JP2003300378A - Ink jet recording sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ink jet recording sheet with a coloring material receiving layer capable of forming an image which has satisfactory ink absorption and high resolving power and an excellent ink receiving performance displaying superiority in terms of water resistance, bleeding over time and glossiness and also sufficient ozone resistance for a long time. <P>SOLUTION: In the ink jet recording sheet with a coloring material receiving layer formed on a support, the coloring material receiving layer contains a hydroxamic acid. <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 inkjet recording using ink or the like, and more particularly to an inkjet recording sheet having excellent ink receiving performance and improved ozone resistance of a recorded image.

[0002]

2. Description of the Related Art In recent years, along 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 and put into 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 No)), (7) Water resistance, light resistance, and ozone resistance of the printed area are good, (8) Whiteness of the recording sheet is high,
(9) Storability of the recording sheet is good (no yellowing and coloring even after long-term storage, images do not bleed after long-term storage (good bleeding over time)), (10) Stable and dimensionally stable And the curl is sufficiently small, and (11) hard running property is good. Further, in the use of photo glossy paper used for the purpose of obtaining so-called photo-like high quality recorded matter, in addition to the above-mentioned characteristics, glossiness, glossiness of printed area, surface smoothness, and silver salt photograph are similar. The texture of photographic paper is also required.

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 colorant receiving layer containing fine inorganic pigment particles and a water-soluble resin and having a high porosity is provided on a support. Inkjet recording sheets have been proposed. These recording sheets, especially,
An ink jet recording sheet provided with a coloring material receiving layer having a porous structure using silica as the inorganic pigment fine particles,
With this configuration, it is possible to exhibit excellent ink absorbency, high ink receptivity capable of forming a high resolution image, and high gloss.

However, trace gases in the air, particularly ozone, cause fading of recorded images over time. The recording material consisting of the colorant receiving layer having the above-mentioned porous structure,
Since there are many voids, there is a problem that the recorded image is easily discolored by ozone gas in the air. Therefore, for the recording material having the above-described porous colorant receiving layer, the resistance to ozone in the air (ozone resistance) is
This is a very important property.

In order to prevent fading due to the above ozone,
JP 2001-260519 A proposes an inkjet recording material containing a sulfinic acid compound, a thiosulfonic acid compound, or a thiosulfinic acid compound.
Further, EP1138509 proposes an ink jet recording material containing a thioether compound having a hydrophilic group. All of these are effective in ozone resistance, but the effect is not long-lasting, and there is a problem that sufficient ozone resistance cannot be imparted.

[0008]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is that the colorant-receptive layer can form an image having good ink absorbency and high resolution, and the formed image is
It is an object of the present invention to provide an ink jet recording sheet having sufficient ozone resistance for a long period of time, while having an ink receptive property excellent in blurring with time and glossiness.

[0009]

The means of the present invention for solving the above problems are as follows. <1> An inkjet recording sheet having a colorant receiving layer on a support, wherein the colorant receiving layer contains hydroxamic acids.

<2> The ink jet recording sheet according to <1>, wherein the hydroxamic acid is a compound represented by the following general formula (1).

[0011]

[Chemical 2]

In the general formula (1), R ¹ represents an aliphatic group, an aromatic group or a heterocyclic group. R ² and R ³ are each independently a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, Alternatively, it represents a sulfamoyl group.

<3> The ink jet recording sheet according to <1> or <2>, wherein the color material receiving layer further contains a water-soluble resin. <4> The water-soluble resin is at least one selected from polyvinyl alcohol resins, cellulose resins, ether bond resins, carbamoyl group-containing resins, carboxyl group-containing resins, and gelatins. The inkjet recording sheet according to <3>. <5> The inkjet recording sheet according to <3> or <4>, wherein the color material receiving layer further contains a crosslinking agent capable of crosslinking the water-soluble resin.

<6> The ink jet recording sheet according to any one of <1> to <5>, wherein the color material receiving layer further contains fine particles. <7> The inkjet recording sheet according to <6>, wherein the fine particles are at least one selected from silica fine particles, colloidal silica, alumina fine particles, and pseudo-boehmite. <8> The inkjet recording sheet according to any one of <1> to <7>, wherein the coloring material receiving layer further contains a mordant.

<9> The color material receiving layer is a layer obtained by cross-linking and curing a coating layer applied with a coating liquid containing at least fine particles and a water-soluble resin, and the cross-linking curing is performed by the coating liquid and / or the following. Add a crosslinking agent to the basic solution, and
(1) When the coating liquid is applied to form a coating layer,
Or (2) a basic solution having a pH of 8 or more is applied to the coating layer during the drying of the coating layer formed by applying the coating liquid and before the coating layer exhibits the rate-decreasing drying. <1>, which is performed by giving
The inkjet recording sheet according to any one of <8>.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The ink jet recording sheet of the present invention is characterized in that the coloring material receiving layer provided on the support contains hydroxamic acids. By containing the hydroxamic acids, the ozone resistance of the inkjet recording sheet is remarkably improved. In addition, the colorant receiving layer preferably has a porous structure in order to have both ink absorbability (quick drying) and gloss. Hereinafter, the inkjet recording sheet of the present invention will be described in detail.

(Hydroxamic Acids) The ink jet recording sheet of the present invention is characterized in that the coloring material receiving layer provided on the support contains hydroxamic acids. As the hydroxamic acids in the present invention, compounds represented by the following general formula (1) are preferable.

[0018]

[Chemical 3]

In the general formula (1), R ¹ represents an aliphatic group, an aromatic group or a heterocyclic group. R ² and R ³ are each independently a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, Alternatively, it represents a sulfamoyl group.

The general formula (1) will be described in detail below. When R ¹ , R ² and R ³ represent an aliphatic group,
Examples of the aliphatic group include an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, and the like, and these groups may further have a substituent. Among these, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aralkyl group, and a substituted aralkyl group are preferable,
Particularly, an alkyl group and a substituted alkyl group are preferable. Further, the above aliphatic group may be a chain aliphatic group or a cyclic aliphatic group, and the chain aliphatic group may further have a branch.

Examples of the alkyl group include linear, branched, and cyclic alkyl groups, and the number of carbon atoms in the alkyl group is preferably 1-30, more preferably 1-20. The number of carbon atoms in the alkyl portion of the substituted alkyl group is also preferably within the above range. Specific examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, 2-ethylhexyl group, t-octyl group, decyl group, dodecyl group, octadecyl group, cyclohexyl group. Group, cyclopentyl group, neopentyl group, isopropyl group, isobutyl group and the like.

Examples of the substituent of the substituted alkyl group include a carboxyl group, a sulfo group, a cyano group, a halogen atom (eg, fluorine atom, chlorine atom, bromine atom), a hydroxy group, and an alkoxycarbonyl group having 30 or less carbon atoms (eg, , A methoxycarbonyl group, an ethoxycarbonyl group, a benzyloxycarbonyl group), an aryloxycarbonyl group having 30 or less carbon atoms (for example, a phenoxycarbonyl group), an alkylsulfonylaminocarbonyl group having 30 or less carbon atoms (for example, a methylsulfonylaminocarbonyl group) , Octylsulfonylaminocarbonyl group), arylsulfonylaminocarbonyl group (eg, toluenesulfonylaminocarbonyl group), acylaminosulfonyl group having 30 or less carbon atoms (eg, benzoylaminosulfonyl group, acetyl) Minosuruhoniru group, pivaloyl aminosulfonyl group), number 30 an alkoxy group having a carbon (e.g., methoxy group, an ethoxy group, a benzyloxy group, phenoxyethoxy group, a phenethyloxy group, etc.),
Arylthio groups and alkylthio groups having 30 or less carbon atoms (for example, phenylthio group, methylthio group, ethylthio group,
Dodecylthio group, etc.), an aryloxy group having 30 or less carbon atoms (eg, phenoxy group, p-tolyloxy group, 1-
Naphthoxy group, 2-naphthoxy group, etc.), nitro group, alkyl group having 30 or less carbon atoms, alkoxycarbonyloxy group (eg, methoxycarbonyloxy group, stearyloxycarbonyloxy group, phenoxyethoxycarbonyloxy group), aryloxycarbonyloxy A group (for example, a phenoxycarbonyloxy group, a chlorophenoxycarbonyloxy group);

An acyloxy group having 30 or less carbon atoms (eg, acetyloxy group, propionyloxy group, etc.), an acyl group having 30 or less carbon atoms (eg, acetyl group, propionyl group, benzoyl group, etc.), carbamoyl group (eg, carbamoyl group) Group, N, N-dimethylcarbamoyl group, morpholinocarbonyl group, piperidinocarbonyl group, etc.), sulfamoyl group (for example, sulfamoyl group,
N, N-dimethylsulfamoyl group, morpholinosulfonyl group, piperidinosulfonyl group, etc., alkylsulfonyl group having 30 or less carbon atoms (for example, methylsulfonyl group,
Trifluoromethylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, dodecylsulfonyl group), arylsulfonyl group (for example, benzenesulfonyl group, toluenesulfonyl group, naphthalenesulfonyl group, pyridinesulfonyl group, quinolinesulfonyl group), carbon number 30
The following aryl groups (eg phenyl group, dichlorophenyl group, toluyl group, methoxyphenyl group, diethylaminophenyl group, acetylaminophenyl group, methoxycarbonylphenyl group, hydroxyphenyl group, t-octylphenyl group, naphthyl group), substituted amino groups (Eg, amino group, alkylamino group, dialkylamino group, arylamino group, diarylamino group, acylamino group, etc.), substituted phosphono group (eg, phosphono group, diethylphosphono group, diphenylphosphono group), heterocyclic Group (for example, pyridyl group, quinolyl group, furyl group, thienyl group, tetrahydrofurfuryl group, pyrazolyl group, isoxazolyl group, isothiazolyl group, imidazolyl group,
Oxazolyl group, thiazolyl group, pyridazyl group, pyrimidyl group, pyrazyl group, triazolyl group, tetrazolyl group, benzoxazolyl group, benzimidazolyl group, isoquinolyl group, thiadiazolyl group, morpholino group, piperidino group, piperazino group, indolyl group, isoindolyl group , Thiomorpholino group), ureido group (eg, methylureido group, dimethylureido group, phenylureido group, etc.), sulfamoylamino group (eg, dipropylsulfamoylamino group, etc.), alkoxycarbonylamino group (eg, ethoxy) Carbonylamino group, etc.), aryloxycarbonylamino group (eg, phenyloxycarbonylamino group), alkylsulfinyl group (eg, methylsulfinyl group), arylsulfinyl group (eg, phenylamino). Nils sulfinyl group), a silyl group (e.g., trimethoxysilyl group, triethoxysilyl group), silyloxy groups (for example, trimethylsilyloxy group) and the like.

The above-mentioned carboxyl group, sulfo group, hydroxy group and phosphono group may form a salt.
At that time, as a cation which forms a salt, an organic cationic compound, a transition metal coordination complex cation (Patent 27911)
No. 43) or metal cations (for example, Na ⁺ , K ⁺ , Li ⁺ , Ag ⁺ , Fe ²⁺ , Fe ³⁺ , Cu).
⁺ , Cu ²⁺ , Zn ²⁺ , Al ³⁺ , 1 / 2Ca ^2+, etc.) are preferable. Examples of the organic cationic compound include 4
Quaternary ammonium cation, quaternary pyridinium cation,
Examples thereof include quaternary quinolinium cations, phosphonium cations, iodonium cations, sulfonium cations, and dye cations.

Specific examples of the quaternary ammonium cation include tetraalkylammonium cations (eg, tetramethylammonium cation, tetrabutylammonium cation), tetraarylammonium cations (eg, tetraphenylammonium cation) and the like. Examples of the quaternary pyridinium cation include N-alkylpyridinium cations (for example,
N-methylpyridinium cation), N-arylpyridinium cation (for example, N-phenylpyridinium cation), N-alkoxypyridinium cation (for example, 4-phenyl-N-methoxy-pyridinium cation), N-benzoylpyridinium cation, and the like. To be Examples of the quaternary quinolinium cation include N-
An alkyl quinolinium cation (for example, N-methyl quinolinium cation), an N-aryl quinolinium cation (for example, N-phenyl quinolinium cation), etc. are mentioned. Examples of the phosphonium cation include a tetraarylphosphonium cation (eg, tetraphenylphosphonium cation). As the iodonium cation, a diaryl iodonium cation (for example, a diphenyliodonium cation)
Etc. As the sulfonium cation,
Examples thereof include triarylsulfonium cations (eg, triphenylsulfonium cation).

Further, as a cation which forms a salt, paragraphs [0020] to [00] of JP-A-9-188686.
38] and the like.

Examples of the alkenyl group include linear, branched, and cyclic alkenyl groups, and the number of carbon atoms in the alkenyl group is preferably 2-30, more preferably 2-20. The number of carbon atoms in the alkenyl portion of the substituted alkenyl group is also preferably within the above range. Specific examples of the alkenyl group include, for example, vinyl group, allyl group, prenyl group, geranyl group, oleyl group, cycloalkenyl group (for example, 2-cyclopenten-1-yl group,
2-cyclohexen-1-yl group), bicyclo [2,2
2,1] hept-2-en-1-yl, bicyclo [2,2]
2,2] oct-2-en-4-yl and the like can be mentioned.
Specific examples of the substituent of the substituted alkenyl group include the same substituents as in the case of the substituted alkyl group.

Examples of the alkynyl group include linear, branched, and cyclic alkynyl groups, and the number of carbon atoms of the alkynyl group is preferably 2-30, more preferably 2-20. The above range is also preferable for the number of carbon atoms in the alkynyl portion of the substituted alkynyl group. Specific examples of the alkynyl group include ethynyl group, propargyl group, trimethylsilylethynyl group and the like. Specific examples of the substituent of the substituted alkynyl group include the same substituents as in the case of the substituted alkyl group.

Examples of the aralkyl group include linear, branched, and cyclic aralkyl groups, and the number of carbon atoms in the aralkyl group is preferably 7 to 35, more preferably 7 to 25. The above range is also preferable for the number of carbon atoms in the aralkyl portion of the substituted aralkyl group. Specific examples of the aralkyl group include, for example, benzyl group, methylbenzyl group, octylbenzyl group, dodecylbenzyl group, hexadecylbenzyl group, dimethylbenzyl group, octyloxybenzyl group, octadecylaminocarbonylbenzyl group, chlorobenzyl group and the like. Is mentioned. Specific examples of the substituent of the substituted aralkyl group include the same substituents as in the case of the substituted alkyl group.

When R ¹ , R ² and R ³ represent an aromatic group, examples of the aromatic group include an aryl group and a substituted aryl group. The number of carbon atoms in the aryl group is preferably 6 to 30, more preferably 6 to 20.
The number of carbon atoms in the aryl portion of the substituted aryl group is also preferably within the above range. Specific examples of the aryl group include a phenyl group, an α-naphthyl group, a β-naphthyl group, and the like. These aromatic groups may have a substituent. Examples of the substituent of the substituted aromatic group include the same substituents as in the case of the substituted alkyl group.

When R ¹ , R ² and R ³ represent a heterocyclic group, the heterocyclic group may be a heterocyclic group containing a nitrogen atom, an oxygen atom or a sulfur atom, such as furyl. Group, thienyl group, pyridyl group, pyrazolyl group, isoxazolyl group, isothiazolyl group, imidazolyl group, oxazolyl group, thiazolyl group, pyridazyl group, pyrimidyl group, pyrazyl group, triazolyl group, tetrazolyl group, quinolyl group, benzothiazolyl group, benzoxazolyl Group, benzimidazolyl group, isoquinolyl group, thiadiazolyl group, morpholino group, piperidino group, thiomorpholino group, tetrahydrofurfuryl group, piperazino group, indolyl group, isoindolyl group and the like. These heterocyclic groups may have a substituent. Examples of the substituent of the substituted heterocyclic group include the same substituents as in the case of the above substituted alkyl group.

When R ² and R ³ represent an acyl group, examples of the acyl group include an aliphatic acyl group, an aromatic acyl group and a heterocyclic acyl group. The number of carbon atoms of the acyl group is preferably 1 to 30, and 1 to 20.
Is more preferable. The number of carbon atoms in the acyl moiety of the substituted acyl group is also preferably within the above range. Specific examples of the acyl group include, for example, acetyl group, propionyl group, pivaloyl group, chloroacetyl group, trifluoroacetyl group, 1-methylcyclopropylcarbonyl group, 1
-Ethylcyclopropylcarbonyl group, 1-benzylcyclopropylcarbonyl group, benzoyl group, 4-methoxybenzoyl group, pyridylcarbonyl group, thenoyl group and the like can be mentioned. These acyl groups may have a substituent. Examples of the substituent of the substituted acyl group include the same substituents as in the case of the substituted alkyl group.

When R ² and R ³ represent an alkoxycarbonyl group, examples of the alkoxycarbonyl group include an alkoxycarbonyl group having a substituent and an unsubstituted alkoxycarbonyl group. The number of carbon atoms of the alkoxycarbonyl group is preferably 2-20. Specific examples of the alkoxycarbonyl group include, for example, a methoxycarbonyl group, an ethoxycarbonyl group, an allyloxycarbonyl group, a methoxyethylcarbonyl group, an octyloxycarbonyl group, and the like. Examples of the substituent of the alkoxycarbonyl group having a substituent include the same substituents as in the case of the substituted alkyl group.

When R ² and R ³ represent an aryloxycarbonyl group, examples of the aryloxycarbonyl group include an aryloxycarbonyl group having a substituent and an unsubstituted aryloxycarbonyl group. The number of carbon atoms of the aryloxycarbonyl group is 7 to 3
0 is preferred. Specific examples of the aryloxycarbonyl group include a phenoxycarbonyl group and a naphthoxycarbonyl group. Examples of the substituent of the aryloxycarbonyl group having a substituent include the same substituents as in the case of the above substituted alkyl group.

When R ² and R ³ represent a carbamoyl group, examples of the carbamoyl group include a carbamoyl group having a substituent and an unsubstituted carbamoyl group. The carbamoyl group preferably has 1 to 20 carbon atoms. Specific examples of the carbamoyl group include a carbamoyl group, a methylcarbamoyl group, and a dimethylcarbamoyl group. Examples of the substituent of the carbamoyl group having a substituent include the same substituents as in the case of the substituted alkyl group.

When R ² and R ³ represent an alkylsulfonyl group, examples of the alkylsulfonyl group include a substituted alkylsulfonyl group and an unsubstituted alkylsulfonyl group. The alkylsulfonyl group preferably has 1 to 20 carbon atoms. Specific examples of the alkylsulfonyl group include a methylsulfonyl group, an ethylsulfonyl group, a dodecylsulfonyl group, a trifluoromethylsulfonyl group, and the like. Examples of the substituent of the alkylsulfonyl group having a substituent include the same substituents as in the case of the substituted alkyl group.

When R ² and R ³ represent an arylsulfonyl group, examples of the arylsulfonyl group include an arylsulfonyl group having a substituent and an unsubstituted arylsulfonyl group. The arylsulfonyl group preferably has 6 to 30 carbon atoms. Specific examples of the arylsulfonyl group include a phenylsulfonyl group, a toluenesulfonyl group, a chlorophenylsulfonyl group, a methoxyphenylsulfonyl group, an acetylaminophenylsulfonyl group, and a naphthylsulfonyl group. Examples of the substituent of the arylsulfonyl group having a substituent include the same substituents as in the case of the substituted alkyl group.

When R ² and R ³ represent a sulfamoyl group, examples of the sulfamoyl group include a sulfamoyl group having a substituent and an unsubstituted sulfamoyl group. Specific examples of the sulfamoyl group include a sulfamoyl group, a dimethylsulfamoyl group, and a di (hydroxyethyl) sulfamoyl group. Examples of the substituent of the sulfamoyl group having a substituent include the same substituents as in the case of the substituted alkyl group.

Among the compounds represented by the general formula (1),
The R ¹ is preferably an aliphatic group or an aromatic group. R ² is preferably a hydrogen atom, an aliphatic group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, an alkylsulfonyl group or an arylsulfonyl group, and particularly preferably a hydrogen atom, an aliphatic group or an acyl group. is there. Preferred as R ³ is a hydrogen atom, an aliphatic group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group,
A sulfamoyl group is preferable, and a hydrogen atom, an acyl group, and an alkoxycarbonyl group are particularly preferable.

Specific examples of the compound represented by the general formula (1) in the present invention are shown below, but the present invention is not limited to these compounds.

[0041]

[Chemical 4]

[0042]

[Chemical 5]

[0043]

[Chemical 6]

In the present invention, when the hydroxamic acids are contained in the colorant receiving layer, a water-soluble organic solvent such as alcohol (methanol, ethanol, isopropyl alcohol, ethylene glycol, diethylene glycol, diethylene glycol monobutyl ether, polyethylene glycol, polypropylene) is used. Glycol, glycerin, diglycerin, trimethylolpropane, trimethylolbutane, etc.), ether compounds (tetrahydrofuran, dioxane, etc.), amide compounds (dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc.), ketone compounds (acetone, etc.), etc. It may be added in a state of being mixed and having an increased affinity for water.

When the hydroxamic acids do not have sufficient water solubility, hydrophobic organic solvents such as ester compounds (ethyl acetate, dioctyl adipate, butyl phthalate, methyl stearate, tricresyl phosphite) are used.
Etc.), 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 (hydroxyacetophenone, benzophenone,
Cyclohexane) or the above-mentioned water-soluble organic solvent may be mixed and added. Also, it may be contained as an aqueous dispersion. The form of addition may be oil drops, latex, solid dispersion, polymer dispersion, or the like.

The content of the colorant-receiving layer of the hydroxamic ^{acids, 0.01g / m 2 ~5g / m} 2 are preferred, 0.
05g / m ² ~3g / m ² is more preferable.

(Water-Soluble Resin) In the ink jet recording sheet of the present invention, the coloring material receiving layer preferably contains a water-soluble resin together with the hydroxamic acid.
Examples of the water-soluble resin include polyvinyl alcohol resins that are resins having a hydroxy group as a hydrophilic structural unit [polyvinyl alcohol (PVA), acetoacetyl-modified polyvinyl alcohol, cation-modified polyvinyl alcohol, anion-modified polyvinyl alcohol,
Silanol-modified polyvinyl alcohol, polyvinyl acetal, etc.], cellulose resin [methyl cellulose (M
C), ethyl cellulose (EC), hydroxyethyl cellulose (HEC), carboxymethyl cellulose (C
MC), hydroxypropylcellulose (HPC), hydroxyethylmethylcellulose, hydroxypropylmethylcellulose, etc.], chitins, chitosans, starch, resins having an ether bond [polyethylene oxide (PEO), polypropylene oxide (PPO),
Polyethylene glycol (PEG), polyvinyl ether (PVE), etc.], a resin 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. In addition, examples of water-soluble resins other than polyvinyl alcohol resins include the compounds described in [0011] to [0014] of JP-A No. 11-165461. These water-soluble resins may be used alone or in combination of two or more.

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

(Fine Particles) In the ink jet recording sheet of the present invention, the coloring material receiving layer preferably contains fine particles together with the hydroxamic acid, and it is more preferable to use the fine particles and the water-soluble resin in combination. .

The coloring material receiving layer of the ink jet recording sheet contains fine particles to obtain a porous structure,
This improves the ink absorption performance. In particular, when the solid content of the fine particles in the coloring material receiving layer is 50% by mass or more, more preferably more than 60% by mass, it becomes possible to form a better porous structure, and sufficient ink absorption is achieved. It is preferable since an inkjet recording sheet having the property can be obtained. Here, the solid content of the 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. The fine particles used in the present invention may be either organic fine particles or inorganic fine particles, but inorganic fine particles are preferable from the viewpoint of ink absorbability and image stability.

Preferable organic fine particles include, for example, emulsion polymerization, microemulsion polymerization,
Examples of the polymer fine particles obtained by soap-free polymerization, seed polymerization, dispersion polymerization, suspension polymerization, and the like, specifically, polyethylene, polypropylene, polystyrene, polyacrylate, polyamide, silicone resin, phenol resin, natural polymer Examples thereof include powder, latex or emulsion fine polymer particles.

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 fine particles may be used as primary particles as they are, or may be used in a state where secondary particles are formed. The average primary particle size of these fine particles is preferably 2 μm or less, more preferably 200 nm or less. Furthermore, silica fine particles having an average primary particle size of 20 nm or less, colloidal silica having an average primary particle size of 30 nm or less,
Alumina fine particles having an average primary particle diameter of 20 nm or less, or pseudo-boehmite having an average pore radius of 2 to 15 nm is more preferable, and silica fine particles, alumina fine particles, and pseudo-boehmite are particularly preferable.

The 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-mentioned vapor grown 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 above-mentioned vapor grown silica has a particularly large specific surface area, it has a high ink absorbing property and a high holding 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.

Further, 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.

As the inorganic fine particles used in the present invention, alumina fine particles, alumina hydrate, and a mixture or composite thereof are also preferable. 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. Although various forms of alumina hydrate can be used, sol-like boehmite is preferably used 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.
cc / g is preferable, and 0.5 to 1.5 cc / 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 fine particles are used for an ink jet recording sheet, for example, JP-A-10-81064 is used.
No. 10-119423 and 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
The embodiments disclosed in Japanese Patent Application Laid-Open No. 92777, Japanese Patent Application Laid-Open No. 2001-301314 and the like can also be preferably used.

The above-mentioned water-soluble resin and the above-mentioned fine particles, which mainly constitute the coloring material receiving layer in the present invention, may each be a single material, or may be a mixed system of a plurality of materials. From the viewpoint of maintaining transparency, the type of water-soluble resin combined with fine particles, especially silica fine particles, is important. When the vapor phase silica is used, 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 99.5.
% Polyvinyl alcohol resin is particularly preferred.

The polyvinyl alcohol resin has a hydroxyl group in its structural unit. Since the hydroxyl group and a 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 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
The amount is preferably 50% by mass or more, more preferably 70% by mass or more.

<Content Ratio of Fine Particles to Water-Soluble Resin> The mass content ratio [PB ratio (x: y)] of the fine particles (x) to the water-soluble resin (y) is the film structure and film of the colorant receiving layer. It also has a great impact on strength. That is, when the mass content ratio [PB ratio] increases, the porosity, pore volume, surface area (per unit mass)
, But the density and strength tend to decrease.

The coloring material-receptive layer of the present invention has the above-mentioned mass content ratio [PB ratio (x: y)], which prevents reduction in film strength and cracking during drying due to the PB ratio being too large. In addition, when the PB ratio is too small, the voids are likely to be clogged with the resin, and the ink absorbency is prevented from being lowered due to the reduction of the void ratio.
5: 1 to 10: 1 is preferred.

Since the recording sheet may be stressed when passing through the conveying 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, a gas phase method silica fine particle 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, it is preferable that the coating layer containing the water-soluble resin further contains a crosslinking agent capable of crosslinking the water-soluble resin. A preferred embodiment is a combination of fine particles and the water-soluble resin, and a porous layer cured by a crosslinking reaction between the crosslinking agent and the water-soluble resin.

Boron compounds are preferred for crosslinking the above water-soluble resins, especially polyvinyl alcohol resins. Examples of the boron compound include borax, boric acid, borate (eg orthoborate, InBO ₃ , ScBO ₃ , YB).
_{O 3, LaBO 3, Mg 3} (BO 3) 2, Co 3 (BO 3) 2, two borates _{(e.g., Mg 2 B 2 O 5,} Co 2 B 2 O 5), metaborate salts (e.g., LiBO ₂ , Ca (BO ₂ ) ₂ , NaBO ₂ , K
BO ₂ ), tetraborate (for example, Na ₂ B ₄ O ₇ · 10H
₂ O), pentaborate (eg KB ₅ O ₈ .4H ₂ O, Ca _{2
B 6 O 11 · 7H 2 O} , can be cited CsB ₅ O ₅₎ or the like. Among them, borax, boric acid, and borate are preferable, and boric acid is particularly preferable, because a crosslinking reaction can be rapidly caused.

As the crosslinking agent for the above 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. 301728
No. 0 and No. 2983611, aziridine compounds; US Pat. No. 3,100,704, carboximide compounds; glycerol triglycidyl ether and other epoxy compounds; 1,6-hexamethylene- Ethyleneimino compounds such as N, N′-bisethyleneurea; halogenated carboxaldehyde compounds such as mucochloric acid and mucophenoxycyclolic acid;
Dioxane compounds such as 3-dihydroxydioxane;
Titanium lactate, aluminum sulfate, chrome alum, potassium alum,
Examples thereof include metal-containing compounds such as zirconyl acetate and chromium acetate, polyamine compounds such as tetraethylenepentamine, hydrazide compounds such as adipic acid dihydrazide, and low molecular weight or polymers containing two or more oxazoline groups. The above crosslinking agents may be used alone or in combination of two or more.

Crosslinking and curing are carried out by adding a crosslinking agent to a coating solution containing fine particles, a water-soluble resin and the like (hereinafter sometimes referred to as "coating solution A") and / or the following basic solution, and
(1) When the coating liquid is applied to form a coating layer,
Or (2) a basic solution having a pH of 8 or more (hereinafter, referred to as “coating layer”), either during the drying of the coating layer formed by applying the coating solution and before the coating layer shows the rate-decreasing drying. It is preferable to apply it to the coating layer). The cross-linking agent is preferably applied as described below using a boron compound as an example. That is, the coloring material receiving layer contains a water-soluble resin containing fine particles and polyvinyl alcohol (coating liquid A).
In the case of a layer obtained by cross-linking and curing the coating layer coated with, the cross-linking curing is performed by (1) coating the coating liquid to form the coating layer and (2) coating the liquid by coating the coating liquid. It is performed by applying a basic solution (coating solution B) having a pH of 8 or more (coating solution B) to the coating layer at any time during the dry coating of the layer and before the coating layer shows the rate reduction drying. The boron compound as the crosslinking agent may be contained in either the coating liquid A or the coating liquid B, or may be contained in both the coating liquid A and the coating liquid B. The amount of the cross-linking agent used is preferably from 1 to 50% by mass, more preferably from 5 to 40% by mass, based on the water-soluble resin.

(Mordant) In the present invention, it is preferable that a mordant is 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 may be added to the coating liquid A containing fine particles and a water-soluble resin, or may be added to the coating liquid B when there is a fear of aggregation with the fine particles. Available.

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 (mordant monomer) having a primary to tertiary amino group and a salt thereof, or a quaternary ammonium salt group, or the mordant monomer and another 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 and derivatives thereof, and salts thereof 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 (for example, as the salt, , Hydrochloride, acetate, sulfate, etc.), diallylethylamine and salts thereof (as the salt, for example, hydrochloride, acetate, sulfate, etc.), diallyldimethylammonium salt (chloride as the counter anion of the salt, Acetate ion sulfate ion and the like). Since these allylamine and diallylamine derivatives have poor polymerizability in the form of amine, it is common to polymerize them in the form of a salt and desalt them if necessary. Also,
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-mordanting 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 ink jet 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 cyclohexyl (meth) acrylate; (meth) acrylic acid aryl ester such as phenyl (meth) acrylate;
Aralkyl esters such as benzyl (meth) acrylate;
Aromatic vinyls such as styrene, vinyltoluene and α-methylstyrene; vinyl esters such as vinyl acetate, vinyl propionate and vinyl versatate; allyl esters such as allyl acetate; halogen-containing units such as vinylidene chloride and vinyl chloride Polymers: vinyl cyanide such as (meth) acrylonitrile; olefins such as ethylene and propylene.

As the above-mentioned (meth) acrylic acid alkyl ester, the alkyl moiety has a carbon number of 1 to 18 (meth)
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, dicyandiamine-kaotine resin typified by dicyandiamide-formalin polycondensate, dicyanamide-diaminetriamine polycondensate polyamine-based kaothin resin typified by 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. Nos. 2,484,430 and 2,548,564;
No. 3148061, No. 3309690, No. 4115
No. 124, No. 4124386, No. 4193800,
No. 4273853, No. 4282305, No. 4450
Nos. 224, JP-A-1-161236 and 1
0-81064, 10-119423, 10-
157277, 10-217601, 11-3.
48409, JP 2001-138621 A, 20
00-43401, 2000-212135, 2000-309157, 2001-96897.
No. 2001-138627, JP-A-11-912.
No. 42, No. 8-2087, No. 8-2090, No. 8-
2091, 8-2093, 8-174992.
No. 11-192777, JP 2001-3013A.
No. 14, Japanese Patent Publication No. 5-35162, No. 5-35163
No. 5-35164, No. 5-88846, No. 7-118333, No. 2000-344990,
Examples thereof include those described in Japanese Patent Nos. 2648847 and 2661677. Among them, polyallylamine and its derivatives are particularly preferable.

The organic mordant used in the present invention has a mass 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.

As the polyallylamine or its derivative in the present invention, various known allylamine polymers and their derivatives can be used. As such a derivative, a salt of polyallylamine and an acid (as the 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 of these,
A salt of only a portion of allylamine), a polymer derivative of polyallylamine, a copolymer of polyallylamine and another copolymerizable monomer (specific examples of the monomer are (meth) acrylic acid esters). , Styrenes, (meth) acrylamides, acrylonitrile, vinyl esters, etc.).

Specific examples of polyallylamine and its derivatives include JP-B-62-31722 and JP-B-2-14.
No. 364, Japanese Patent Publication No. 63-43402, No. 63-4340
No. 3, No. 63-5721, No. 63-29881, No. 1-26362, No. 2-56365, No. 2-5
No. 7084, No. 4-41686, No. 6-2780,
6-45649, 6-15592 and 4-68.
No. 622, Patent Nos. 3199227 and 30083369.
No. 10-330427 and 11-21321.
No. 2000-281728, 2001-10
6736, JP-A-62-256801, JP-A-7-
173286, 7-213897, 9-235.
No. 318, No. 9-302026, No. 11-21321
No. 5, WO99 / 21901, WO99 / 19372, JP-A-5-140213, and JP-A No. 11-506488.

An inorganic mordant may be used as the mordant of the present invention, and examples of the inorganic mordant 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,
Mention may be made of salts or complexes of metals selected from erbium, ytterbium, hafnium, tungsten, 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.

As the inorganic mordant in the present invention, an aluminum-containing compound, a titanium-containing compound, a zirconium-containing compound and a metal compound (salt or complex) of Group IIIB series of the Periodic Table of the Elements are preferable. In the present invention, the amount of the mordant contained in the color material receiving layer is 0.01 g / m ^{2 to} 5 g / m ^2.
Is preferred, and 0.1 g / m ^{2 to} 3 g / m ² is more preferred.

(Other Components) The ink jet recording sheet of the present invention may further contain various known additives such as an acid, an ultraviolet absorber, an antioxidant, an optical brightener, a monomer and a polymerization, if necessary. Initiator, 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 A method (coating method). For example, the measurement can be carried out using a paper surface PH measurement set “type MPC” manufactured by Kyoritsu Riken Kagaku Kenkyusho, which corresponds 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 color material receiving layer becomes 3 to 8. The above acids are metal salts (for example, sodium, potassium, calcium, cesium, zinc,
Copper, iron, aluminum, zirconium, lanthanum, yttrium, magnesium, strontium, cerium, etc.) or an amine salt (for example, ammonia, triethylamine, tributylamine, piperazine, 2-methylpiperazine, polyallylamine, etc.) May be.

In the present invention, it is preferable that the colorant receiving layer contains a preservative improving agent such as an ultraviolet absorber, an antioxidant and a blur preventing agent. As these ultraviolet absorbers, antioxidants, and anti-bleeding agents, alkylated phenol compounds (including hindered phenol compounds), alkylthiomethylphenol compounds, hydroquinone compounds, alkylated hydroquinone compounds, tocopherol compounds, thiodiphenyl ether compounds, 2 Compounds having the above thioether bond, bisphenol compounds, O-, N-
And an S-benzyl compound, a hydroxybenzyl compound,
Triazine compound, phosphonate compound, acylaminophenol compound, ester compound, amide compound, ascorbic acid, amine antioxidant, 2- (2-hydroxyphenyl) benzotriazole compound, 2-hydroxybenzophenone compound, acrylate, water-soluble or hydrophobic Metal salt, organometallic compound, metal complex, hindered amine compound (including TEMPO compound), 2- (2-
Hydroxyphenyl) 1,3,5-triazine compound,
Metal deactivators, phosphite compounds, phosphonite compounds, hydroxyamine compounds, nitrone compounds, peroxide scavengers, polyamide stabilizers, polyether compounds, basic co-stabilizers, nucleating agents, benzofuranone compounds, indolinone compounds, phosphine compounds , Polyamine compounds, thiourea compounds, urea compounds, hydrazito compounds, amidine compounds, sugar compounds, hydroxybenzoic acid compounds, dihydroxybenzoic acid compounds, trihydroxybenzoic acid compounds and the like.

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.
No. 005, JP-A-10-182621, JP-A-2
No. 001-260519, Japanese Patent Publication No. 4-34953, Japanese Patent Publication No. 4-34513, JP-A No. 11-170686,
JP-B-4-34512, EP1138509, JP-A-60-67190, JP-A-7-276808, JP-A-2001-94829, and JP-A-47-10537.
No. 58-111942, No. 58-212844.
59, 19945, 59-46646, 59-109055, 63-53544, 36-66466, 42-26187, 48-.
30492, 48-31255, 48-415
72, 48-54965, 50-10726, U.S. Pat. Nos. 2,719,086 and 3,7.
07,375, 3,754,919, 4,22
Each specification of 0,711,

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,
JP-B Nos. 48-43295 and 48-33212, U.S. Pat. Nos. 4,814,262 and 4,98027.
Those described in each specification of No. 5 and the like can be mentioned.

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. The addition amount of the other components in the ink jet recording sheet of the present invention is 0.01 to 10
g / m ² is preferred.

The surface of the inorganic fine particles may be treated with a silane coupling agent for the purpose of improving the dispersibility of the inorganic fine particles. Examples of the silane coupling agent include an organic functional group (for example, vinyl group, amino group (primary to tertiary amino group, quaternary ammonium salt group), epoxy group, mercapto, etc., in addition to the site for coupling treatment. Group, chloro group,
Those having an alkyl group, a phenyl group, an ester group, etc.) are preferable.

In the present invention, the coating liquid for the colorant receiving layer (coating liquid A) preferably contains a surfactant. As the surfactant, any of cationic, anionic, nonionic, amphoteric, fluorine-based, and silicon-based surfactants can be used. As the nonionic surfactant,
Polyoxyalkylene alkyl ethers and polyoxyalkylene alkyl phenyl ethers (for example, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether,
Polyoxyethylene nonylphenyl ether, etc.), oxyethylene / oxypropylene block copolymer, sorbitan fatty acid esters (eg, sorbitan monolaurate, sorbitan monooleate, sorbitan trioleate, etc.), polyoxyethylene sorbitan fatty acid esters (eg, poly Oxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate, etc.),
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 glycerin, mono) Oleic acid polyoxyethylene glycerin, etc.), polyoxyethylene fatty acid esters (polyethylene glycol monolaurate, polyethylene glycol monooleate, etc.), polyoxyethylene alkylamine, acetylene glycols (eg 2, 4,
7,9-tetramethyl-5-decyne-4,7-diol, and ethylene oxide adducts and propylene oxide adducts of the diol) and the like, among which polyoxyalkylene alkyl ethers are preferable. The nonionic surfactant can be used in the coating liquid A and the coating liquid B. Further, the nonionic surfactants may be used alone or in combination of two or more kinds.

Examples of the amphoteric surfactants 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,
Those described in JP-A-5-303205, JP-A-8-262742, JP-A-10-282619 and the like can be preferably used. Among the above amphoteric surfactants, amino acid type, carboxyammonium betaine type, and sulfolammonium betaine type are preferable. The above 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 fluorinated surfactant include compounds derived from an intermediate having a perfluoroalkyl group by a method such as electrolytic fluorination, telomerization, or 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.

The silicone surfactant is preferably an organic group-modified silicone oil, which has a structure in which the side chain of a siloxane structure is modified with an organic group, both ends are modified, or one end is modified. It can have a structure. 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.

The content of the surfactant in the present invention is 0.001 with respect to the coating liquid for the colorant receiving layer (coating liquid A).
Is preferably 2.0% to 2.0%, more preferably 0.01% to 1.0%. 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 point 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) As the support of the present invention, either a transparent support made of a transparent material such as plastic or an opaque support made of an opaque material such as paper can be used.
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 that can be used for the transparent support, a material that 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, plastic films such as polysulfone, polyphenylene oxide, polyimide, polycarbonate and polyamide are made opaque by containing a white pigment or the like (may be subjected to surface calendering treatment). ) A high-gloss film; or a high-gloss film containing the above various paper supports, the above-mentioned transparent support, or a white pigment, etc., provided with a polyolefin coating layer containing or not containing a white pigment. A support etc. are mentioned. 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 it 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 raw 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, NBSP,
Any of LDP, NDP, LUKP, and NUKP can be used, but LBKP, NBSP, which has a large amount of short fibers,
It is preferable to use more 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 may be subjected to a calendering process at the papermaking stage or after the papermaking to give high smoothness. Base paper density is 0.7-1.2g / m2 (JI
SP-8118) is common. Furthermore, the stiffness of the base paper is 20 under the conditions specified in JIS P-8143.
~ 200g is preferred.

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 and back surfaces of the base paper is mainly low-density polyethylene (LDPE) and / or
Alternatively, high density polyethylene (HDPE) may be used, but other LLDPE, polypropylene or the like may be partially used.

In particular, the polyethylene layer on the side for forming the colorant-receiving layer contains rutile or anatase type titanium oxide, an optical brightening agent, and ultramarine blue added to polyethylene, as is widely used in photographic printing paper. However, those having improved opacity, whiteness and hue are preferred. Here, the titanium oxide content is about 3 to 2 relative to polyethylene.
0 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, or when a polyethylene is melt-extruded on the surface of a 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 receiving layer of the inkjet recording sheet of the present invention is prepared, for example, by applying a coating liquid A containing at least fine particles and a water-soluble resin on the surface of a support, and (1) Simultaneous with application, or (2)
Either during the drying of the coating layer formed by the coating and before the coating layer shows the decreasing rate of drying, the pH is set to 8
After applying the coating liquid B described above, a method of crosslinking and curing the coating layer to which the coating liquid B is applied (wet-on-wet method)
Is preferably formed by Here, the hydroxamic acids of the present invention are preferably contained in at least one of the coating liquid A and the coating liquid B. The cross-linking agent capable of cross-linking the water-soluble resin is the coating liquid A or the coating liquid B.
It is preferable to contain in at least one or both. 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 because a large amount of the mordant is present in a predetermined portion of the coloring material receiving layer, so that the coloring material of the ink jet is sufficiently mordanted 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 that case, the coating liquid A and the coating liquid B are included.
The mordants may be the same or different.

In the present invention, the coating liquid for the colorant receiving layer (coating liquid A) containing at least fine particles (for example, vapor phase silica) and water-soluble resin (for example, polyvinyl alcohol) is as follows, for example. Can be prepared. That is, by adding fine particles such as vapor phase method silica and a dispersant to water (for example, silica fine particles in water are 10 to 20% by mass), a high-speed rotary wet colloid mill (for example, "M Technique Co., Ltd." CLEARMIX "), for example, 10000 rpm (preferably 5000 to 20000)
After dispersing for 20 minutes (preferably 10 to 30 minutes) under the condition of high speed rotation of (rpm), a polyvinyl alcohol (PVA) aqueous solution (for example, PVA having a mass of about 1/3 of the vapor phase method silica) is used. When the hydroxamic acids according to the present invention are contained in the coating material for the colorant-receiving layer, they are added and dispersion is performed 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. A disperser can be used, but a medium stirring type disperser, a colloid mill disperser, or a high-pressure disperser is preferable from the viewpoint of efficiently dispersing the formed lump-shaped fine particles.

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 chaotic polymer can be used as the dispersant. Examples of the chaotic 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 liquid for the colorant-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 coating of the coating liquid for the color material receiving layer (coating liquid A), but the coating liquid B reduces the amount of the coating layer after coating. It may be applied before the specific drying rate is exhibited. That is, after the coating liquid for the color material receiving layer (coating liquid A) is coated, the coating liquid B is introduced while the coating layer shows a constant rate of drying, so that it is suitably manufactured. The coating liquid B may contain a mordant.

The term "before the coating layer starts to exhibit a decreasing rate of dryness" usually refers to a process for a few minutes immediately after coating the coating liquid for the colorant receiving layer, and during this period, 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 the coating liquid A is coated, the coating layer is dried until it exhibits a rate of reduction drying, and this drying is generally at 40 to 180 ° C. for 0.5 to 10 minutes (preferably Is performed for 0.5 to 5 minutes). The drying time naturally depends on the coating amount, but the above range is usually appropriate.

As the method for applying the above first coating layer before it exhibits the rate of decrease in drying rate, the coating solution B is further applied onto the coating layer, the method of spraying by a method such as spraying, and the coating method. Examples include a method of immersing the support having the coating layer formed therein in the liquid B.

In the above method, the coating method for applying the coating liquid B is, for example, a curtain flow coater,
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, or a bar coater can be used. However, it is preferable to use a method, such as an extrusion die coater, 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 coating liquid B, it is generally 40 to 180.
It is heated at 0 ° C. for 0.5 to 30 minutes to be dried and cured. Above all, it is preferable to heat at 40 to 150 ° C. for 1 to 20 minutes.

When the coating liquid B is applied simultaneously with the coating of the colorant-receptive layer coating liquid (coating liquid A), the coating liquid A and the coating liquid B are contacted with the support. A colorant-receptive layer can be formed by simultaneous coating (multilayer coating) on a support, followed by drying and curing.

The simultaneous coating (multi-layer 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, for example, by 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, it is preferable to coat the coating liquid A and the coating liquid B together with the barrier layer liquid (intermediate layer liquid) for simultaneous triple layer coating.

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 applying a calendering treatment under heat and pressure through a roll nip using, for example, a super calender or a gloss calender. It is possible to improve the 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, more preferably from 40 to 100 ° C. Further, the linear pressure between the rolls at the time of calendar treatment is preferably 50 to 400 kg / cm, and 10
0 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, since 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 using a mercury porosimeter (trade name “Boa Sizer 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.

The constituent layers of the ink jet recording sheet of the present invention (for example, a color material receiving layer or a back layer) include
A polymer fine particle dispersion may be added. This polymer fine particle dispersion has dimensional stability, curl prevention, adhesion prevention,
It is used for the purpose of improving the physical properties of the film, such as preventing the film from cracking. For the polymer fine particle dispersion, see JP-A-62-1
No. 245258, No. 62-1316648,
It is described in each publication of the above-mentioned 62-110066. 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. Curling can also be prevented by adding a polymer fine particle dispersion having a high glass transition temperature to the back layer.

Further, the ink jet recording sheet of the present invention is disclosed in JP-A-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.

[0151]

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 "weight average degree of polymerization".

(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.

In order to adjust the surface size of the 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 mass, dried and then calendered to obtain a base paper adjusted to a density of 1.05 g / cc. Obtained.

The wire surface (back surface) side of the obtained base paper was subjected to corona discharge treatment and then coated with high density polyethylene using a melt extruder to a thickness of 19 μm, and a resin layer consisting 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 Solution A for Coloring Material Receiving Layer) Fine particles of vapor phase method silica in the following composition, ion-exchanged water, and “PAS-M-1”
Were mixed and dispersed using KD-P (manufactured by Shinmaru Enterprises Co., Ltd.) 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. Add a solution containing
The dispersion was carried out again for 20 minutes at m to prepare a coating material A for the colorant receiving layer. The mass ratio (PB ratio = :) of the silica fine particles to the water-soluble resin was 4.5: 1, and the pH of the coating material A for the colorant receiving layer was 3.5, which was acidic.

[0157] <Composition of colorant receiving layer coating liquid A> Gas phase method silica fine particles (inorganic fine particles) 10.0 parts   ("Roleoseal QS-30" 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

(Preparation of Inkjet Recording Sheet) After the front surface of the support was subjected to corona discharge treatment, 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 after that, it was immersed in a mordant solution B having the following composition for 30 seconds, and 20 g / m ² thereof was applied onto the coating layer.
(Step of applying the mordant solution), and further 80 ° C
It was dried under 10 minutes (drying step). As a result, an inkjet recording sheet (1) of the present invention provided with a coloring material receiving layer having a dry film thickness of 32 μm was produced.

[0159] <Composition of mordant coating liquid B> Boric acid (crosslinking agent) 0.65 parts Polyallylamine "PAA-10C" 10% aqueous solution 25 parts   (Mordant, manufactured by Nittobo Co., Ltd.) 2.5 parts of the following compound (a) 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.)

[0160]

[Chemical 7]

[Examples 2 to 6] In Examples 1 to 6 except that the compound (a) was changed to the following compounds (b) to (f) in <Composition of the coating material A for colorant receiving layer> of Example 1. Inkjet recording sheet (2) of the present invention in the same manner as in 1.
(6) was produced.

[0162]

[Chemical 8]

[Example 7] [PAS-M-1] 0.83 in <Composition of coating liquid A for colorant receiving layer> of Example 1
Part is dimethyldiallylammonium chloride (Daiichi Kogyo Seiyaku Co., Ltd. "Sharol DC-902P", 50%
Example 1 except that the amount of the aqueous solution was changed to 0.6 part.
An ink jet recording sheet (7) of the present invention was produced in the same manner as in.

[Embodiment 8] In the composition of <Coating liquid A for coloring material receiving layer> of Embodiment 1, basic aluminum chloride (Al ₂ (OH) ₅ Cl, “PAC #” manufactured by Taki Chemical Co., Ltd.) is used.
The ink jet recording sheet (8) of the present invention was produced in the same manner as in Example 1 except that 0.63 part of "1000", 40% aqueous solution) was added.

[Example 9] The same as Example 1 except that 0.6 part of zirconyl acetate (30% aqueous solution) was added to <Composition of coating liquid A for coloring material receiving layer> of Example 1. Then, the ink jet recording sheet (9) of the present invention
Was produced.

Comparative Example 1 <Mordant coating liquid B of Example 1
Composition>, a comparative inkjet recording sheet (10) was prepared in the same manner as in Example 1 except that the compound (a) was not used.

[Comparative Example 2] <Mordant coating liquid B of Example 1>
In the composition>, instead of the compound (a), HO (C
A comparative inkjet recording sheet (11) was produced in the same manner as in Example 1 except that 2.5 parts of H ₂ ) ₂ S (CH ₂ ) ₂ S (CH ₂ ) ₂ OH was used. .

(Evaluation Test) Inkjet recording sheets (1) to (9) of the present invention obtained as described above, and comparative inkjet recording sheets (10) and (11).
The following evaluation tests were performed for each of the above. The test results are shown in Table 1 below.

<Ozone resistance> A solid image of magenta and cyan was printed on each ink jet recording sheet using an ink jet printer ("PM-900C" manufactured by Seiko Epson Corp.) to obtain an ozone concentration of 2. 5
It was stored in a ppm environment for 16 hours. The magenta and cyan densities before and after storage were measured using a reflection densitometer (Xrite
"Xrite 938" manufactured by the company), and the residual ratios of the magenta and cyan densities were calculated. When the residual rate is 80% or more, it is A, when it is 70-80%, it is B, and 60-7.
The case of less than 0% was evaluated as C, and the case of less than 60% was evaluated as D.

[0170]

[Table 1]

From the results shown in Table 1 above, the ink jet recording sheets of the present invention (Examples 1 to 9) containing a hydroxamic acid in the colorant receiving layer were stored even in a high concentration ozone environment for a long time. It was found that the formed image has a high density residual ratio and is a recording sheet excellent in ozone resistance. Further, the ink jet recording sheets of the present invention (Examples 8 and 9) in which a metal compound was used in combination also improved the bleeding of images over time. Further, the ink jet recording sheet of the present invention was excellent in all of glossiness, ink absorption speed, image area density and water resistance. On the other hand, the inkjet recording sheet for comparison, which did not use hydroxamic acids, had a low residual density of the image after the test and had insufficient ozone resistance.

[0172]

EFFECTS OF THE INVENTION According to the present invention, the coloring material receiving layer can form an image having a good ink absorbency and a high resolution, and the formed image is excellent in water resistance, bleeding with time, and gloss. It is possible to provide an inkjet recording sheet that has sufficient ozone resistance for a long period of time while having ink receiving performance.

Claims (9)

[Claims] 1. An ink jet recording sheet having a colorant receiving layer on a support, wherein the colorant receiving layer contains hydroxamic acids. 2. The ink jet recording sheet according to claim 1, wherein the hydroxamic acid is a compound represented by the following general formula (1). [Chemical 1] [In the general formula (1), R ¹ represents an aliphatic group, an aromatic group, or a heterocyclic group. R ² and R ³ are each independently a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, Alternatively, it represents a sulfamoyl group. ] 3. The ink jet recording sheet according to claim 1, wherein the color material receiving layer further contains a water-soluble resin. 4. The water-soluble resin is at least one selected from 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 3, wherein 5. The ink jet recording sheet according to claim 3, wherein the color material receiving layer further contains a crosslinking agent capable of crosslinking the water-soluble resin. 6. The ink jet recording sheet according to claim 1, wherein the color material receiving layer further contains fine particles. 7. The inkjet recording sheet according to claim 6, wherein the fine particles are at least one selected from silica fine particles, colloidal silica, alumina fine particles, and pseudo-boehmite. 8. The ink jet recording sheet according to claim 1, wherein the color material receiving layer further contains a mordant. 9. The color material receiving layer is a layer obtained by cross-linking and curing a coating layer coated with a coating liquid containing at least fine particles and a water-soluble resin, and the cross-linking and curing is performed by the coating liquid and / or a base described below. Cross-linking agent is added to the acidic solution, and (1)
Either at the same time when the coating liquid is applied to form a coating layer, or (2) during the drying of the coating layer formed by coating the coating liquid and before the coating layer shows the rate-decreasing drying. The inkjet recording sheet according to any one of claims 1 to 8, which is performed by applying a basic solution having a pH of 8 or more to the coating layer.