JP2003335043A - Ink jet recording sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ink jet recording sheet which is strong and free from a crack or the like, has a good ink absorbing property and is excellent in storage stability of an image part without using a boron compound which is a substance regulated by emission standards. <P>SOLUTION: A receptive layer of a coloring material on a substrate contains (a) a water soluble resin having a functional group to be selected from a carboxyl group, a sulflic group, an acetoacetyl group and an reactive ketone group, (b) a crosslinking agent capable of being reacted with the functional group and (c) a fine particle, and has a three-dimensional mesh structure of 50-80% in a void volume to provide the ink jet recording sheet. <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 an ink or the like, and more particularly to an inkjet recording sheet which can be manufactured without using boron and has little blur over time.

[0002]

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

Further, with the recent increase in resolution of ink jet printers, it has become possible to obtain so-called photograph-like high quality recorded matter. With the progress of such hardware (device), ink jet recording is 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) The storage stability of the recording sheet is good (no yellowing coloring occurs even after long-term storage, images do not bleed after long-term storage (good aging blur)), and (10) stable and dimensional stability And the curl is sufficiently small, and (11) hard running property is good. Further, in the application of photo glossy paper used for the purpose of obtaining so-called photographic-like high quality recorded matter, in addition to the above-mentioned characteristics, gloss, surface smoothness, photographic paper-like texture similar to silver halide photography, etc. 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 coloring material receiving layer containing fine inorganic pigment particles and a water-soluble resin and having a high porosity is provided on a support. Ink jet recording sheets have been proposed. These recording sheets, particularly ink jet recording sheets provided with a coloring material receiving layer having a porous structure using silica as the inorganic pigment fine particles, have excellent ink absorbability due to the constitution and form a high resolution image. It is said that it has a high ink receiving performance to be obtained and can exhibit high gloss. Furthermore, as a means for improving the coating strength of these colorant receiving layers and preventing cracks,
It is widely known to cure a water-soluble resin with a curing agent. As specific examples of such a curing agent, conventionally, epoxy compounds, aldehydes, polyisocyanates, methylol urea, active halogenated compounds, boron and its salts, borax, alum and the like are known. Of these, boric acid and its salts are said to be most preferable.

However, since the boron compound is a wastewater-regulated substance, it is desired to use a substitute thereof in consideration of environmental problems. Ink jet recording sheets provided with a colorant receiving layer having a porous structure that does not use a boron compound are disclosed in JP-A-2001-253661 and JP-A-2001.
-71633, JP-A-2000-253661, and the like. However, these methods cannot obtain sufficient film strength.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to solve the above-mentioned problems of the prior art and achieve the following objects. That is, an object of the present invention is to provide an inkjet recording sheet which does not contain boric acid which is an environmental pollutant, has sufficient film strength, and does not cause blurring with time even when stored for a long time. Especially.

[0008]

In view of the above situation, the present inventors have conducted diligent research and found that the following ink jet recording sheet can solve the above problems without using boric acid. And completed the present invention. That is, the present invention provides the following.

<1> In an ink jet recording sheet having a color material receiving layer on a support, the color material receiving layer is
a) a water-soluble resin having one or more functional groups selected from a carboxyl group, a sulfoxyl group, an acetoacetyl group and a reactive ketone group, b) a crosslinking agent capable of reacting with the functional groups, and c) fine particles. 3 with a porosity of 50-80%
An inkjet recording sheet having a three-dimensional network structure. <2> A metal salt, an amine compound, a hydrazine compound, in which the water-soluble resin is a water-soluble resin having a carboxyl group or a sulfoxyl group, and the cross-linking agent has a valence of 2 or more.
The inkjet recording sheet according to <1>, which is one or more selected from an epoxy compound, an N-methylol compound, an aziridine compound, and an oxazoline compound. <3> The water-soluble resin is a water-soluble resin having an acetoacetyl group, and the crosslinking agent is a metal salt having a valence of 2 or more,
The inkjet recording sheet according to <1>, which is one or more selected from amine compounds, hydrazine compounds, epoxy compounds, and N-methylol compounds. <4> The inkjet recording sheet according to <1>, wherein the water-soluble resin is a water-soluble resin having a reactive ketone group, and the crosslinking agent is an amine compound and / or a hydrazine compound having a valence of 2 or more. <5> The water-soluble resin having a functional group is one or more selected from polyvinyl alcohol resins, polysaccharides, gelatins and acrylic resins <1> to <4
> The ink jet recording sheet according to any one of <1>. <6> One amine compound having a valence of 2 or more
<2> which is a polymer having a secondary, secondary or tertiary amino group
<5> The inkjet recording sheet according to any one of <5>. <7> The inkjet recording sheet according to any one of <1> to <6>, wherein the fine particles are one kind or two or more kinds selected from silica fine particles, alumina fine particles, and pseudo-boehmite. <8><1> to <7>, wherein the colorant receiving layer further contains a mordant capable of fixing an anionic dye.
> The ink jet recording sheet according to any one of <1>. <9> The coloring material receiving layer is formed by applying the coating liquid A containing fine particles and a water-soluble resin on the surface of the support, and (1) simultaneously with the coating, and (2) the coating layer formed by the coating. It is obtained by applying the coating liquid B containing a mordant to the coating layer during drying, before the coating layer shows a rate-decreasing drying, or (3) after drying the coating layer to form a coating film. Any one of <1> to <8>, which is obtained by adding a cross-linking agent to one or more of coating liquid A, coating liquid B, and coating liquid C other than these coating liquids. The inkjet recording sheet described above.

BEST MODE FOR CARRYING OUT THE INVENTION In the ink jet recording sheet of the present invention, the coloring material receiving layer has one or more functional groups selected from a) a carboxyl group, a sulfoxyl group, an acetoacetyl group and a reactive ketone group. Water-soluble resin having a group,
b) A cross-linking agent capable of reacting with the functional group, and c) having fine particles, and having a three-dimensional network structure with a porosity of 50 to 80% do not use boric acid and can reduce bleeding over time. It is characterized by that. Hereinafter, the present invention will be described in detail.

(Water-Soluble Resin) In the present invention, the water-soluble resin contained in the colorant receiving layer is one or more functional groups selected from a carboxyl group, a sulfoxyl group, an acetoacetyl group and a reactive ketone group. Has a group.

The polymer having a carboxyl group can be obtained, for example, by (co) polymerizing a monomer having a carboxyl group. Examples of the monomer having a carboxyl group include (meth) acrylic acid, vinylbenzoic acid, maleic anhydride, and itaconic anhydride. Further, a carboxyl group may be added to the polymer by a polymer reaction. For example, (co) polymerization of a monomer having a carboxylic acid ester group (for example, (meth) acrylate (for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, benzyl (meth) acrylate)). The method of hydrolyzing the polymer obtained by, or carboxylic acid anhydride (for example, malonic anhydride, succinic anhydride,
Trimellitic anhydride, etc.) can be added. Is mentioned. Further, as the polymer having a carboxyl group, polysaccharides (for example, alginic acid, pectin, carboxymethyl cellulose, etc.) or gelatins may be used.

The polymer having a sulfoxyl group can be obtained by (co) polymerizing a monomer having a sulfoxyl group.
Examples of the monomer having a sulfoxyl group include styrenesulfonic acid, (meth) acrylamido-2-methylpropanesulfonic acid, 3-sulfopropyl (meth) acrylate, and allylsulfonic acid. Further, a polysaccharide may be used as the water-soluble resin having a sulfoxyl group, and specific examples thereof include carrageenan and agarose.

The water-soluble resin having an acetoacetyl group is
It is obtained by (co) polymerization of a monomer having an acetoacetyl group. Examples of such a monomer include acetoacetoxyethyl (meth) acrylate. Alternatively, an acetoacetyl group may be added by a polymer reaction.

The water-soluble resin having a reactive ketone group can be obtained by (co) polymerizing a monomer having a reactive ketone group. Examples of such a monomer include diacetone (meth) acrylamide.

Preferred water-soluble resins in the present invention include modified PVA having the above functional groups (eg anion-modified PVA, acetoacetyl-modified PVA, diacetone acrylamide-modified PVA), polysaccharides (eg alginic acid, pectin), gelatins, An acrylic resin (for example, polyacrylic acid) is mentioned, and modified PVA is particularly preferable.

These water-soluble resins may be used alone or in combination of two or more, or may be used in combination with other water-soluble resins. 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.

(Crosslinking Agent) (Crosslinking Agent) In the coloring material receiving layer of the ink jet recording sheet of the present invention, the coating layer containing the fine particles and the water-soluble resin further contains a crosslinking agent capable of crosslinking the water-soluble resin, A porous layer cured by a crosslinking reaction between the crosslinking agent and a water-soluble resin. The cross-linking agent for the water-soluble resin in the present invention forms a cross-link by reacting with a carboxyl group, a sulfoxyl group, an acetoacetyl group or a reactive ketone group contained in the water-soluble resin.

When the water-soluble resin is a water-soluble resin having a carboxyl group or a sulfoxyl group, the crosslinking agent is a metal salt having a valence of 2 or more, an amine compound, a hydrazine compound, an epoxy compound, an N-methylol compound. , One or more selected from aziridine compounds and oxazoline compounds.

Specific examples of metal salts include calcium chloride, calcium sulfate, calcium acetate, calcium propionate, magnesium chloride, magnesium sulfate, zinc chloride, zinc sulfate, zinc acetate, aluminum chloride, aluminum sulfate, aluminum lactate, and tetrachloride. Titanium, titanium lactate, tetraisopropyl titanate, zirconium acetate, zirconium oxychloride, zirconium ammonium carbonate, chrome alum, potassium alum, basic polyaluminum hydroxide, cobalt chloride, first chloride
Iron, ferrous sulfate, ferric chloride, chromium acetate, barium acetate and the like can be mentioned.

Specific examples of the amine compound include ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, isophoronediamine, dicyclohexylmethane-4,4'-diamine, phenylenediamine, diethylenetriamine, Examples thereof include triethylenetetramine, triaminopropane, polymers having an amino group (for example, polyvinylamine, polyethyleneimine, polyallylamine) and the like.

Specific examples of the hydrazine compound include carbohydrazide, thiocarbohydrazide, ethylene-1,
2-dihydrazine, propylene-1,3-dihydrazine, butylene-1,4-dihydrazine, oxalic acid dihydrazide, propionic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide. , Maleic acid dihydrazide, fumaric acid dihydrazide,
Examples thereof include itaconic acid dihydrazide, salicylic acid dihydrazide, isophthalic acid dihydrazide, 4,4′-oxybenzenesulfonyl hydrazide, and a hydrazide group-containing vinyl polymer (for example, aminopolyacrylamide).

Specific examples of the epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, adipic acid diglycidylate, o-phthalic acid diglycidylate, and p-phthalic acid diglycidylate. , Hydroquinone quinglycidyl ether,
Bisphenol diglycidyl ether, resorcin diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane diglycidyl ether, trimethylolpropane triglycidyl ether, neopentyl glycol diglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether , Sorbitol tetraglycidyl ether, pentaerythritol tetraglycidyl ether, diglycerol triglycidyl ether, triglycidyl-tris (2-hydroxyethyl) isocyanurate, and the like.

Specific examples of the N-methylol compound include:
N-methylol urea, methylol dimethyl hydantoin, methylol melamine, etc. are mentioned. Specific examples of the aziridine compound include trimethylolpropane-tri-β-azyldinylpropionate, tetramethylolmethane-tri-β-aziridinylpropionate, N,
N'-diphenylmethane-4,4'-bis (1-aziridinecarbosamide), N.V. N'-hexamethylene-1,
6'-bis (1-aziridinecarboxamide), N,
Specific examples of the oxazoline compound such as N′-toluene-2,4′-bis (1-aziridinecarbosamide) are 1,2-dioxazolinylethane and 1,4.
-Dioxazolinyl butane, 1,4-dioxazolinylbenzene, N, N'-dioxazolinylethylenediamine, vinyl polymers having an oxazolinyl group and the like can be mentioned.

Among these crosslinking agents, aluminum salts,
Zirconium salt, ethylenediamine, triethylenetetramine, polyallylamine, ethylene glycol diglycidyl ether are particularly preferred.

When the water-soluble resin is a water-soluble resin having an acetoacetyl group, the crosslinking agent is selected from metal salts having a valence of 2 or more, amine compounds, hydrazine compounds, epoxy compounds and N-methylol compounds. One type or two or more types are preferable. Specific examples of the crosslinking agent are the same as the above examples. Among these crosslinking agents, aluminum salts, zirconium salts, ethylenediamine, triethylenetetramine, polyallylamine and ethylene glycol diglycidyl ether are particularly preferable.

When the water-soluble resin is a water-soluble resin having a reactive ketone group, the crosslinking agent is preferably one or more selected from amine compounds and hydrazine compounds having a valence of 2 or more. Specific examples of the cross-linking agent include:
It is similar to the above example. Among these crosslinking agents, polyallylamine, adipic acid dihydrazide and aminopolyacrylamide are particularly preferable.

The water-soluble resin / crosslinking agent combination is 1
You may use individually by 1 type or in combination of 2 or more types. The amount of the crosslinking agent used is preferably 1 to 50% by mass, more preferably 5 to 40% by mass, based on the water-soluble resin.

(Fine Particles) In the ink jet recording sheet of the present invention, the coloring material receiving layer contains fine particles in addition to the above water-soluble resin and crosslinking agent. The coloring material receiving layer of the ink jet recording sheet has a porous structure by containing fine particles, which improves the ink absorbing 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 forming the color material receiving layer. The fine particles used in the present invention include organic fine particles,
Although any of the inorganic fine particles may be used, the inorganic fine particles are preferable from the viewpoint of ink absorbency and image stability.

Preferred examples of the organic fine particles include polymer fine particles obtained by emulsion polymerization, microemulsion polymerization, soap-free polymerization, seed polymerization, dispersion polymerization, suspension polymerization, and the like. , Polypropylene, polystyrene, polyacrylate, polyamide, silicone resin, phenol resin, natural polymer powder, latex or emulsion polymer particles, and the like.

Examples of the 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.

Among them, the silica fine particles are generally roughly classified into wet method particles and dry method (gas phase method) particles according to their 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), 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. The main method is to obtain anhydrous silica by (Arc method),
“Vapor-phase silica” means anhydrous silica fine particles obtained by the gas-phase method. As the silica fine particles used in the present invention, vapor phase method silica fine particles are particularly preferable.

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

Since the above-mentioned vapor grown silica has a particularly large specific surface area, it has high ink absorption and retention efficiency, and also 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, and 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. Therefore, when the average primary particle diameter is 30 nm or less, a structure having a large porosity can be formed, and ink absorption characteristics can be effectively improved. Can be improved.

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

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, it is preferable to use sol-like boehmite as a raw material because a smooth layer can be easily obtained.

Regarding the pore structure of pseudo-boehmite, the average pore radius thereof is preferably 1 to 30 nm, more preferably 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 phase method alumina is preferably 30 nm or less, more preferably 20 nm or less. Further, colloidal silica having an average primary particle size of 30 nm or less is also preferable. The inorganic fine particles used in the present invention include silica fine particles, alumina fine particles,
Pseudo-boehmite is preferred.

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 JP-A No. 92777, JP 2001-301314 A and the like can also be preferably used.

<Content Ratio of Fine Particles and Water-Soluble Resin> Mass ratio of fine particles (x) and water-soluble resin (y) [PB ratio (x
/ Y)] has a great influence on the film structure and film strength of the colorant receiving layer. That is, as the mass content ratio [PB ratio] increases, the porosity, pore volume, and surface area (per unit mass) increase, but the density and strength tend to decrease.

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 too large PB ratio. 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.
5-10 are preferable.

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

For example, gas phase method silica fine particles having an average primary particle diameter of 20 nm or less and a water-soluble resin are mixed in a mass ratio (x /
y) When a coating solution completely dispersed in an aqueous solution in 2 to 5 is coated on a support and the coating layer is dried, a three-dimensional network structure having secondary particles of silica fine particles as a network chain is formed, The average pore diameter is 25 nm or less, the porosity is 50 to 80%,
Pore specific volume 0.5ml / g or more, specific surface area 100m
It is possible to easily form a light-transmitting porous film having a weight ratio of ² / g or more.

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

The mordant is added to the coating liquid containing the fine particles and the water-soluble resin (coating liquid A), or is added to the coating liquid B when there is a fear of aggregation with the fine particles.

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

Examples of the above-mentioned monomer (mordanting monomer) include trimethyl-p-vinylbenzylammonium chloride, trimethyl-m-vinylbenzylammonium chloride, triethyl-p-vinylbenzylammonium chloride and triethyl-m-vinylbenzylammonium. Chloride, N, N-dimethyl-N-ethyl-N-p-vinylbenzylammonium chloride,
N, N-diethyl-N-methyl-N-p-vinylbenzylammonium chloride, N, N-dimethyl-Nn
-Propyl-N-p-vinylbenzyl ammonium chloride, N, N-dimethyl-Nn-octyl-N-p
-Vinylbenzylammonium chloride, N, N-dimethyl-N-benzyl-Np-vinylbenzylammonium chloride, N, N-diethyl-N-benzyl-
N-p-vinylbenzylammonium chloride, N,
N-dimethyl-N- (4-methyl) benzyl-Np-
Vinylbenzylammonium chloride, N, N-dimethyl-N-phenyl-Np-vinylbenzylammonium chloride;

Trimethyl-p-vinylbenzylammonium bromide, trimethyl-m-vinylbenzylammonium bromide, trimethyl-p-vinylbenzylammonium sulfonate, trimethyl-m-vinylbenzylammonium sulfonate, trimethyl-p-vinylbenzylammonium acetate, trimethyl- m
-Vinylbenzyl ammonium acetate, N, N, N
-Triethyl-N-2- (4-vinylphenyl) ethylammonium chloride, N, N, N-triethyl-N
-2- (3-vinylphenyl) ethylammonium chloride, N, N-diethyl-N-methyl-N-2- (4
-Vinylphenyl) ethylammonium chloride,
N, N-diethyl-N-methyl-N-2- (4-vinylphenyl) ethylammonium acetate;

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

Specifically, for example, monomethyldiallylammonium chloride, trimethyl-2- (methacryloyloxy) ethylammonium chloride, triethyl-2- (methacryloyloxy) ethylammonium chloride, trimethyl-2- (acryloyloxy) ethylammonium chloride. , Triethyl-2-
(Acryloyloxy) ethylammonium chloride, trimethyl-3- (methacryloyloxy) propylammonium chloride, triethyl-3- (methacryloyloxy) propylammonium chloride, trimethyl-2- (methacryloylamino) ethylammonium chloride, triethyl-2- (methacryloyl) Amino) ethylammonium chloride, trimethyl-
2- (acryloylamino) ethylammonium chloride, triethyl-2- (acryloylamino) ethylammonium chloride, trimethyl-3- (methacryloylamino) propylammonium chloride, triethyl-3- (methacryloylamino) propylammonium chloride, trimethyl-3- (Acryloylamino) propyl ammonium chloride, triethyl-
3- (acryloylamino) propyl ammonium chloride;

N, N-dimethyl-N-ethyl-2- (methacryloyloxy) ethylammonium chloride,
N, N-diethyl-N-methyl-2- (methacryloyloxy) ethylammonium chloride, N, N-dimethyl-N-ethyl-3- (acryloylamino) propylammonium chloride, trimethyl-2- (methacryloyloxy) ethylammonium Bromide, trimethyl-3- (acryloylamino) propylammonium bromide, trimethyl-2- (methacryloyloxy) ethylammonium sulfonate, trimethyl-
3- (acryloylamino) propyl ammonium acetate etc. can be mentioned. In addition, as the copolymerizable monomer, N-vinylimidazole, N-vinyl-2-methylimidazole and the like can also be mentioned.

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

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

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, dicyandiamide-kaotine resin typified by dicyandiamide-formalin polycondensate, dicyanamide-diaminetriamine polycondensation polyamine-based kaothin resin typified by polycondensate, epichlorohydrin- Dimethylamine addition polymer, dimethyldialine ammonium chloride-SO ₂ copolymer, diallylamine salt-SO Preferable examples thereof include a 2 copolymer, a (meth) acrylate-containing polymer having a quaternary ammonium salt group-substituted alkyl group in the ester moiety, and a styryl type polymer 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, 2,548,564, 3,148,061, 3,330,690, and 41,151.
No. 24, No. 4124386, No. 4193800, No. 4273853, No. 4282305, No. 44502.
24, JP-A-1-161236, 10-8106.
No. 4, No. 10-119423, No. 10-157277.
No. 10-217601 and No. 11-348409.
No. 2001-138621 and 2000-43.
401, 2000-212135, 2000-
309157, 2001-96897, 200
1-138627, JP-A-11-91242 and 8
-2087, 8-2090, 8-2091,
8-2093, 8-174992, 11-1
92777, JP 2001-301314 A, JP-B 5-35162, 5-35163 and 5-351.
No. 64, No. 5-88846, JP-A-7-118333.
No. 2000-344990 and Japanese Patent No. 26488.
No. 47, No. 2661677, etc. are mentioned. Among them, polyallylamine and its derivatives are particularly preferable.

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

As the polyallylamine or its derivative of the present invention, various known allylamine polymers and their derivatives can be used. Examples of such derivatives include salts of polyallylamine and an acid (as the acid, hydrochloric acid, sulfuric acid, phosphoric acid,
Inorganic acid such as nitric acid, methanesulfonic acid, toluenesulfonic acid, acetic acid, propionic acid, cinnamic acid, organic acid such as (meth) acrylic acid, or a combination thereof, or a salt of only allylamine), poly Derivatives of macromolecule reaction of allylamine, copolymers of polyallylamine and other copolymerizable monomers (specific examples of the monomers are (meth) acrylic acid esters, styrenes, (meth) acrylamides, acrylonitrile, Vinyl esters and the like).

Specific examples of polyallylamine and its derivatives include JP-B-62-31722 and JP-B2-1.
No. 4364, Japanese Patent Publication No. 63-43402, No. 63-434
03, 63-45721, 63-29881,
Japanese Patent Publication No. 1-263632, No. 2-56365, No. 2-5
7084, 4-41686, 6-2780, 6-45649, 6-15592, 4-6862.
No. 2, Patent No. 3199227, No. 30083369,
JP-A-10-330427, JP-A-11-21321,
JP-A-2000-281728, 2001-1067
36, JP-A-62-256801, JP-A-7-17
No. 3286, No. 7-213897, No. 9-23531
No. 8, No. 9-302026, No. 11-21321,
The compounds described in WO99 / 21901, WO99 / 19372, JP-A-5-140213, and JP-A-11-506488 may be mentioned.

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, dislopro Mention may be made of salts or complexes of metals selected from sium, erbium, ytterbium, hafnium, tungsten and 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. , Cupric chloride, ammonium copper (II) chloride dihydrate, copper sulfate, cobalt chloride, cobalt thiocyanate, cobalt sulfate, nickel sulfate hexahydrate,
Nickel chloride hexahydrate, nickel acetate tetrahydrate, nickel ammonium sulfate hexahydrate, nickel amidosulfate tetrahydrate, aluminum sulfate, aluminum alum, basic polyaluminum hydroxide, aluminum sulfite, aluminum thiosulfate, Polyaluminum chloride, aluminum nitrate nonahydrate, aluminum chloride hexahydrate, ferrous bromide, ferrous chloride, ferric chloride, ferrous sulfate, ferric sulfate, zinc phenolsulfonate, odor Zinc oxide, zinc chloride,
Zinc nitrate hexahydrate, zinc sulfate, titanium tetrachloride, tetraisopropyl titanate, titanium acetylacetonate,
Titanium lactate, zirconium acetylacetonate, zirconyl acetate, zirconyl sulfate, ammonium zirconium carbonate, zirconyl stearate, zirconyl octylate, zirconyl nitrate, zirconium oxychloride, zirconium hydroxychloride, chromium acetate, chromium sulfate, magnesium sulfate, magnesium chloride hexahydrate Hydrate, magnesium citrate nonahydrate, sodium phosphotungstate,
Sodium tungsten citrate, 12 tungstophosphoric acid n hydrate, 12 tungstosilicic acid 26 hydrate, molybdenum chloride, 12 molybdophosphoric acid n hydrate, gallium nitrate, germanium nitrate, strontium nitrate, yttrium acetate, yttrium chloride, Yttrium nitrate, indium nitrate, lanthanum nitrate, lanthanum chloride, lanthanum acetate, lanthanum benzoate, cerium chloride, cerium sulfate,
Examples thereof include cerium octylate, praseodymium nitrate, neodymium nitrate, samarium nitrate, europium nitrate, gadolinium nitrate, dysprosium nitrate, erbium nitrate, ytterbium nitrate, hafnium chloride and bismuth nitrate.

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

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

In the present invention, the coloring material receiving layer may contain an acid. By adding an acid, the surface pH of the colorant receiving layer is adjusted to 3 to 8, preferably 5 to 7.5. This is preferable because the yellowing resistance of the white background portion is improved. The surface pH is measured by the Japan Pulp and Paper Technology Association (J. TAPP
In the measurement of the surface PH defined in I), the measurement is performed by the 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, Mg, etc.), 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-mentioned acids are metal salts (for example, salts of sodium, potassium, calcium, cesium, zinc, copper, iron, aluminum, zirconium, lanthanum, yttrium, magnesium, strontium, cerium, etc.) or amine salts (for example, ammonia, Triethylamine, tributylamine, piperazine, 2-methylpiperazine, polyallylamine, etc.).

In the present invention, it is preferable that the colorant receiving layer contains a preservative improving agent such as an ultraviolet absorber, an antioxidant and a bleeding inhibitor. 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 deactivator, phosphite compound, phosphonite compound, hydroxyamine compound, nitrone compound,
Peroxide scavenger, polyamide stabilizer, polyether compound, basic co-stabilizer, nucleating agent, benzofuranone compound, indolinone compound, phosphine compound, polyamine compound, thiourea compound, urea compound, hydrazito compound, amidine compound, sugar compound, Examples thereof include hydroxybenzoic acid compounds, dihydroxybenzoic acid compounds and trihydroxybenzoic acid compounds.

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

Specific examples of compounds include Japanese Patent Application No. 2002
-13005, 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
No. 72, No. 48-54965, No. 50-10726.
U.S. Pat. Nos. 2,719,086 and 3,707,
375, 3,754,919, 4,220,7
No. 11,

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

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

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

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. Examples of the nonionic surfactants include polyoxyalkylene alkyl ethers and polyoxyalkylene alkylphenyl ethers (for example, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxy). Ethylene nonyl phenyl ether, etc.), oxyethylene / oxypropylene block copolymer, sorbitan fatty acid esters (eg, sorbitan monolaurate, sorbitan monooleate, sorbitan trioleate, etc.), polyoxyethylene sorbitan fatty acid esters (eg, polyoxyethylene) Sorbitan monolaurate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan Rioreto etc.), polyoxyethylene sorbitol fatty acid esters (e.g., polyoxyethylene sorbit tetraoleate and the like), glycerol fatty acid esters (e.g.,
Glycerol monooleate etc.), polyoxyethylene glycerin fatty acid esters (polyoxyethylene glycerin monostearate, polyoxyethylene glycerin monooleate etc.), polyoxyethylene fatty acid esters (polyethylene glycol monolaurate, polyethylene glycol monooleate etc.) ), Polyoxyethylene alkylamines, acetylene glycols (eg,
2,4,7,9-Tetramethyl-5-decyne-4,7-
Diols, ethylene oxide adducts and propylene oxide adducts of the diols), 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,
What is described in Unexamined-Japanese-Patent No. 5-303205, 8-262742, 10-282619 etc. can be used conveniently. As the amphoteric surfactant,
Amino acid-type amphoteric surfactants are preferable, and the amino acid-type amphoteric surfactants are, for example, derivatized from amino acids (glycine, glutamic acid, histidic acid, etc.) as described in JP-A-5-303205. Examples thereof include N-aminoacyl acid having a long-chain acyl group introduced and salts thereof. The amphoteric surfactants may be used alone or in combination of two or more.

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

Examples of the above-mentioned fluorine-containing surfactants include compounds that are derived via an intermediate having a perfluoroalkyl group using 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 and perfluoroalkyl phosphates.

As the silicone-based surfactant, an organic group-modified silicone oil is preferred, which has a structure in which the side chain of a siloxane structure is modified with an organic group, a structure in which 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.

In the present invention, the content of the surfactant is 0.001 to 2 with respect to the coating liquid for the colorant receiving layer (coating liquid A).
0% is preferable, and 0.01 to 1.0% is more preferable.
When two or more coating liquids for the color material receiving layer are used for coating, it is preferable to add a surfactant to each coating liquid.

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

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

As the highly glossy opaque support, it is preferable that the surface on the side where the color material receiving layer is provided has a glossiness of 40% or more. 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 papers, coated papers, cast coated papers, and baryta papers used for silver salt photographic supports; polyesters such as polyethylene terephthalate (PET); nitrocellulose. Cellulose esters such as cellulose acetate and cellulose acetate butyrate, and plastic films such as polysulfone, polyphenylene oxide, polyimide, polycarbonate and polyamide are made opaque by containing a white pigment and the like (may be subjected to surface calendering treatment). High-gloss film; or a high-gloss film containing the above various paper supports, the above-mentioned transparent supports or white pigments, etc., provided with a polyolefin coating layer containing or not containing a white pigment. And a support or the like. A white pigment-containing expanded polyester film (for example, expanded PET in which polyolefin fine particles are contained and voids are formed by stretching) can also be preferably mentioned. Further, resin coated paper used for silver salt photographic printing paper is also suitable.

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

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

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

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

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

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

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

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

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

In particular, the polyethylene layer on the side for forming the colorant receiving layer contains rutile or anatase type titanium oxide, a fluorescent 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 content of titanium oxide is generally 3 to 3 with respect to polyethylene.
20 mass% is preferable and 4-13 mass% is more preferable. The thickness of the polyethylene layer is not particularly limited, but 10 to 50 μm is suitable for both the front and back layers. Further, an undercoat layer may be provided on the polyethylene layer in order to impart adhesion to the coloring material receiving layer. As the undercoat layer, aqueous polyester, gelatin and PVA are preferable. Further, the thickness of the undercoat layer is preferably 0.01 to 5 μm.

The polyethylene-coated paper can be used as a glossy paper, or when a polyethylene is melt-extruded on the surface of a base paper for coating, a so-called patterning 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, hydrohalloysite, 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) For the coloring material receiving layer of the inkjet recording sheet of the present invention, for example, a coating solution A containing fine particles and a water-soluble resin is applied to the surface of a support, and (1) Simultaneously with the coating, (2) during the drying of the coating layer formed by the coating and before the coating layer shows a reduction rate drying, or (3) after drying the coating layer to form a coating film. Coating liquid B containing a mordant in any of
It is obtained by adding. At this time, the crosslinking agent is the coating liquid A,
It is added to one or more of the coating liquid B and the coating liquid C other than these coating liquids.

It is preferable to provide the colorant receiving layer thus cross-linked and cured, from the viewpoints of ink absorbability and prevention of film cracking.

When the mordant is added to the coating liquid B, a large amount of the mordant is present in the vicinity of the surface of the colorant receiving layer, so that the ink jet colorant is sufficiently mordant and the water resistance of characters and images after printing is improved. preferable. A part of the mordant may be contained in the coating liquid A, and in this case, the mordants of the coating liquid A and the coating liquid B may be the same or different.

In the present invention, the coating liquid for the colorant receiving layer (coating liquid A) containing at least fine particles (for example, vapor phase silica) and the above water-soluble resin is prepared, for example, as follows. You can That is, fine particles such as silica in the vapor phase method and a dispersant are added to water (for example, silica fine particles in water are 10 to 20% by mass), and a high-speed rotating wet colloid mill (for example, "M Technique Co., Ltd." CLEARMIX "), for example, for 20 minutes (preferably 10 to 30 minutes) under the condition of high-speed rotation of 10000 rpm (preferably 5000 to 20000 rpm), and then the cross-linking agent (in addition to the coating liquid A It may be prepared by adding an aqueous solution of a water-soluble resin (for example, so that the water-soluble resin has a mass of about 1/3 of the vapor grown silica) and dispersing under the same rotation conditions as above. be able to. 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, in the preparation of an aqueous dispersion comprising the above fine particles and a dispersant, a fine particle aqueous dispersion may be prepared in advance, and the aqueous dispersion may be added to the dispersant aqueous solution, or the dispersant aqueous solution may be added to the fine particles. It may be added to the aqueous dispersion or mixed at the same time. Further, instead of an aqueous dispersion of fine particles, fine particles of powder may be added to the aqueous dispersant solution as described above. After mixing the above-mentioned fine particles and the dispersant, the mixed solution is finely pulverized using a disperser to give an average particle diameter of 50 to 3
An aqueous dispersion of fine particles of 00 nm can be obtained. As a disperser used to obtain 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. You can use a disperser,
From the viewpoint of efficiently dispersing the formed lump-shaped fine particles, a medium stirring type disperser, a colloid mill disperser or a high pressure disperser is preferable.

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). It may be applied before the specific drying rate is exhibited. That is, after being coated with the coating liquid for the colorant receiving layer (coating liquid A), it is suitably manufactured by introducing a mordant while the coating layer exhibits a constant rate of drying.

The term "before the coating layer starts to exhibit the rate of decrease in drying rate" usually refers to a process for a few minutes immediately after the coating of the coating liquid for the colorant receiving layer, and during this period, the coating is performed. The phenomenon of "constant drying rate" in which the content of the solvent (dispersion medium) in the formed 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 solution A is coated, the coating layer is dried until it exhibits a rate-of-decrease 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 a method of applying before the first coating layer shows the rate of decrease in drying rate, a method of further coating the coating solution B on the coating layer, a method of spraying by a method such as a spray, and a coating method Examples include a method of immersing the support having the coating layer formed therein in the liquid B.

In the above method, as a coating method for coating the coating liquid B, 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.
Drying and curing are carried out by heating at 0 ° C. for 0.5 to 30 minutes. 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 receiving layer can be formed by simultaneous coating (multi-layer coating) on a support and subsequent 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, when simultaneously coating as described above, the barrier layer liquid (intermediate layer liquid) is applied together with the coating of the coloring material receiving layer coating liquid (coating liquid A) and the mordant solution (coating liquid B).
It is preferable that the two layers are intervened between the above two liquids and simultaneous triple layer coating is performed.

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

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

The average pore diameter of the color material receiving layer is preferably 0.005 to 0.025 μm, more preferably 0.01 to 0.025 μm.
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.

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

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

[0122]

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".
"Polymerization degree" means "mass average molecular weight" and "mass average polymerization degree".

(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 parts of epoxidized behenic acid amide, 1.0 part of anionic polyacrylamide, and polyamide polyamine epichlorohydrin of 0.5 part were added. 1 part and 0.5 part 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 above 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 have an absolute dry weight of 0.5 g / m ^2, and 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 high density polyethylene was coated to a thickness of 19 μm using a melt extruder, and a resin layer consisting of a matte surface was formed. Was formed (hereinafter, the resin layer surface is referred to as “rear surface”). Corona discharge treatment is further applied to the resin layer on the back side, and thereafter, aluminum oxide (“Alumina sol 100” manufactured by Nissan Chemical Industries, Ltd.) and silicon dioxide (manufactured by Nissan Chemical Industries, Ltd.) are used as antistatic agents. Snowtex O ") was dispersed in water in a mass ratio of 1: 2, and the 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 brightener 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 A1 for Coloring Material Receiving Layer) Gas phase method silica fine particles having the following composition, ion-exchanged water and "PAS-M-"
1 "was mixed and dispersed using a high-speed rotating colloid mill (" Clearmix "manufactured by M Technique Co., Ltd.) at a rotation speed of 10,000 rpm for 20 minutes, and then the following anion-modified PVA and polyoxyethylene were mixed. A solution containing lauryl ether and ion-exchanged water was added, and dispersion was performed again at a rotation speed of 10,000 rpm for 20 minutes,
A coating liquid A1 for a color material receiving layer was prepared. The mass ratio (PB ratio = /) of the silica fine particles to the water-soluble resin was 4.5, and the pH of the coating material A1 for colorant receiving layer was 4.8, indicating acidity.

[0128]   <Composition of coating liquid A1 for colorant receiving layer> Gas phase method silica fine particles (inorganic fine particles) 10.0 parts   ("Leoseal QS30" manufactured by Tokuyama Corp., average primary particle diameter 7 nm) Deionized water 51.7 parts "PAS-M-1" (60% aqueous solution) 0.83 parts   (Dispersant, manufactured by Nitto Boseki Co., Ltd.) Anion-modified PVA (water-soluble resin) 8% aqueous solution 27.8 parts   ("PVA KL318" manufactured by Kuraray Co., Ltd.) 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 colorant receiving layer coating solution A1 obtained above was applied to the front surface of the support by an extrusion die coater. 200m using
A coating amount of 1 / m ² was applied (coating step), and the coating layer was dried at 80 ° C. (air velocity 3 to 8 m / sec) until the solid concentration of the coating layer reached 20%. This coating layer exhibited a constant drying rate during this period. Immediately after that, it was immersed in a mordant solution B1 having the following composition for 30 seconds, and 20 g /
m ² attached (step of applying mordant solution), and further 8
It was dried at 0 ° C. for 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.

[0130]   <Composition of mordant coating liquid B1> Polyallylamine "PAA-10C" 10% aqueous solution 25 parts   (Mordant / Crosslinking agent, Nitto Boseki Co., Ltd.) Deionized water 59.7 parts Ammonium chloride (surface pH adjuster) 0.8 parts Polyoxyethylene lauryl ether (surfactant) 10 parts   ("Emulgen 109P" manufactured by Kao Corporation, 2% aqueous solution, HLB value 13.6) MegaFac “F1405” 10% aqueous solution 2.0 parts   (Fluorine-based surfactant manufactured by Dainippon Ink and Chemicals, Inc.)

Example 2 Example 1 was repeated except that the composition of the coating material A1 for colorant receiving layer in Example 1 was changed to the composition of the coating solution A2 for colorant receiving layer.
An ink jet recording sheet according to Example 2 was prepared in the same manner as

[0132]   <Composition of coating material A2 for colorant receiving layer> Gas phase method silica fine particles (inorganic fine particles) 10.0 parts   ("Leoseal QS30" manufactured by Tokuyama Corp., average primary particle diameter 7 nm) Deionized water 51.7 parts "PAS-M-1" (60% aqueous solution) 0.83 parts   (Dispersant, manufactured by Nitto Boseki Co., Ltd.) Anion-modified PVA (water-soluble resin) 8% aqueous solution 13.9 parts   ("PVA KL318" manufactured by Kuraray Co., Ltd.)   Polyvinyl alcohol (water-soluble resin) 8% aqueous solution 13.9 parts   ("PVA124" manufactured by Kuraray Co., Ltd.) 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

Example 3 The procedure of Example 2 was repeated except that the anion-modified PVA (PVA KL-318; manufactured by Kuraray Co., Ltd.) was changed to the anion-modified PVA (PVA KM618) in <Coloring material receiving layer coating solution A2>. Example 2
An ink jet recording sheet according to Example 3 was produced in the same manner as in.

Example 4 Similar to Example 2 except that the anion-modified PVA (PVA KL-318; manufactured by Kuraray Co., Ltd.) was changed to polyacrylic acid in <Colorant Receptor Layer Coating Solution A2> of Example 2. Then, an inkjet recording sheet according to Example 4 was produced.

Example 5 In the same manner as in Example 2 except that the anion-modified PVA (PVA KL-318; manufactured by Kuraray Co., Ltd.) was changed to carboxymethyl cellulose in <Coating liquid A2 for coloring material receiving layer> of Example 2. Thus, an inkjet recording sheet according to Example 5 was produced.

Example 6 Anion-modified PVA (PVA “KL-318” manufactured by Kuraray Co., Ltd.) was used as an acetoacetyl-modified PVA (Japan Synthetic Chemical Industry Co., Ltd.) in <Coating liquid A1 for coloring material receiving layer> of Example 1. An ink jet recording sheet according to Example 6 was produced in the same manner as in Example 1 except that the production sheet was changed to "Z200").

Example 7 For ink jet recording according to Example 7 in the same manner as in Example 1 except that the <composition of mordant coating liquid B1> in Example 1 was changed to the following <composition of mordant coating liquid B2>. A sheet was prepared.

[0138]   <Composition of mordant coating liquid B2> Aluminum lactate (crosslinking agent) 0.65 parts Polyallylamine "PAA-10C" 10% aqueous solution 25 parts   (Mordant / Crosslinking agent, Nitto Boseki Co., Ltd.) Deionized water 59.7 parts Ammonium chloride (surface pH adjuster) 0.8 parts Polyoxyethylene lauryl ether (surfactant) 10 parts   ("Emulgen 109P" manufactured by Kao Corporation, 2% aqueous solution, HLB value 13.6) MegaFac “F1405” 10% aqueous solution 2.0 parts   (Fluorine-based surfactant manufactured by Dainippon Ink and Chemicals, Inc.)

Example 8 An ink jet recording sheet according to Example 8 was prepared in the same manner as in Example 6 except that <Composition of mordant coating liquid B1> in Example 6 was changed to <Mordant coating liquid B3>.

[0140]   <Composition of mordant coating liquid B3> Zirconium acetate (crosslinking agent) 0.65 parts Polyallylamine "PAA-10C" 10% aqueous solution         25 copies   (Mordant / Crosslinking agent, Nitto Boseki Co., Ltd.) Deionized water 59.7 parts Ammonium chloride (surface pH adjuster) 0.8 parts Polyoxyethylene lauryl ether (surfactant) 10 parts   ("Emulgen 109P" manufactured by Kao Corporation, 2% aqueous solution, HLB value 13.6) MegaFac “F1405” 10% aqueous solution 2.0 parts   (Fluorine-based surfactant manufactured by Dainippon Ink and Chemicals, Inc.)

Example 9 An ink jet recording sheet according to Example 9 was prepared in the same manner as in Example 8 except that zirconium acetate was changed to triethylenetetramine in <Composition of mordant coating liquid B3> of Example 8. Made

Example 10 An ink jet recording sheet according to Example 10 was prepared in the same manner as in Example 8 except that zirconium acetate was changed to adipic dihydrazide in <Composition of mordant coating liquid B3> of Example 8. Made

Example 11 The <mordanting agent coating solution B3> of Example 8 was replaced with <mordanting agent coating solution B>.
Example 11 is carried out in the same manner as in Example 8 except that it is changed to 4>.
The inkjet recording sheet according to

[0144]   <Composition of mordant coating liquid B4> Triethylene tetramine (crosslinking agent) 0.65 parts Basic polyaluminum chloride 10% aqueous solution (mordant) 25 parts   (Al2 (OH) 5Cl, "PAC # 1000" manufactured by Taki Chemical Co., Ltd.) Deionized water 59.7 parts Ammonium chloride (surface pH adjuster) 0.8 parts Polyoxyethylene lauryl ether (surfactant) 10 parts   ("Emulgen 109P" manufactured by Kao Corporation, 2% aqueous solution, HLB value 13.6) MegaFac “F1405” 10% aqueous solution 2.0 parts   (Fluorine-based surfactant manufactured by Dainippon Ink and Chemicals, Inc.)

Example 12 Except that <Coloring material receiving layer coating liquid A1> of Example 1 was changed to <Coloring material receiving layer coating liquid A3> and <Mordant coating liquid B1> was changed to <Mordant coating liquid B5>. An ink jet recording sheet according to Example 12 was produced in the same manner as in Example 1.

[0146]   <Composition of coating material A3 for colorant receiving layer> Gas phase method silica fine particles (inorganic fine particles) 10.0 parts   ("Leoseal QS30" manufactured by Tokuyama Corp., average primary particle diameter 7 nm) Deionized water 51.7 parts "PAS-M-1" (60% aqueous solution) 0.83 parts   (Dispersant, manufactured by Nitto Boseki Co., Ltd.) Diacetone acrylamide modified PVA (water-soluble resin) 8% aqueous solution 27.8 parts   ("D700" manufactured by Unitika Ltd.) 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

[0147]   <Composition of mordant coating liquid B5> Adipic acid dihydrazide (crosslinking agent) 0.65 parts Polyallylamine "PAA-10C" 10% aqueous solution 25 parts   (Mordant / Crosslinking agent, Nitto Boseki Co., Ltd.) Deionized water 59.7 parts Ammonium chloride (surface pH adjuster) 0.8 parts Polyoxyethylene lauryl ether (surfactant) 10 parts   ("Emulgen 109P" manufactured by Kao Corporation, 2% aqueous solution, HLB value 13.6) MegaFac “F1405” 10% aqueous solution 2.0 parts   (Fluorine-based surfactant manufactured by Dainippon Ink and Chemicals, Inc.)

Example 13 The same as Example 12 except that the adipic acid hydrazide of <Mordant coating liquid B5> of Example 12 was changed to polyacrylic acid hydrazide (“APA-H” manufactured by Otsuka Chemical Co., Ltd.). Then, an inkjet recording sheet according to Example 13 was produced.

Example 14 <Synthesis Example 1> Polyallylamine (“PA manufactured by Nittobo Co., Ltd.”
A-10C ") 10% aqueous solution 114.0 parts, acrylonitrile 2.7 parts was added, and the mixture was stirred at room temperature for 8 hours,
By adjusting the concentration by adding water, a 10% aqueous solution of polyallylamine derivative 1 (a compound obtained by cyanoethylating a part of amino groups of polyallylamine) was obtained.

An ink jet recording sheet according to Example 14 was prepared in the same manner as in Example 8 except that the polyallylamine "PAA-10C" in the mordant coating solution B3 of Example 8 was changed to the above polyallylamine derivative 1. did.

Example 15 The same procedure as in Example 8 was carried out in the same manner as in Example 8 except that the vapor-phase method silica fine particles were changed to the vapor-phase method alumina fine particles in <Color material receiving layer coating liquid A1> of Example 8. Such an inkjet recording sheet was produced.

Comparative Example 1 PVA K in Coating Solution A1 for Coloring Material Receiving Layer of Example 1
L318 is a PVA124 containing no functional group according to the present invention
An inkjet recording sheet according to Comparative Example 1 was produced in the same manner as in Example 1 except that the sheet was manufactured by Kuraray Co., Ltd.

Comparative Example 2 PVA K in Coating Solution A1 for Coloring Material Receiving Layer of Example 7
An inkjet recording sheet according to Comparative Example 1 was produced in the same manner as in Example 7 except that P318 was changed to PVA124 (manufactured by Kuraray Co., Ltd.).

Comparative Example 3 An ink jet recording sheet according to Comparative Example 3 was produced in the same manner as in Example 8 except that the mordant coating solution B3 of Example 8 was changed to the mordant coating solution B6.

[0155]   <Composition of mordant coating liquid B6> 10% aqueous solution of poly (trimethylvinylbenzyl ammonium chloride)                                                                   25 copies   (mordant) Deionized water 59.7 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.)

Comparative Example 4 An ink jet recording sheet according to Comparative Example 4 was prepared in the same manner as in Example 12 except that the mordant coating solution B5 of Example 12 was changed to the mordant coating solution B6.

Comparative Example 5 Comparative Example 5 was carried out in the same manner as in Example 1 except that the coloring material receiving layer coating liquid A1 in Example 1 was changed to the coloring material receiving layer coating liquid A4 and the mordant coating liquid B1 was changed to the mordant coating liquid B7. The inkjet recording sheet according to No. 5 was produced.

[0158] [Composition of coating liquid A4 for colorant receiving layer] Gas phase method silica fine particles (inorganic fine particles) 10.0 parts   ("Leoseal QS30" manufactured by Tokuyama Corp., average primary particle diameter 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

[0159]   <Composition of mordant coating liquid B7> Boric acid (crosslinking agent) 0.65 parts Polyallylamine "PAA-10C" 10% aqueous solution 25 parts   (Mordant, manufactured by Nittobo Co., Ltd.) Deionized water 59.7 parts Ammonium chloride (surface pH adjuster) 0.8 parts Polyoxyethylene lauryl ether (surfactant) 10 parts   ("Emulgen 109P" manufactured by Kao Corporation, 2% aqueous solution, HLB value 13.6) MegaFac “F1405” 10% aqueous solution 2.0 parts   (Fluorine-based surfactant manufactured by Dainippon Ink and Chemicals, Inc.)

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

<Cracks> Cracks on the surface of each ink jet recording sheet were visually evaluated. A indicates that no cracks were found, and B indicates that some cracks were found.
Evaluated as.

<Ink absorbency> Ink jet printer ("PM-900C" manufactured by Seiko Epson Corp.)
By using the yellow on each inkjet recording sheet,
Solid prints of magenta, cyan, black, blue, green, and red were printed, and after 10 seconds, the paper was contact-pressed on the image, and the degree of transfer of the ink to the paper was evaluated. The case where the ink transfer was not recognized was evaluated as A, and the case where the partial transfer was recognized was evaluated as B.

<Water resistance> Solid images of yellow, magenta, cyan, black, blue, green, and red are printed on each inkjet recording sheet using an inkjet printer ("PM-900C" manufactured by Seiko Epson Corp.). Was printed, left for 3 hours, immersed in water for 1 minute, and the degree of outflow of the ink into the water was visually evaluated. The case where the dye outflow was not observed was evaluated as A, and the case where the dye outflow was observed and the image density was gradually decreased was evaluated as B.

<Rainbow over time> An inkjet printer (“PM-900C” manufactured by Seiko Epson Corporation) was used to form a grid-like linear pattern (magenta and black ink side by side on each inkjet recording sheet). A line width of 0.28 mm) was printed. After leaving for 3 hours after printing, it was stored in a thermo-hygrostat at a temperature of 40 ° C. and a relative humidity of 90% for 3 days, and the line width of the black portion was measured and evaluated according to the following criteria. When the line width is less than 0.30 mm and almost no generation of bleeding with time is observed, the line width is A.
The evaluation was performed by setting B when a slight bleeding with time was observed in the range of 30 to less than 0.35 mm and C when a bleeding with time was remarkably observed with a line width of 0.35 mm or more.

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

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

[0167]

[Table 1]

From the results shown in Table 1 above, the ink jet recording sheets (Examples 1 to 15) comprising the combination of the water-soluble resin / crosslinking agent of the present invention were strong with no cracks and the like, and were water resistant. It was found that the ink absorbency was excellent. Further, the ink jet recording sheet of the present invention has suppressed image blurring under high humidity conditions, has a high density residual ratio of images under a high-concentration ozone environment and after a xenon irradiation test, and has excellent storage stability. Turned out to be a sheet.

[0169]

EFFECTS OF THE INVENTION The ink jet recording sheet of the present invention does not use a boron compound which is a drainage control substance,
An ink jet recording sheet that is strong without cracking, has good ink absorbability, and has excellent storage stability in the image area.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 2C056 EA13 FC06                 2H086 BA01 BA15 BA33 BA35 BA37                       BA41 BA57                 4D075 BB24Z BB96Y CA35 CA38                       CA48 CB02 CB04 CB06 DA06                       DB18 DB31 DB48 DB53 DC27                       EA06 EB07 EB19 EB22 EB55                       EB56 EC07 EC08 EC24 EC37

Claims (9)

[Claims] 1. An ink jet recording sheet having a colorant receiving layer on a support, wherein the colorant receiving layer is one of a) a carboxyl group, a sulfoxyl group, an acetoacetyl group and a reactive ketone group, or An ink jet recording sheet having a three-dimensional network structure having a porosity of 50 to 80%, containing a water-soluble resin having two or more functional groups, b) a crosslinking agent capable of reacting with the functional groups, and c) fine particles. 2. A metal salt, an amine compound, a hydrazine compound, an epoxy compound, an N-methylol compound, wherein the water-soluble resin is a water-soluble resin having a carboxyl group or a sulfoxyl group, and the cross-linking agent has a valence of 2 or more. The ink jet recording sheet according to claim 1, which is one kind or two or more kinds selected from the following: an aziridine compound and an oxazoline compound. 3. The water-soluble resin is a water-soluble resin having an acetoacetyl group, and the cross-linking agent is selected from metal salts having a valence of 2 or more, amine compounds, hydrazine compounds, epoxy compounds and N-methylol compounds. The inkjet recording sheet according to claim 1, which is one kind or two or more kinds. 4. The water-soluble resin is a water-soluble resin having a reactive ketone group, and the crosslinking agent is an amine compound and / or a hydrazine compound having a valence of 2 or more.
The inkjet recording sheet described above. 5. The water-soluble resin having a functional group is one or more selected from polyvinyl alcohol resins, polysaccharides, gelatins and acrylic resins.
5. The inkjet recording sheet according to any one of items 4 to 4. 6. The ink jet recording sheet according to claim 2, wherein the amine compound having a valence of two or more is a polymer having a primary, secondary or tertiary amino group. 7. The ink jet recording sheet according to claim 1, wherein the fine particles are one kind or two or more kinds selected from silica fine particles, alumina fine particles and pseudo-boehmite. 8. The coloring material-receptive layer further contains a mordant capable of fixing an anionic dye.
8. The ink jet recording sheet according to any one of items 1 to 7. 9. A coloring material receiving layer is coated with a coating liquid A containing fine particles and a water-soluble resin on the surface of the support, and (1)
Simultaneously with the coating, (2) during the drying of the coating layer formed by the coating and before the coating layer shows a reduction rate drying, or (3) after drying the coating layer to form a coating film. It is obtained by applying a coating solution B containing a mordant to any one of the above, and is obtained by adding a cross-linking agent to one or more of the coating solution A, the coating solution B, and the coating solution C other than these coating solutions. The inkjet recording sheet according to any one of claims 1 to 8, wherein