surface of the base paper is mainly low-density polyethylene (LDPE) and / or high-density polyethylene (HDPE), but other LLDPE, polypropylene or the like can be partially used.

In particular, the polyethylene layer on the side for forming the colorant-receiving layer contains rutile or anatase type titanium oxide, a fluorescent whitening agent, and ultramarine blue in polyethylene, as is commonly used in photographic printing paper. However, those having improved opacity, whiteness and hue are preferred. Here, the content of titanium oxide is generally 3 to 3 with respect to polyethylene.
20 mass% is preferable and 4-13 mass% is more preferable. The thickness of the polyethylene layer is not particularly limited, but 10 to 50 μm is suitable for both the front and back layers. Further, an undercoat layer may be provided on the polyethylene layer in order to impart adhesion to the coloring material receiving layer. As the undercoat layer, aqueous polyester, gelatin and PVA are preferable. Further, the thickness of the undercoat layer is preferably 0.01 to 5 μm.

The polyethylene-coated paper can be used as a glossy paper, and when polyethylene is melt-extruded on the surface of the base paper for coating, a so-called embossing treatment is performed to obtain a matte surface or a matte surface obtained by ordinary photographic printing paper. It is also possible to use those having a silk surface.

A back coat layer may be provided on the support, and the components that can be added to this back coat layer are:
Examples include white pigments, aqueous binders, and other components. Examples of the white pigment contained in the back coat layer include light calcium carbonate, heavy calcium carbonate, kaolin, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulfide, zinc carbonate, satin white, and aluminum silicate. , Diatomaceous earth, calcium silicate, magnesium silicate, synthetic amorphous silica, colloidal silica,
Colloidal alumina, pseudo-boehmite, aluminum hydroxide, alumina, lithopone, zeolite, hydrohaloisite, magnesium carbonate, white inorganic pigments such as magnesium hydroxide, styrene plastic pigment, acrylic plastic pigment, polyethylene, microcapsule, urea resin, melamine Examples include organic pigments such as resins.

Examples of the aqueous binder used in the back coat layer include styrene / maleate copolymer, styrene / acrylate copolymer, polyvinyl alcohol, silanol-modified polyvinyl alcohol, starch,
Examples thereof include water-soluble polymers such as cationized starch, casein, gelatin, carboxymethyl cellulose, hydroxyethyl cellulose and polyvinylpyrrolidone, and water-dispersible polymers such as styrene butadiene latex and acrylic emulsion. Examples of other components contained in the back coat layer include a defoaming agent, a defoaming agent, a dye, a fluorescent brightening agent, a preservative, and a water resistance agent.

(Preparation of Inkjet Recording Sheet) The coloring material-receptive layer of the inkjet recording sheet of the present invention comprises, for example, a first coating liquid containing at least inorganic fine particles and a water-soluble resin on the surface of a support (hereinafter referred to as “coating”). Liquid (A) "is applied, and (1) at the same time as the application, (2) while the application layer formed by the application is being dried and before the application layer exhibits a rate of decrease in drying rate. (3) After the coating layer is dried to form a coating film, a second coating liquid (basic solution, hereinafter "coating liquid (B)") containing at least a mordant and having a pH of 8 or more It may be said that) is applied, and then the coating layer to which the second coating liquid is applied is crosslinked and cured (Wet-on-Wet method). Here, the surface treatment agent (a) and the polymer (b) according to the present invention are preferably contained in at least one of the coating liquid (A) and the coating liquid (B), but the coating liquid (A) is particularly preferable. ) Is more preferable. The cross-linking agent capable of cross-linking the water-soluble resin is the coating liquid (A).
Alternatively, it is preferably contained in at least one of the coating liquid (B) and the third coating liquid different from these coating liquids. It is preferable to provide the color material-receptive layer cross-linked and cured in this way from the viewpoints of ink absorbency and prevention of film cracking.

The above-mentioned method is preferable since a large amount of the mordant is present near the surface of the colorant-receiving layer, so that the ink-jet colorant is sufficiently mordant and the water resistance of characters and images after printing is improved. A part of the mordant may be contained in the coating liquid (A), and in this case, the mordants of the coating liquid (A) and the coating liquid (B) may be the same or different.

In the present invention, the coating liquid for the colorant receiving layer (coating liquid (A)) containing at least inorganic fine particles (for example, vapor-phase method silica) and a water-soluble resin (for example, polyvinyl alcohol) is, for example, It can be prepared as follows. That is, gas phase method silica fine particles, a surface treating agent (a) and a polymer (b) are added to water (for example,
Silica fine particles in water are 10 to 20% by mass), for example, 10,000 rpm by using a high-speed rotating wet colloid mill (for example, "Clearmix" manufactured by M Technique Co., Ltd.).
After being dispersed for 20 minutes (preferably 10 to 30 minutes) under the condition of high-speed rotation of m (preferably 5000 to 20000 rpm), a crosslinking agent (boron compound), polyvinyl alcohol (PVA) aqueous solution (for example, the above-mentioned gas So that the PVA has about 1/3 the mass of the phase method silica)
Can be added, and dispersion is carried out under the same rotation conditions as described above. The obtained coating liquid is in a uniform sol state, and a porous coloring material-receptive layer having a three-dimensional network structure can be formed by coating it on a support by the following coating method and drying it. .

Further, for the preparation of the aqueous dispersion comprising the above vapor phase silica and the dispersant, an aqueous dispersion of vapor phase silica may be prepared in advance, and the aqueous dispersion may be added to the aqueous dispersant solution. The aqueous dispersant solution may be added to the aqueous silica dispersion of the vapor phase method, or may be mixed at the same time. Further, instead of an aqueous dispersion of vapor-phase method silica, powdery vapor-phase method silica may be added to the dispersant aqueous solution as described above. After mixing the vapor phase silica and the dispersant described above, the mixture is atomized using a disperser to obtain an aqueous dispersion having an average particle diameter of 50 to 300 nm. As the disperser used for obtaining the aqueous dispersion, various conventionally known dispersers such as a high-speed rotation disperser, a medium stirring type disperser (ball mill, sand mill, etc.), an ultrasonic disperser, a colloid mill disperser, a high-pressure disperser, etc. Although a disperser can be used, in order to efficiently disperse the lump-shaped fine particles to be formed, a stirring-type disperser,
A colloid mill disperser or a high pressure disperser is preferred.

Further, water, an organic solvent, or a mixed solvent thereof can be used as a solvent in each step. Examples of the organic solvent that can be used for this coating include alcohols such as methanol, ethanol, n-propanol, i-propanol and methoxypropanol, ketones such as acetone and methyl ethyl ketone, tetrahydrofuran, acetonitrile, ethyl acetate, toluene and the like. To be

A dispersant may be added to improve the dispersibility of the coating solution. A cationic polymer can be used as the dispersant. Examples of the cationic polymer include the examples of the mordant described above. It is also preferable to use a silane coupling agent as the dispersant. The amount of the dispersant added to the fine particles is 0.
1% to 30% is preferable, and 1% to 10% is more preferable.

The coating of the coating solution for the color material receiving layer is carried out, for example, by
It can be performed by a known coating method such as an extrusion die coater, an air doctor coater, a bread coater, a rod coater, a knife coater, a squeeze coater, a reverse roll coater, and a bar coater.

The coating liquid (B) is applied to the coating layer at the same time as or after the application of the coating liquid (coating liquid (A)) for the colorant receiving layer. It may be applied before the subsequent coating layer begins to exhibit a decreasing rate of drying. That is, after the coating liquid for the color material receiving layer (coating liquid (A)) is applied, a mordant is introduced while the coating layer shows a constant rate of drying.

The term "before the coating layer starts to exhibit the rate of reduction drying rate" usually refers to a process for a few minutes immediately after the coating liquid for the color material receiving layer is applied, and during this period, the coating is performed. The phenomenon of "constant rate of drying" in which the content of the solvent (dispersion medium) in the applied coating layer decreases in proportion to time is shown. Regarding the time indicating this "constant rate of drying", see, for example, Chemical Engineering Handbook (pages 707 to 712, published by Maruzen Co., Ltd., Showa 5).
October 25, 5).

As described above, after coating the first coating liquid, the coating layer is dried until it exhibits a rate of reduction drying, and this drying is generally at 50 to 180 ° C. for 0.5 to 10 minutes. (Preferably 0.5 to 5 minutes). The drying time naturally depends on the coating amount, but the above range is usually appropriate.

As a method of applying the above-mentioned first coating layer before the rate of drying is decreased, a method of further coating the coating solution (B) on the coating layer, a method of spraying by a method such as spraying, etc. , A method of immersing the support on which the coating layer is formed in the coating liquid (B), and the like.

In the above-mentioned method, the coating method for coating the coating liquid (B) is, for example, a curtain flow coater, an extrusion die coater, an air doctor coater, a bread coater, a rod coater, a knife coater, a squeeze coater, a reverse roll coater. A well-known coating method such as a bar coater can be used. However, the extrusion die coater,
It is preferable to use a method such as a curtain flow coater or a bar coater in which the coater does not directly contact the already formed first coating layer.

After applying the mordant solution (coating solution (B)), it is generally heated at 40 to 180 ° C. for 0.5 to 30 minutes to be dried and cured. Among them, 40-1
It is preferable to heat at 50 ° C. for 1 to 20 minutes.

The mordant solution (coating solution (B))
Is applied simultaneously with the application of the colorant-receptive layer coating solution (coating solution (A)), the colorant-receptive layer coating solution (coating solution (A))
And a mordant solution (coating solution (B)) are simultaneously coated on the support (multilayer coating) so that the colorant-receptive-layer coating solution (coating solution (A)) is in contact with the support, and then dried and cured. By doing so, the coloring material receiving layer can be formed.

The simultaneous coating (multilayer coating) can be carried out by a coating method using an extrusion die coater or a curtain flow coater. After the simultaneous coating, the formed coating layer is dried, and the drying in this case is generally 0.5 to 10 at 40 to 150 ° C.
It is carried out by heating for a minute, preferably 40 to
It is carried out by heating at 100 ° C. for 0.5 to 5 minutes.

When the above simultaneous coating (multilayer coating) is carried out by, for example, an extrusion die coater,
The two types of coating liquids discharged at the same time are layered in the vicinity of the discharge port of the extrusion die coater, that is, before being transferred onto the support, and in that state, they are layered on the support. The two layers of coating liquid that have been overlaid before coating tend to undergo a cross-linking reaction at the interface between the two liquids when they are transferred to the support. As a result, the viscosity tends to increase, which may hinder the coating operation. Therefore, in the simultaneous coating as described above, the barrier layer liquid (intermediate layer liquid) is applied together with the coating of the colorant receiving layer coating liquid (coating liquid (A)) and the mordant solution (coating liquid (B)). It is preferable to apply the three layers simultaneously by interposing between the liquids.

The barrier layer liquid can be selected without any particular limitation. For example, an aqueous solution containing a trace amount of a water-soluble resin, water and the like can be mentioned. The above-mentioned water-soluble resin is used in consideration of coatability for the purpose of a thickener and the like, and for example, a cellulosic resin (for example, hydroxypropylmethylcellulose, methylcellulose, hydroxyethylmethylcellulose). Etc.), polyvinylpyrrolidone, and polymers such as gelatin. The mordant may be contained in the barrier layer liquid.

After the color material receiving layer is formed on the support, the surface of the color material receiving layer is smoothed by calendering through a roll nip under heat and pressure using, for example, a super calender or a gloss calender. It is possible to improve properties, glossiness, transparency and coating film strength. However, the calendering process may cause a decrease in the porosity (that is, the ink absorbency may decrease), and therefore, it is necessary to set conditions under which the decrease in the porosity is small.

The roll temperature for calendering treatment is preferably from 30 to 150 ° C., and from 40 to 100 ° C.
C is more preferred. Further, the linear pressure between the rolls during the calendar treatment is preferably 50 to 400 kg / cm,
100 to 200 kg / cm is more preferable.

In the case of ink jet recording, the layer thickness of the color material receiving layer needs to be determined in relation to the porosity in the layer, because it is necessary to have an absorption capacity enough to absorb all the droplets. is there. For example, if the ink amount is 8 nL / mm ²
If the porosity is 60%, the layer thickness is about 15 μm.
The above film is required. Considering this point, in the case of inkjet recording, the layer thickness of the colorant receiving layer is 1
0 to 50 μm is preferable.

The pore diameter of the color material receiving layer is preferably 0.005 to 0.030 μm in terms of median diameter, and 0.01 to
0.025 μm is more preferable. The porosity and the median pore diameter can be measured by using a mercury porosimeter (trade name “Boresizer 9320-PC2” manufactured by Shimadzu Corporation).

The colorant-receiving layer preferably has excellent transparency. As a guideline, the haze value when the colorant-receiving layer is formed on a transparent film support is 30.
% Or less, and more preferably 20% or less. The haze value is a haze meter (HG
M-2DP: It can be measured using Suga Test Instruments Co., Ltd.

A polymer fine particle dispersion may be added to the constituent layers of the ink jet recording sheet of the present invention (for example, a color material receiving layer or a back layer). This polymer fine particle dispersion is used for the purpose of improving physical properties of the film such as dimensional stabilization, curl prevention, adhesion prevention, and film cracking prevention. For the polymer fine particle dispersion, see Japanese Patent Laid-Open No.
2-245258, 62-1316648, 6
It is described in each publication of 2-110066. When a polymer fine particle dispersion having a low glass transition temperature (40 ° C. or lower) is added to the layer containing the mordant, cracking or curling of the layer can be prevented. Further, even if a polymer fine particle dispersion having a high glass transition temperature is added to the back layer,
Curling can be prevented.

The ink jet recording sheet of the present invention is disclosed in JP-A Nos. 10-81064 and 10-11942.
No. 3, No. 10-157277, No. 10-217601.
No. 11-348409, JP 2001-1386 A.
21, No. 2000-43401, No. 2000-21
No. 1235, No. 2000-309157, No. 2001.
-96897, 2001-138627, JP-A-11-91242, 8-2087, 8-209.
It can also be prepared by the method described in each publication of No. 0, No. 8-2091, and No. 8-2093.

[0150]

EXAMPLES The present invention will now be described in detail with reference to examples, but the present invention is not limited to these examples. In addition, "parts" and "%" in Examples represent "parts by mass" and "mass%" unless otherwise specified, and "average molecular weight".
And "degree of polymerization" represent "weight average molecular weight" and "mass average degree of polymerization".

First, synthetic examples of the polymer (b) according to the present invention used in Examples and the polymers used in Comparative Examples will be shown. (Synthesis Example 1) N- [2- (methacryloyloxy) ethyl] -N, N, N-trimethylammonium chloride 2
2.1 parts of 3-mercaptopropyltrimethoxysilane (2.94 parts) was dissolved in 100 parts of methanol and heated to 65 ° C. under a nitrogen stream to obtain 2,2′-azobis (2-amidinopropane) dihydrochloride (Wako Pharmaceuticals Co., Ltd., trade name: V-
50) 0.081 part was added and the mixture was further heated for 4 hours to obtain a 25% methanol solution of polymer 1 (weight average molecular weight: 2000).

Synthesis Example 2 Polymer 2 was prepared in the same manner as in Synthesis Example 1 except that N- [2- (methacryloyloxy) ethyl] -N, N, N-trimethylammonium chloride was changed to 2-hydroxyethyl acrylate. A 25% methanol solution of (weight average molecular weight: 1500) was obtained.

(Synthesis Example 3) N- [2- (methacryloyloxy) ethyl] -N, N, N-trimethylammonium chloride 10.8 parts, methyl methacrylate 10.8
Part, 3-mercaptopropyltrimethoxysilane 2.9
Dissolve 4 parts in 100 parts of methanol and 65 under a nitrogen stream.
Heat to ℃, add (V-50) 0.081 parts and further 4
Polymer 3 (weight average molecular weight: 160
A 25% methanol solution of 0) was obtained.

Synthesis Example 4 Methacryloyloxypropyltrimethoxysilane 5.4 parts, N- [2- (methacryloyloxy) ethyl] -N, N, N-trimethylammonium chloride 19.6 parts, 2-mercaptoethanol 0 156 parts of methanol was dissolved in 65 parts of methanol, the mixture was heated to 65 ° C. under a nitrogen stream, 0.081 parts of (V-50) was added, and the mixture was further heated for 4 hours to give Polymer 4 (weight average molecular weight: 10000). A 25% methanol solution was obtained.

(Synthesis Example 5) The same as Synthesis Example 4 except that N- [2- (methacryloyloxy) ethyl] -N, N, N-trimethylammonium chloride of Synthesis Example 4 was changed to 2-hydroxyethyl acrylate. Polymer 5
A 25% methanol solution of (weight average molecular weight: 8000) was obtained.

(Synthesis Example 6) Methacryloyloxypropyltrimethoxysilane 5.4 parts, N- [2- (methacryloyloxy) ethyl] -N, N, N-trimethylammonium chloride 14.2 parts, methyl methacrylate 5.
4 parts, 0.156 parts of 2-mercaptoethanol are dissolved in 100 parts of methanol and heated to 65 ° C. under a nitrogen stream,
25% of the polymer 6 (weight average molecular weight: 7000) was obtained by adding 0.081 part of (V-50) and heating for 4 hours.
A methanol solution was obtained.

Synthesis Example 7 Polymer 7 was prepared in the same manner as in Synthesis Example 1, except that 3-mercaptopropyltrimethoxysilane in Synthesis Example 1 was changed to 2-mercaptoethanol.
A 25% methanol solution of (weight average molecular weight: 2000) was obtained.

(Synthesis Example 8) N- [2- (methacryloyloxy) ethyl] -N, N, N-trimethylammonium chloride 19.6 parts, methyl methacrylate 5.4 parts,
2-mercaptoethanol 0.156 parts with methanol 1
It is dissolved in 00 parts and heated to 65 ° C. under a nitrogen stream, (V-
50) 0.081 part was added and the mixture was heated for another 4 hours to obtain a 25% methanol solution of polymer 8 (weight average molecular weight: 10,000).

(Preparation of Support) Wood pulp consisting of 100 parts of LBKP was beaten with a double disc refiner to a Canadian freeness of 300 ml, and 0.5 part of epoxidized behenic acid amide, 1.0 part of anionic polyacrylamide, and 0.1 part of polyamide polyamine epichlorohydrin. 1 part and 0.5 parts of cationic polyacrylamide were added at an absolutely dry mass ratio to the pulp, and weighed with a Fourdrinier paper machine to make 170 g / m ² of base paper.

To adjust the surface size of the above-mentioned base paper, 0.04% of a fluorescent whitening agent ("Whitex BB" manufactured by Sumitomo Chemical Co., Ltd.) was added to a 4% aqueous solution of polyvinyl alcohol.
The base paper was added and impregnated into the above-mentioned base paper so as to be 0.5 g / m ^{2 in} terms of absolute dry weight, dried, and then calendered to obtain a base paper whose density was adjusted to 1.05 g / ml. Obtained.

The wire surface (back surface) side of the obtained base paper was subjected to corona discharge treatment, and then high density polyethylene was coated to a thickness of 19 μm using a melt extruder, and a resin layer composed of a matte surface was formed. Was formed (hereinafter, the resin layer surface is referred to as “back surface”). The resin layer on the back side is further subjected to corona discharge treatment, and then, as an antistatic agent, aluminum oxide (“Alumina sol 100” manufactured by Nissan Chemical Industries, Ltd.) and silicon dioxide (manufactured by Nissan Chemical Industries, Ltd.) Snowtex O ") was dispersed in water at a mass ratio of 1: 2, and the resulting dispersion was applied so that the dry mass would be 0.2 g / m ² .

Further, after the corona discharge treatment was applied to the felt surface (front surface) side where the resin layer was not provided, anatase type titanium dioxide 10%, a trace amount of ultramarine blue, and an optical brightening agent 0.01% ( Polyethylene) and low density polyethylene with MFR (melt flow rate) 3.8 are extruded using a melt extruder to a thickness of 29 μm, and a high-gloss thermoplastic resin layer is provided on the surface side of the base paper. (Hereinafter, this high-gloss surface is referred to as "front surface") to form a support.

Example 1 <Preparation of Coating Liquid A for Coloring Material Receiving Layer> Gas phase method silica fine particles having the following composition, ion-exchanged water, the polymer 1 and the compound 1-1 were mixed and rotated at high speed. Using a formula colloid mill (“Clearmix” manufactured by M Technique Co., Ltd.), the mixture was dispersed at a rotation speed of 10,000 rpm for 20 minutes, and then the following polyvinyl alcohol, boric acid, polyoxyethylene lauryl ether, and ion-exchanged water. Was added and the dispersion was carried out again at a rotation speed of 10000 rpm for 20 minutes to prepare a coating liquid A for a color material receiving layer. Mass ratio of fine silica particles and water-soluble resin (PB ratio =
:) is 4.5: 1, and is the coating liquid A for the colorant receiving layer.
Its pH was 3.5 and it was acidic.

[0164] (Composition of coating solution A for colorant receiving layer) Gas phase method silica fine particles (inorganic fine particles) 10.0 parts   ("Roseir QS30" manufactured by Tokuyama Corp., average primary particle size 7 nm) Deionized water 51.7 parts Polymer 1 (25% methanol solution) 0.4 part Compound 1-1 (molecular weight: 236, 10% methanol solution) 1.0 part Polyvinyl alcohol (water-soluble resin) 8% aqueous solution 27.8 parts   ("PVA124" manufactured by Kuraray Co., saponification degree 98.5%, polymerization degree 2400) Boric acid (crosslinking agent) 0.4 parts Polyoxyethylene lauryl ether (surfactant) 1.2 parts ("Emulgen 109P" (10% aqueous solution, manufactured by Kao Corporation, HLB value 13.6) Deionized water 33.0 parts

<Preparation of Inkjet Recording Sheet> The front surface of the support was subjected to corona discharge treatment, and then the coating solution A for the colorant receiving layer obtained above was applied to the front surface of the support by an extrusion die coater. 200 ml using
/ M ² coating amount (coating process), and the solid content concentration of the coating layer is 2 at 80 ° C. (air velocity 3 to 8 m / sec) with a hot air dryer.
It was dried to 0%. This coating layer exhibited a constant drying rate during this period. Immediately thereafter, it is immersed in a mordant solution A (basic solution) having the following composition for 30 seconds to adhere 20 g / m ² thereof onto the coating layer (step of applying the mordant solution), and further dried at 80 ° C. for 10 minutes. (Drying step). Thus, the ink jet recording sheet of Example 1 provided with the color material receiving layer having a dry film thickness of 32 μm was produced. The pH of the mordant solution A was 9.6.

[0166] (Composition of mordant solution A) Boric acid (crosslinking agent) 0.65 parts Polyallylamine "PAA-10C" 10% aqueous solution 25 parts   (Mordant, manufactured by Nittobo Co., Ltd.) Deionized water 59.7 parts Ammonium chloride (surface pH adjuster) 0.8 parts Polyoxyethylene lauryl ether (surfactant) 10 parts   ("Emulgen 109P" manufactured by Kao Corporation, 2% aqueous solution, HLB value 13.6) MegaFac “F1405” 10% aqueous solution 2.0 parts   (Fluorine-based surfactant manufactured by Dainippon Ink and Chemicals, Inc.)

(Examples 2 to 10) Compound 1 of Example 1-
Inkjet recording sheets of Examples 2 to 10 were prepared in the same manner as in Example 1 except that the compounds and polymers shown in Table 1 were used instead of 1 and polymer 1, respectively.

Example 11 Mordant Solution A of Example 7
An ink jet recording sheet of Example 11 was produced in the same manner as in Example 7 except that the above was changed to the mordant solution B shown below. The pH of the mordant solution B is 9.4.
Met. The polyallylamine derivative 1 was synthesized as follows.

(Synthesis of Polyallylamine Derivative 1) Polyallylamine ("PAA-10C" manufactured by Nitto Boseki Co., Ltd.)
Of 10% aqueous solution of 114.0 parts of acrylonitrile 2.7
Parts and stirred at room temperature for 8 hours, and water was added to adjust the concentration to obtain a 10% aqueous solution of polyallylamine derivative 1 (compound obtained by cyanoethylating a part of amino groups of polyallylamine). .

[0170] (Composition of mordant solution B) Boric acid (crosslinking agent) 2.5 parts Ion-exchanged water 69.5 parts Polyallylamine derivative 1 10% aqueous solution 25 parts Polyoxyethylene lauryl ether 2 parts Ammonium chloride 1 part

(Example 12) In Example 1 (composition of coating material A for colorant receiving layer), compound 1-1 was added to basic aluminum chloride (Al ₂ (OH) ₅ Cl, molecular weight: 175, 4).
Example 1 except that the 0.25 part of 0% aqueous solution) was used.
An ink jet recording sheet of Example 12 was produced in the same manner as in.

(Example 13) In Example 2 (composition of coating material A for colorant receiving layer), compound 1-1 was changed to 0.3 part of zirconyl acetate (molecular weight: 225, 30% aqueous solution). In the same manner as in Example 1, an ink jet recording sheet of Example 13 was produced.

(Comparative Example 1) An ink jet recording sheet of Comparative Example 1 was prepared in the same manner as in Example 1 except that the coating material A for coloring material receiving layer of Example 1 was changed to the coating solution B for coloring material receiving layer. Was produced.

[0174] (Composition of coating liquid B for colorant receiving layer) Gas phase method silica fine particles (inorganic fine particles) 10.0 parts   ("Roseir QS30" manufactured by Tokuyama Corp., average primary particle size 7 nm) Deionized water 51.7 parts Polymer 1 (25% aqueous solution) 0.4 part   (Dispersant, manufactured by Nitto Boseki Co., Ltd.) Polyvinyl alcohol (water-soluble resin) 8% aqueous solution 27.8 parts   ("PVA124" manufactured by Kuraray Co., saponification degree 98.5%, polymerization degree 2400) Boric acid (crosslinking agent) 0.4 parts Polyoxyethylene lauryl ether (surfactant) 1.2 parts ("Emulgen 109P" (10% aqueous solution, manufactured by Kao Corporation, HLB value 13.6) Deionized water 33.0 parts

(Comparative Example 2) Inkjet recording of Comparative Example 2 was carried out in the same manner as Comparative Example 1 except that the polymer 1 was changed to the polymer 4 in the composition of the coloring material receiving layer coating liquid B of Comparative Example 1. A sheet was prepared.

Comparative Examples 3 to 4 In the same manner as in Example 1 except that the polymer 1 was changed to the polymer 7 or the polymer 8 in the composition of the coating material A for the colorant receiving layer of Example 1. As a result, inkjet recording sheets of Comparative Examples 3 to 4 were produced.

(Comparative Example 5) A color material-receptive layer coating solution A of Example 1 was changed to the colorant-receptive layer coating solution C shown below.
An inkjet recording sheet of Comparative Example 5 was produced in the same manner as in Example 1.

[0178] (Composition of coating liquid C for colorant receiving layer) Gas phase method silica fine particles (inorganic fine particles) 10.0 parts   ("Roseir QS30" manufactured by Tokuyama Corp., average primary particle size 7 nm) Deionized water 51.7 parts Silane coupling agent (Compound 1-1) (20% methanol solution) 1.0 part "PAS-M-1" (60% aqueous solution) 0.83 parts   (Dispersant, manufactured by Nitto Boseki Co., Ltd.) Polyvinyl alcohol (water-soluble resin) 8% aqueous solution 27.8 parts   ("PVA124" manufactured by Kuraray Co., saponification degree 98.5%, polymerization degree 2400) Boric acid (crosslinking agent) 0.4 parts Polyoxyethylene lauryl ether (surfactant) 1.2 parts ("Emulgen 109P" (10% aqueous solution, manufactured by Kao Corporation, HLB value 13.6) Deionized water 33.0 parts

(Comparative Example 6) Comparative Example 6 was carried out in the same manner as in Example 1 except that the coloring material-receptive layer coating solution A in Example 1 was changed to the following coloring material-receptive layer coating solution D. An inkjet recording sheet was prepared.

[0180] (Composition of coating liquid D for colorant receiving layer) Gas phase method silica fine particles (inorganic fine particles) 10.0 parts   ("Roseir QS30" manufactured by Tokuyama Corp., average primary particle size 7 nm) Deionized water 51.7 parts "PAS-M-1" (60% aqueous solution) 0.83 parts   (Dispersant, manufactured by Nitto Boseki Co., Ltd.) Polyvinyl alcohol (water-soluble resin) 8% aqueous solution 27.8 parts   ("PVA124" manufactured by Kuraray Co., saponification degree 98.5%, polymerization degree 2400) Boric acid (crosslinking agent) 0.4 parts Polyoxyethylene lauryl ether (surfactant) 1.2 parts ("Emulgen 109P" (10% aqueous solution, manufactured by Kao Corporation, HLB value 13.6) Deionized water 33.0 parts

(Evaluation Test) The following evaluation tests were carried out on each of the ink jet recording sheets of the present invention obtained as described above. The test results are shown in Table 1 below.

<Water resistance> Ink jet recording printer ("PM-900C" manufactured by Seiko Epson Corp.)
On each ink jet recording sheet, using yellow, magenta, cyan, black, green, blue,
A solid image of red and red was printed, and after 10 seconds, a paper was contacted and pressed on the solid image, and the degree of transfer of the ink to the paper was evaluated according to the following evaluation criteria. [Evaluation Criteria] A: Ink transfer is not recognized B: Partial transfer is recognized

<Printing Density> A black solid image was printed on each inkjet recording sheet using an inkjet printer (“PM-900C” manufactured by Seiko Epson Corp.), and the printing screen was left after standing for 3 hours. The reflection density of was measured with a Macbeth reflection densitometer and evaluated according to the following evaluation criteria. [Evaluation Criteria] A: When the reflection density is 2.4 or more B: When the reflection density is 2.0 to less than 2.4 C: When the reflection density is less than 2.0

<Time-lapse rainbow-1> Inkjet printer (“PM-900” manufactured by Seiko Epson Corporation)
C ”) was used to print a grid-like linear pattern (line width 0.28 mm) in which magenta and black ink were adjacent to each other on each inkjet recording sheet. After leaving for 3 hours after printing, it was stored in a thermo-hygrostat at a temperature of 40 ° C. and a relative humidity of 90% for 3 days, and the line width of the black portion was measured and evaluated according to the following evaluation criteria. [Evaluation Criteria] A: When the line width is less than 0.30 mm and almost no bleeding with time is observed B: When the line width is 0.30 to less than 0.35 mm and some bleeding with time is observed C: When the line width is 0.35 mm or more and marked bleeding with time is observed

<Time-dependent rainbow-2> Inkjet printer (“PM-900” manufactured by Seiko Epson Corporation)
C ”) was used to print a grid-like linear pattern (line width 0.28 mm) in which magenta and black ink were adjacent to each other on each inkjet recording sheet. Immediately after printing, seal the recording sheet in a clear file and set the temperature to 35
The sample was stored in a thermo-hygrostat at 85 ° C and a relative humidity of 85% for 3 days, and the line width of the black part was measured and evaluated according to the following evaluation criteria. [Evaluation Criteria] A: When the line width is less than 0.30 mm and almost no bleeding with time is observed B: When the line width is 0.30 to less than 0.35 mm and some bleeding with time is observed C: When the line width is 0.35 mm or more and marked bleeding with time is observed

<Light resistance> A solid image of magenta was printed on each ink jet recording sheet using an ink jet printer ("PM-900C" manufactured by Seiko Epson Corporation), and then ultraviolet rays in a wavelength range of 365 nm or less were used. Xenon Wea through a filter that cuts
Using a ther-ometer Ci65A (manufactured by ATLAS), the lamp was lit for 3.8 hours under environmental conditions of temperature 25 ° C and relative humidity 32%, and then the lamp was extinguished at a temperature of 20 ° C and relative humidity 91%. A cycle of standing for 1 hour under environmental conditions was performed for 168 hours. The image density of each color before and after this test was measured using a reflection densitometer (Xrit
"Xrite 938" manufactured by e.), and the residual ratio of each color density was calculated and evaluated according to the following evaluation criteria. [Evaluation Criteria] A: When the residual rate is 90% or more B: When the residual rate is 80 to less than 90% C: When the residual rate is 70 to less than 80% D: When the residual rate is less than 70%

<Gas resistance> A solid image of cyan was printed on each inkjet recording sheet using an inkjet printer ("PM-900C" manufactured by Seiko Epson Corp.), and the ozone concentration was 2.5 ppm. It was stored in the environment for 24 hours. The cyan densities before and after storage were measured using a reflection densitometer (“Xrite 9 manufactured by Xrite”).
38 ") to calculate the residual ratio of the cyan density,
It evaluated according to the following evaluation criteria. [Evaluation Criteria] A: When the residual rate is 80% or more B: When the residual rate is 70 to less than 80% C: When the residual rate is 60 to less than 70% D: When the residual rate is less than 60%

[0188]

[Table 1]

From Table 1, the ink jet recording sheets of the present invention (Examples 1 to 13) containing a surface treating agent for inorganic fine particles and a polymer having a bonding group to the inorganic fine particles are
It was revealed that the recording sheet has a high image density after printing and has little blurring under high temperature and high humidity. Further, it was found that even after a cycle test of irradiation with xenon and leaving at high humidity, the residual density of the formed image was high, and the recording sheet was excellent in light resistance, particularly in magenta color development. It was found that even after storage for a long time in a high-concentration ozone environment, the formed image has a high density residual ratio and is a recording sheet excellent in gas resistance. Further, the ink jet recording sheet of the present invention was excellent in glossiness, ink absorption speed and water resistance. On the other hand, the ink jet recording sheets of Comparative Examples 1, 2 and 6 in which the surface treatment agent for inorganic fine particles according to the present invention was not used had a low residual density of the image after the light resistance test, and thus the polymer according to the present invention In the ink jet recording sheets of Comparative Examples 3 to 6 which were not used, the image density after printing was low, and bleeding with time occurred.

[0190]

EFFECTS OF THE INVENTION According to the present invention, it is strong without cracks and the like, has good ink absorbability, is excellent in image density, and is excellent in light resistance, water resistance and gas resistance of the image area. Further, it is possible to provide an inkjet recording sheet that does not cause bleeding over time even when stored for a long time in a high temperature and high humidity environment.

Claims (14)

[Claims] 1. A sheet for ink jet recording having a colorant-receiving layer on a support, wherein the colorant-receiving layer comprises at least inorganic fine particles and a surface treatment agent having a molecular weight of less than 1000, which modifies the inorganic fine particles. a) and a group capable of forming a bond with the inorganic fine particles by a chemical reaction, and having a weight average molecular weight of 1,000 to 50,000.
And a polymer (b) of 0. 2. The ink jet recording sheet according to claim 1, wherein the inorganic fine particles are inorganic fine particles modified with a surface treatment agent (a). 3. The surface treating agent (a) contains S in the molecule.
The inkjet recording sheet according to claim 1 or 2, which is a compound having at least one selected from the group consisting of i, Ti, Al, and Zr. 4. The polymer (b) is a polymer type silane coupling agent, according to any one of claims 1 to 3.
The inkjet recording sheet according to any one of 1. 5. The polymer (b) has the following general formula (1):
The inkjet recording sheet according to any one of claims 1 to 4, which is represented by the following formula. [Chemical 1] [In the general formula (1), R ¹ , R ² , and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms which may include a saturated or unsaturated cyclic structure, and a carbon number 1 To 8 represent an alkoxy group or an aryloxy group, R
^At least one of ¹ , R ² and R ³ is an alkoxy group or an aryloxy group, and Q represents a divalent linking group having a total of 1 to 18 carbon atoms, which may have a heteroatom, and is substituted. It may have a group. A is a repeating unit provided from a cationic monomer, and B is a repeating unit provided from a nonionic monomer. m and n respectively represent the mol% of the A component and the B component, and m and n are each independently 0 to 100 mol%. ] 6. The ink jet recording sheet according to claim 1, wherein the polymer (b) is at least a polymer represented by the following general formula (2). [Chemical 2] [In the general formula (2), R ⁴ , R ⁵ , and R ⁶ are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms which may contain a saturated or unsaturated cyclic structure, and a carbon number 1 To 8 represent an alkoxy group or an aryloxy group, R
^At least one of ⁴ , R ⁵ and R ⁶ is an alkoxy group or an aryloxy group, and J represents a divalent linking group having 1 to 18 total carbon atoms which may pass through a hetero atom, and a substituent May have. X represents a repeating unit provided from a cationic monomer, and Y represents a repeating unit provided from a nonionic monomer. r, p, and q represent mol% of each repeating unit, and r is 1 to 50.
Mol%, p and q are each independently 0 to 99 mol%. ] 7. The inorganic fine particles are at least one selected from the group consisting of silica fine particles, colloidal silica, alumina fine particles, and pseudo-boehmite, according to any one of claims 1 to 6. The inkjet recording sheet described above. 8. The inkjet recording sheet according to claim 1, wherein the color material receiving layer further contains a water-soluble resin. 9. The water-soluble resin is at least one selected from the group consisting of polyvinyl alcohol resins, cellulose resins, resins having an ether bond, resins having a carbamoyl group, resins having a carboxyl group, and gelatins. The inkjet recording sheet according to claim 8, which is a seed. 10. The ink jet recording sheet according to claim 8, wherein the color material receiving layer further contains a crosslinking agent capable of crosslinking the water-soluble resin. 11. The ink jet recording sheet according to claim 10, wherein the crosslinking agent is a boron compound. 12. The ink jet recording sheet according to claim 1, wherein the color material receiving layer further contains a mordant capable of fixing an anionic dye. 13. The ink jet recording sheet according to claim 12, wherein the mordant is at least one selected from polyallylamine or a derivative thereof, polyvinylamine or a derivative thereof. 14. The first coating liquid, wherein the coloring material receiving layer contains at least inorganic fine particles, the surface treatment agent (a), the polymer (b), and a water-soluble resin on the surface of the support. (1) at the same time as the coating, (2) during the drying of the coating layer formed by the coating and before the coating layer shows a decreasing rate of drying, or (3) drying the coating layer. After forming a coating film by applying the second coating liquid having a pH of 8 or more to any of the above, the crosslinking agent is added to the first coating liquid and the second coating liquid, or the first coating liquid and The ink jet recording sheet according to any one of claims 1 to 13, which is obtained by adding and applying it to at least one of the third coating liquids different from the second coating liquid. .