JP2002362012A - Ink jet recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ink jet recording material, which has a high photograph- like gloss, a high ink absorbency and an improved preservability. SOLUTION: In the ink jet recording material, which is formed by providing an ink accepting layer on a support, the ink accepting layer includes a repeating structure selected from hydrazine derivative structures or non-cyclic hydroxylamine derivative structures and a cation type polymer having a repeating structure different from the above repeating structure and giving cationic properties.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ink jet recording, and more particularly, to a photo-like high gloss,
The present invention relates to an ink jet recording material having excellent ink absorbency and improved storage stability after printing.

[0002]

2. Description of the Related Art The ink jet recording method is a printing method in which small droplets of an ink composition fly and adhere to a recording medium such as paper to perform printing. This method has a feature that high-resolution and high-quality images can be printed at a high speed with a relatively inexpensive apparatus, and is widely used in printers and facsimile machines.

[0003] However, the ink jet recording ink that is usually used is water-based, and there is a problem that when the obtained image comes into contact with water, the coloring material is dissolved or dispersed again, and the image bleeds or flows. In order to solve this problem, for example, polyethyleneimine, polydiallylamine, polyallylamine, alkylamine polymer, JP-A-59-20696, JP-A-59-33176, and JP-A-5-33176.
9-33177, 59-15088, 60-
Nos. 11389, 60-49990, 60-838
No. 82, No. 60-109894, No. 62-19849
No. 3, 63-49478, 63-115780
No. 63-280681, JP-A-1-40371
No. 6,234,268, No. 7-125411, No. 10-193776, etc., a method of adding a polymer having a primary to tertiary amino group and a quaternary ammonium base is known. According to this method, although the water resistance of the image is considerably improved, there is a problem that the weather resistance of the image often deteriorates.

On the other hand, as a recording medium used in the ink jet recording system, in addition to ordinary paper, a base paper having a polymer type ink absorbing layer which absorbs ink by swelling, amorphous silica, There are known those provided with a porous ink absorbing layer comprising inorganic fine particles such as alumina hydrate and a water-soluble binder.

[0005] For example, JP-A-55-51583,
Nos. 6-157, 57-107879, 57-10
No. 7880, No. 59-230787, No. 62-160
No. 277, No. 62-184879, No. 62-1833
Nos. 82 and 64-11877 propose a recording material obtained by applying a silicon-containing pigment such as silica to a paper support together with a water-soluble binder. In addition, Japanese Patent Publication No. 3-55552, Japanese Patent Application Laid-Open No. 2-188287, and
Nos. 0-81064, 10-119423, 10-
No. 175365, No. 10-193776, No. 10-2
No. 03006, No. 10-217601, No. 11-20
No. 300, No. 11-20306, No. 11-34481
Publications include synthetic silica fine particles obtained by a gas phase method (hereinafter, referred to as “silica fine particles”).
The use of fumed silica) is disclosed.
This fumed silica is an ultrafine particle having an average primary particle diameter of several nm to several tens nm, and is characterized in that high gloss is obtained. Further, JP-A-2-276671, JP-A-3-25
1488, 5-16517 and the like show recording materials using alumina hydrate.

[0006] In recent years, with the demand for photo-like recording sheets, glossiness has been increasingly regarded as important, and polyolefin resin-coated paper (laminated with a polyolefin resin such as polyethylene on both sides of paper), polyester film, etc. A recording material in which an ink receiving layer mainly composed of fumed silica, alumina or the like is coated on a water-resistant support described above is advantageously used.

However, a porous recording material using inorganic fine particles such as fumed silica is porous,
There is a problem that a printed image is easily discolored during storage after printing. That is, there is a large problem that discoloration and fading easily occur due to light and particularly a trace amount of gas in the atmosphere.
In addition, in the water-resistant support, unlike the conventionally used paper support, the support itself has no ink absorbing ability, so that the porosity of the porous recording layer is increased and the coating amount is increased. Therefore, it is necessary to secure the ink absorption capacity. As a result of such a design, the above-described image discoloration problem has become particularly serious.

A number of proposals have been made with respect to the goal of suppressing such discoloration and fading and improving the storability of a printed image. For example, Japanese Patent Application Laid-Open No. 57-74193
JP-A-57-87988 and JP-A-62-261478 disclose a method using an ultraviolet absorber.
74192, 57-87989, 60-727
No. 85, No. 61-146591, No. 62-17038
No. 1, 62-61477, JP-A-3-13376
No. 7,314,881, No. 7,314,882, No.8-25796, No.9-267544, etc., describe a method using an antioxidant or an anti-fading agent.
However, all of these methods have an inadequate effect of preventing discoloration and fading, or even having the effect of preventing discoloration, such as coloring itself or discoloring the recording dye immediately after printing. At present, it has not reached a sufficient level of practical use.
As described above, in ink-jet recording materials having a porous ink-receiving layer, the storability of this printed image is a particularly important issue, and urgent measures have been desired.

[0009]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide an ink jet recording material having excellent storage stability at a printing portion, and particularly to a porous ink having high photo-like gloss and high ink absorption. An object of the present invention is to provide an inkjet recording material having a receiving layer.

[0010]

The object of the present invention is to provide an ink jet recording material having an ink receiving layer provided on a support, wherein the ink receiving layer is selected from a hydrazine derivative structure and a non-cyclic hydroxylamine derivative structure. This has been attained by an ink jet recording material characterized by containing a cationic polymer having a repeating structure to be formed and a different repeating structure for imparting cationicity.

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Specific examples of the hydrazine derivative structure contained in the cationic polymer used in the present invention include, for example, hydrazine optionally having a substituent, semicarbazide, thiosemicarbazide, carbonohydrazide, Examples of the structure include carbonohydrazide, carbazic acid, isosemicarbazide, and isocarbonohydrazide. Of these, semicarbazide and carbonohydrazide structures are particularly preferred.

Specific examples of the non-cyclic hydroxylamine derivative structure contained in the cationic polymer used in the present invention include, for example, a non-cyclic hydroxylamine which may have a substituent, a non-cyclic N-hydroxyamide, and a non-cyclic hydroxylamine. Examples of the structure include N-hydroxyurea and acyclic N-hydroxysulfonamide. Among these,
Particularly preferred are N-acylhydroxylamine structures such as N-hydroxyamide and N-hydroxyurea.

As the repeating structure for imparting cationicity used in the present invention, known structures can be used. Among them, a structure containing a tertiary amino group or a quaternary ammonium group is preferable. Examples of the tertiary amino group or quaternary ammonium group include a dialkylamino group, a pyrrolidinyl group, a piperidinyl group, a pyridyl group, an imidazolyl group, a trialkylammonio group, a pyrrolidinio group, a piperidinio group which may have a substituent. Examples include a pyridinio group and an imidazolio group.

In the cationic polymer used in the present invention, the above-mentioned hydrazine derivative structure or acyclic hydroxylamine derivative structure may be incorporated as a part of the polymer main chain or a part of a side chain. Is also good. The ratio of the hydrazine derivative structure or the acyclic hydroxylamine derivative structure to the polymer is 5 to 5.
It is preferably 75 mol%, particularly preferably 10 to 50 mol%. If the ratio is lower than this, the effect of improving the storage stability is small, and if it is too high, it takes time to dissolve in the coating liquid, which is disadvantageous in production.

The polymer of the present invention may contain a structure other than the structures described so far as the properties thereof are not impaired. When these are specifically shown by the structure of the monomer before polymerization, for example, ethylene, styrene, divinylbenzene, acrylic acid, methacrylic acid, methyl methacrylate, n-butyl acrylate, vinyl acetate, hydroxyethyl methacrylate, acrylamide, N ,
Examples include N-dimethylacrylamide, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, acrylonitrile, and the like.

The weight average molecular weight of the cationic polymer used in the present invention is preferably 5,000 or more, more preferably about 5,000 to 100,000. The amount used is 1 to 10% by mass, preferably 2 to 7% by mass, based on the inorganic fine particles described below.

Known methods can be used for producing the cationic polymer used in the present invention. For example, there is a copolymerization of a monomer having a structure for imparting cationicity with a monomer having a hydrazine derivative structure or an acyclic hydroxylamine derivative structure. Further, it can also be obtained by graft-polymerizing a monomer having a hydrazine derivative structure or an acyclic hydroxylamine derivative structure onto a known cationic polymer.

Specific examples of the monomer having a structure for imparting cationicity include, for example, monomers having a tertiary amino group include N, N-dimethylaminopropyl acrylate, N, N-diethylaminoethyl acrylate, N, N N-dimethylaminoethyl methacrylate,
N, N-diethylaminoethyl methacrylate, N, N
-Dimethylaminopropyl methacrylate, N, N-dimethylaminobutyl methacrylate, N, N-dimethylaminoethyl acrylate, N, N-dimethylaminopropylacrylamide, N, N-dimethylaminoethylacrylamide, acryloylmorpholine, 3-dimethylamino- 2-hydroxy-1-propyl methacrylate, 3-diethylamino-2-hydroxy-1-propyl methacrylate and the like can be mentioned.

Examples of the monomer having a quaternary ammonium group include glycidyltrimethylammonium chloride, 3-chloro-2-hydroxypropyltrimethylammonium chloride, 3-chloro-2-hydroxypropyltriethanolammonium chloride, and glycidyldimethylbenzylammonium chloride. Glycidyldimethylbutylammonium chloride, N-2-hydroxy-3-acryloyloxypropyl-N, N, N-trimethylammonium chloride, N-methacryloylaminoethyl-N, N-dimethylbenzylammonium chloride, N-methacryloxy- N, N, N-triethylammonium bromide and the like.

Specific examples of the monomer having a hydrazine derivative structure include, for example, 1,1-dimethyl-2-methallylhydrazine, N-allylaminopiperidine, 1,1
-Diallyl-2,2-dibutylhydrazine, N ', N'
-Dimethylmethacryloylcarbohydrazide, 1,1-
Dimethyl-4- (3-methacryloyloxypropyl)
Semicarbazide, 1,1-cyclopentylene-4- (3
-Methacryloyloxypropyl) semicarbazide, 1
-Acryloyl-4,4-dimethylsemicarbazide,
1,1-diallyl-4,4-dimethylsemicarbazide,
4,4-dimethyl-1- (2-hydroxy-3-methacryloyloxypropyl) semicarbazide, 1,1-dimethyl-4- (3-methacryloxypropyl) thiosemicarbazide, 1,1-diallyl-5,5-dimethyl Carbonohydrazide, 1,1-dimethyl-5- (2-hydroxy-3-methacryloyloxypropyl) carbonohydrazide, 1,1-diethyl-5- (2-hydroxy-3-methacryloyloxypropyl) carbonohydrazide, 1,1-cyclopentylene-5- (2-hydroxy-3-methacryloyloxypropyl) carbonohydrazide, 1,1-dimethyl-5-methacryloylcarbonohydrazide, 1,1-cyclopentylene-5-methacryloylcarbo Nohydrazide, allyl 3,3-dimethylcarbazate, 3 (2-hydroxy-3-methacryloyloxypropyl) carbazic acid, methyl 3- (2-hydroxy-3-methacryloyloxypropyl) carbazate, 3-methacryloylcarbazic acid, ethyl 3-methacryloylcarbazate, 1,1- Dimethyl-O
Methacryloyl isosemicarbazide, 1,1,5,5
-Tetramethyl-O-methacryloylisocarbonohydrazide and the like.

Specific examples of monomers having an acyclic hydroxylamine derivative structure include, for example, N, N-diallylhydroxylamine, N, N-bis (2-hydroxy-3-methacryloyloxypropyl) hydroxylamine, N-methyl -N-hydroxyacrylamide,
N-ethyl-N-hydroxymethacrylamide, N-hydroxyethyl-N-hydroxymethacrylamide, N
-Hydroxy-N '-(3-methacryloyloxypropyl) urea, N-hydroxy-N-methyl-N'-(3
-Methacryloyloxypropyl) urea, N-hydroxy-N-ethyl-N '-(3-methacryloyloxypropyl) urea, N-hydroxy-N'-allyl urea, N
-Hydroxyallyl sulfonamide, N-hydroxy 4
-Vinylbenzenesulfonamide and the like.

The inorganic fine particles used in the present invention include:
Light calcium carbonate, heavy calcium carbonate, magnesium carbonate, kaolin, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulfide, zinc carbonate,
Satin white, aluminum silicate, diatomaceous earth, calcium silicate, synthetic silica, alumina, alumina hydrate,
Examples include magnesium silicate, lithopone, zeolite, and magnesium hydroxide. Among these, synthetic silica, alumina and alumina hydrate are preferred, and fumed silica, alumina and alumina hydrate are particularly preferred. These may be used alone or in combination. In the combination, they may be mixed in the same layer, or may be formed into separate layers and used in a laminated form.

The fumed silica preferably used in the present invention is also called dry silica, and is generally produced by a flame hydrolysis method. Specifically, a method of burning silicon tetrachloride with hydrogen and oxygen is generally known. The fumed silica is commercially available as Aerosil from Nippon Aerosil Co., Ltd. and QS type from Tokuyama Co., Ltd. and can be obtained. Generally, fumed silica is agglomerated into secondary particles having appropriate voids,
It is preferable to pulverize and disperse secondary particles of about 0 to 300 nm with an ultrasonic wave, a high-pressure homogenizer, a facing collision type jet pulverizer or the like, because the ink absorption and gloss are good.

Alumina and alumina hydrate preferably used in the present invention are aluminum oxide and its hydrate, which may be crystalline or amorphous, and have an irregular shape, a spherical shape, a plate shape or the like. Is used. As the alumina, γ-alumina which is a γ-type crystal of aluminum oxide is preferable. γ-alumina can reduce primary particles to about 10 nm, but usually, a secondary particle crystal of several thousands to several tens of thousands nm is subjected to ultrasonic or high-pressure homogenizer,
Those pulverized to about 50 to 300 nm by an opposed collision type jet pulverizer or the like can be preferably used. Alumina hydrate is represented by a constitutive formula of Al2O3.nH2O (n = 1 to 3). The case where n is 1 represents alumina hydrate having a boehmite structure, and the case where n is greater than 1 and less than 3 represents alumina hydrate having a pseudo-boehmite structure. It can be obtained by a known production method such as hydrolysis of aluminum alkoxide such as aluminum isopropoxide, neutralization of aluminum salt with alkali, hydrolysis of aluminate and the like.

The average particle size of the primary particles of the fumed silica, alumina, and alumina hydrate of the present invention is defined as the average particle size of the dispersed particles within a certain area by observation with an electron microscope.
The diameter of a circle equal to the projected area of each of the particles was determined as the particle size of the particles. The average particle size of the primary particles of the fumed silica used in the present invention is 5 to 50 nm, preferably 5 to 50 nm.
30 nm. The average particle size of the primary particles of the alumina and alumina hydrate of the present invention is 10 to 50 nm, preferably 10 to 30 nm.

In the present invention, the amount of the inorganic fine particles used in the recording layer is preferably 8 g / m ² or more, and 10 to 30 g / m ^2.
An m ² range is more preferred. If it is less than this range, the ink absorbency is poor, and if it is more than this, the strength of the ink receiving layer is reduced, which tends to cause problems during production and use.

In the present invention, the inorganic fine particles are mainly contained in the ink receiving layer, that is, 50% by weight or more, preferably 60% by weight or more, more preferably 65% by weight, based on the total solid content of the ink receiving layer. It is preferable to contain the above.

In the present invention, as the hydrophilic binder used together with the inorganic fine particles, various known binders can be used, but a hydrophilic binder which has high transparency and can obtain a higher permeability of the ink is preferably used. In the use of the hydrophilic binder, it is important that the hydrophilic binder does not swell at the initial penetration of the ink and does not close the voids.From this viewpoint, a hydrophilic binder having a relatively low swelling property at around room temperature is preferable. Used. Particularly preferred hydrophilic binders are fully or partially saponified polyvinyl alcohols or cationically modified polyvinyl alcohols.

Particularly preferred among polyvinyl alcohols are those partially or completely saponified with a degree of saponification of 80% or more. Those having an average polymerization degree of 200 to 5000 are preferred.

As the cation-modified polyvinyl alcohol, for example, as described in JP-A-61-10483, a primary to tertiary amino group or a quaternary ammonium group is used as the main chain or side chain of polyvinyl alcohol. It is a polyvinyl alcohol contained therein.

In the present invention, it is preferable to use a crosslinking agent (hardening agent) together with the hydrophilic binder. Specific examples of the crosslinking agent include aldehyde compounds such as formaldehyde and glutaraldehyde, ketone compounds such as diacetyl and chloropentanedione, 2-hydroxy-4,
6-dichloro-1,3,5-triazine, a compound having a reactive halogen as described in U.S. Pat. No. 3,288,775, divinyl sulfone, U.S. Pat.
No. 5,718, compounds having reactive olefins, N-methylol compounds as described in U.S. Pat. No. 2,732,316, isocyanates as described in U.S. Pat. No. 3,103,437, U.S. Pat. 3,017,28
0, 2,983,611; aziridine compounds as described in U.S. Pat. No. 3,100,704; carbodiimide-based compounds as described in U.S. Pat. No. 3,100,704;
No. 7, such as epoxy compounds, halogen carboxaldehydes such as mucochloric acid, dioxane derivatives such as dihydroxydioxane, and inorganic crosslinking agents such as chrome alum, zirconium sulfate, boric acid and borate. It can be used in combination of more than one kind. Among these, boric acid or borate is particularly preferred.

In the recording material of the present invention, the ink receiving layer may contain another cationic compound different from the polymer of the present invention.

Examples of the cationic compound include a cationic polymer and a water-soluble metal compound. Examples of the cationic polymer include polyethyleneimine, polydiallylamine, polyallylamine, and alkylamine polymers, JP-A-59-20696 and JP-A-59-33176.
No. 59-33177, No. 59-155088,
No. 60-11389, No. 60-49990, No. 60
No. 83882, No. 60-109894, No. 62-1
Nos. 98493, 63-49478, 63-115
780, 63-280681, JP-A-1-403
No. 71, No. 6-234268, No. 7-125411
Nos. 1 to 3 described in JP-A-10-193776 and the like.
A polymer having a quaternary amino group and a quaternary ammonium group is preferably used.

The molecular weight of these cationic polymers is
It is preferably 5,000 or more, more preferably about 5,000 to 100,000. The amount used is 1 to 1 with respect to the inorganic fine particles.
0% by weight, preferably 2 to 7% by weight.

The water-soluble metal compound used in the present invention includes, for example, water-soluble polyvalent metal salts. Water-soluble salts of metals selected from calcium, barium, manganese, copper, cobalt, nickel, aluminum, iron, zinc, zirconium, chromium, magnesium, tungsten, and molybdenum. 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, chlorinated chloride Cupric, 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 amide sulfate tetrahydrate, aluminum sulfate, aluminum sulfite, Aluminum thiosulfate, poly aluminum chloride, aluminum nitrate nonahydrate, aluminum chloride hexahydrate,
Ferrous bromide, ferrous chloride, ferric chloride, ferrous sulfate, ferric sulfate, zinc bromide, zinc chloride, zinc nitrate hexahydrate, zinc sulfate, zirconium acetate, zirconium chloride, chloride Zirconium oxide octahydrate, zirconium hydroxychloride, chromium acetate, chromium sulfate, magnesium sulfate, magnesium chloride hexahydrate, magnesium citrate nonahydrate, sodium phosphotungstate, sodium tungsten citrate, 12 tungstophosphate n Hydrate, 12-tungstosilicic acid 26-hydrate, molybdenum chloride, 12-molybdophosphate n-hydrate and the like.

In the present invention, a water-soluble aluminum compound or a water-soluble compound containing a Group 4A element in the periodic table is particularly preferable. As the water-soluble aluminum compound, for example, as an inorganic salt, aluminum chloride or a hydrate thereof, aluminum sulfate or a hydrate thereof, ammonium alum and the like are known. Further, there is a basic polyaluminum hydroxide compound which is an inorganic aluminum-containing cationic polymer. Particularly, a basic polyaluminum hydroxide compound is preferable.

The basic polyaluminum hydroxide compound
Means that the main component is represented by the following formula A, B or C;
If [Al₆(OH)₁₅]³⁺, [Al₈(OH)₂₀]⁴⁺,
[Al ₁₃(OH)₃₄]⁵⁺, [Al_{twenty one}(OH)₆₀]³⁺,etc
Contains basic and high-molecular polynuclear condensed ions such as
Is a water-soluble polyaluminum hydroxide.

[Al ₂ (OH) _{n Cl 6-n} ] _m Formula A [Al (OH) ₃ ] _n AlCl ₃ Formula B Al _n (OH) _m Cl _(3n-m) 0 <m <3n Formula C

These are water treatment agents under the name of polyaluminum chloride (PAC) from Taki Chemical Co., Ltd., and polyaluminum hydroxide (Paho) from Asada Chemical Co., Ltd. It is marketed by RIKEN GREEN under the name Purachem WT and from other manufacturers for the same purpose, and various grades are readily available. In the present invention, these commercial products can be used as they are,
Some substances have an inappropriately low pH, and in such a case, the pH can be appropriately adjusted and used.

The water-soluble compound containing a Group 4A element in the periodic table used in the present invention is not particularly limited as long as it is water-soluble, but a water-soluble compound containing titanium or zirconium is preferred.
For example, as a water-soluble compound containing titanium, titanium chloride,
Titanium sulfate, as water-soluble compounds containing zirconium, zirconium acetate, zirconium chloride, zirconium oxychloride, zirconium hydroxychloride, zirconium nitrate, basic zirconium carbonate, zirconium hydroxide, zirconium ammonium carbonate, zirconium potassium carbonate, zirconium sulfate And zirconium fluoride compounds are known. Some of these compounds have an inappropriately low pH. In such a case, the pH can be appropriately adjusted and used. In the present invention, the term "water-soluble" refers to a condition in which 1% by weight or more is dissolved in water at normal temperature and normal pressure.

In the present invention, the content of the above-mentioned water-soluble metal compound in the ink receiving layer is set at 0.1 to the inorganic fine particles.
The content is preferably 1 to 10% by weight, more preferably 1 to 5% by weight.

Two or more of the above-mentioned cationic compounds can be used in combination. For example, a cationic polymer and a water-soluble metal compound can be used in combination.

In the present invention, the film surface pH of the ink receiving layer
Is preferably 2 to 6, and particularly preferably 3 to 5. The pH of the surface of the ink receiving layer is determined by the method described in J. Org. This is the surface pH measured after 30 seconds using distilled water according to the method described in TAPPI Paper Pulp Test Method N0.49.

The pH of the ink receiving layer is preferably adjusted at the stage of the coating solution. However, since the pH of the coating solution does not always match the pH of the film surface after the coating and drying, the coating solution and the film surface may not be adjusted. It is necessary to determine the relationship with pH in advance by experiments or the like in order to obtain a predetermined film surface pH. The pH of the ink receiving layer coating solution is adjusted by appropriately combining an acid or an alkali. Examples of the acid include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid, and organic acids such as acetic acid, citric acid, and succinic acid. Examples of the alkali include sodium hydroxide, ammonia water, potassium carbonate, and trisodium phosphate. Alternatively, as the weak alkali, an alkali metal salt of a weak acid such as sodium acetate is used.

The ink receiving layer of the present invention can further contain various oil droplets for improving the brittleness of the film.
Such oil droplets include hydrophobic high-boiling organic solvents having a solubility in water at room temperature of 0.01% by weight or less (for example, liquid paraffin, dioctyl phthalate, tricresyl phosphate, silicone oil, etc.) and polymer particles ( For example, particles obtained by polymerizing one or more polymerizable monomers such as styrene, butyl acrylate, divinylbenzene, butyl methacrylate, and hydroxyethyl methacrylate) can be contained. Such oil droplets can be preferably used in the range of 10 to 50% by weight based on the hydrophilic binder.

In the present invention, a surfactant can be added to the ink receiving layer. The surfactant used may be any of anionic, cationic, nonionic and betaine types, and may be of low molecular weight or high molecular weight. One or two or more surfactants are added to the ink receiving layer coating solution. When two or more surfactants are used in combination, an anionic surfactant and a cationic surfactant are used in combination. It is not preferable. The addition amount of the surfactant is preferably 0.001 to 5 g with respect to 100 g of the binder constituting the ink receiving layer,
More preferably, it is 0.01 to 3 g.

In the present invention, the ink receiving layer further comprises:
Publicly known coloring dyes, coloring pigments, fixing agents for ink dyes, ultraviolet absorbers, antioxidants, pigment dispersants, defoamers, leveling agents, preservatives, fluorescent brighteners, viscosity stabilizers, pH regulators, etc. Can be added.

The support used in the present invention is preferably a water-resistant support. As the water-resistant support, a polyester resin such as polyethylene terephthalate, a diacetate resin, a triacetate resin, an acrylic resin, a polycarbonate resin, a polyvinyl chloride, a polyimide resin, a plastic resin film such as cellophane and celluloid, and a polyolefin resin on both sides of paper And resin-coated paper laminated with The thickness of the water-resistant support used in the present invention is preferably about 50 to 300 μm.

The base paper constituting the resin-coated paper preferably used in the present invention is not particularly limited, and generally used paper can be used, and more preferably, for example, a smooth paper such as that used for a photographic support is used. Base paper is preferred. As the pulp constituting the base paper, natural pulp, recycled pulp, synthetic pulp or the like may be used alone or in combination of two or more. This base paper contains sizing agents, paper strength agents, fillers, antistatic agents, fluorescent whitening agents,
Additives such as dyes are blended.

Further, a surface sizing agent, a surface paper-strengthening agent, a fluorescent whitening agent, an antistatic agent, a dye, an anchoring agent and the like may be coated on the surface.

The thickness of the base paper is not particularly limited. However, it is preferable that the base paper has good surface smoothness, for example, by applying pressure by using a calender or the like during or after paper formation, and the basis weight is 30%. ~250g / m ² is preferred.

As the resin of the resin-coated paper, a polyolefin resin or a resin curable by an electron beam can be used.
The polyolefin resin is a low-density polyethylene, high-density polyethylene, polypropylene, polybutene, a homopolymer of an olefin such as polypentene or a copolymer of two or more olefins such as an ethylene-propylene copolymer and a mixture thereof, Those having various densities and melt viscosity indices (melt index) can be used alone or in combination.

In the resin of the resin-coated paper, white pigments such as titanium oxide, zinc oxide, talc and calcium carbonate; fatty acid amides such as stearamide and arachidic amide; zinc stearate; calcium stearate; Aluminum, metal salts of fatty acids such as magnesium stearate, antioxidants such as Irganox 1010 and Irganox 1076, blue pigments and dyes such as cobalt blue, ultramarine blue, cecilian blue, and phthalocyanine blue, cobalt violet, fast violet, and manganese purple It is preferable to add various additives such as magenta pigments and dyes, fluorescent brighteners and ultraviolet absorbers in an appropriate combination.

The resin-coated paper, which is preferably used in the present invention, is produced by a so-called extrusion coating method in which, in the case of a polyolefin resin, a heat-melted resin is cast on a running base paper, both surfaces of which are formed of resin. Coated. In the case of a resin that is cured by an electron beam, the resin is applied by a commonly used coater such as a gravure coater or a blade coater, and then irradiated with an electron beam to cure and coat the resin. Further, before coating the resin on the base paper, the base paper is preferably subjected to an activation treatment such as a corona discharge treatment or a flame treatment. The surface (surface) of the support on which the ink receiving layer is applied has a glossy surface, a matte surface, and the like, depending on the application, and the glossy surface is used particularly advantageously. It is not necessary to coat the back surface with a resin, but it is preferable to coat the resin from the viewpoint of curling prevention. The back surface is usually a matte surface, and the front surface or both front and back surfaces can be subjected to an activation treatment such as a corona discharge treatment or a flame treatment as required. The thickness of the resin coating layer is not particularly limited, but is generally 5 to 50 μm thick on the surface or on both sides.

The support in the present invention may be coated with various back coat layers for antistatic properties, transport properties, curling prevention properties, and the like. The back coat layer can contain an inorganic antistatic agent, an organic antistatic agent, a hydrophilic binder, a latex, a curing agent, a pigment, a surfactant and the like in an appropriate combination.

In the present invention, the method for applying the ink receiving layer is not particularly limited, and a known coating method can be used. For example, there are a slide lip system, a curtain system, an extrusion system, an air knife system, a roll coating system, a rod bar coating system, and the like.

In the present invention, the ink jet recording material may be provided with an ink absorbing layer, an ink fixing layer, an intermediate layer, a protective layer and the like in addition to the ink receiving layer. For example,
The lower layer may be provided with a water-soluble polymer layer, or the upper layer may be provided with a swelling layer.

The ink composition suitably used for the ink jet recording material of the present invention is not particularly limited. For example, JP-A Nos. 9-151345 and 9-1.
65539 and 10-259334 can be used.

As a coloring material of the ink composition, any of dyes and pigments can be used, but it is particularly effective for dyes. Examples of dyes include any of known direct dyes, acid dyes, food dyes, basic dyes, reactive dyes, disperse dyes, vat dyes, soluble vat dyes, reactive disperse dyes, and oil dyes. Among them, a water-soluble dye is preferably used in terms of the performance of the recording liquid. Further, among these dyes, the direct dye having relatively poor storage stability after printing has a remarkable effect of improving the image storage stability of the present invention.

As the solvent for the ink composition, water and an organic solvent are used. Particularly, as the organic solvent, 1,3-dimethyl-2-imidazolidinone, 2-pyrrolidone, N-methyl-2-pyrrolidone, ε Nitrogen-containing cyclic compounds such as caprolactam, and mixtures thereof, and ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol,
Polyhydric alcohols such as 1,3-propanediol, 1,5-pentanediol, 1,2,6-hexanetriol, glycerin, and mixtures thereof are preferred.

In the ink composition, a nonionic acetylene glycol-based surfactant such as Surfynol 465, Surfynol 104, Olfin STG (trade name, manufactured by Nissin Chemical Co., Ltd.), Glycol ethers such as ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, and triethylene glycol monoethyl ether may be used. Further, as a pH adjuster, tri (hydroxyalkyl) amine such as triethanolamine, LiOH, A hydroxide of a metal element selected from the group consisting of elemental group Ia such as NaOH and KOH can be used. If necessary, lower alcohols,
A water-soluble polymer such as sodium alginate, a water-soluble resin, a fluorinated surfactant, a fungicide, a rust preventive, and the like may be added.

[0062]

EXAMPLES The present invention will be described below in detail with reference to examples, but the contents of the present invention are not limited to the examples. In addition, a part means a solid content weight part.

Example 1 As supports, LBKP (50 parts) and LBSP (50 parts) were used.
Part) of a pulp blend of 120 g / m ² , and a 25 g / m ² resin composition comprising low-density polyethylene (70 parts), high-density polyethylene (20 parts) and titanium oxide (10 parts) is applied to the surface of a 120 g / m ² base paper. And high-density polyethylene (50
Parts) and a low-density polyethylene (50 parts) resin coating paper prepared by applying 25 g / m ² .

An ink-receiving layer coating solution having the following composition was prepared, coated on the above support so that the coating amount of fumed silica was 18 g / m ^{2 as a} solid content, and dried, and then an ink jet recording sheet was prepared. It was created. Each recording sheet was adjusted so that the film surface pH of the ink receiving layer was 4.2.

<Recording sheet 1> 100 parts of fumed silica (average primary particle diameter: 7 nm, specific surface area by BET method: 300 m ² / g) 25 parts of polyvinyl alcohol (trade name: PVA235, manufactured by Kuraray Co., Ltd., degree of saponification) 88%, average polymerization degree 3500) Boric acid 4 parts Amphoteric surfactant 0.3 parts (Product name: SWAM AM-2150, manufactured by Nippon Surfactant) Cationic polymer C-1 (Table 1) 10 parts

<Recording Sheets 2 to 10> Recording Sheet 1
Recording sheets 2 to 10 were prepared in the same manner except that the cationic polymer was changed to C-2 to C-10.

<Recording Sheet 11> Instead of 10 parts of the cationic polymer C-1 (Table 1) of the recording sheet 1, C-1 was used.
Recording sheet 11 was prepared in the same manner except that 3 parts of 1 (Table 1) and 5 parts of 1,1-dimethyl-4- (3-methacryloyloxypropyl) semicarbazide were used.

<Recording Sheet 12> Instead of 10 parts of the cationic polymer C-1 (Table 1) of the recording sheet 1, C-1 was used.
Recording sheet 12 was prepared in the same manner except that 3 parts of 1 (Table 1) and 3 parts of 1,1-dimethyl-5- (2-hydroxy-3-methacryloyloxypropyl) carbonohydrazide were used. .

<Recording Sheet 13> Instead of 10 parts of cationic polymer C-1 (Table 1) of recording sheet 1, C-1 was used.
Recording sheet 13 was prepared in the same manner except that 3 parts of Table 1 (Table 1) and 5 parts of N-hydroxy-N '-(3-methacryloyloxypropyl) urea were used.

<Recording Sheet 14> Instead of 10 parts of the cationic polymer C-1 (Table 1) of the recording sheet 1, C-1 was used.
Recording sheet 14 was prepared in the same manner except that three copies of Table 1 (Table 1) were used.

[0071]

[Table 1]

[0072]

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[0073]

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For each of the obtained ink jet recording sheets, a six-color ink jet printer (PM-770 manufactured by Seiko Epson Corporation) using the following dark and light inks was used.
C) was used to evaluate the ink absorbency, storage stability after printing (light fastness and gas fastness), and gloss. Table 2 shows the results.

<Ink Absorbency> C, M, and Y were each 1
Immediately after printing, PPC paper was superimposed on the printed portion and lightly pressed, and the amount of ink transferred to the PPC paper was visually observed and evaluated according to the following criteria. ：: No transfer at all. ×: Transfer.

<Gas Resistance> Solid printing was performed so that the optical density of cyan with the greatest fading was 1.0, and after exposure to an atmosphere having an ozone concentration of 20 ppm for 1.5 hours,
The optical density of the printed portion was measured, and the residual ratio (optical density after exposure / optical density /
(Optical density before exposure) was determined and is shown in Table 2.

<Light fastness> Solid printing was performed in the same manner as in the gas fastness test so that the optical density of cyan became 1.0, and 6 was printed using a Suntest CPS photobleaching tester manufactured by Atlas.
After irradiation at 00 W / m ² for 30 hours, the optical density of the printed portion was measured, and the residual ratio (optical density after irradiation / optical density before irradiation)
And the results are shown in Table 2.

<Glossiness> The glossiness was measured according to the method described in JIS P-8142 (Test method for 75 ° specular glossiness of paper and paperboard).

The composition of the dark and light ink used is as follows.

[Cyan Ink] Direct Blue 199 2.4 g Ethylene glycol 16.01 g Glycerin 9.5 g Finished to 100 ml with pure water.

[Magenta Ink] Direct Red 227 1.8 g Glycerin 3.5 g Diethylene glycol monobutyl ether 21.5 g Finished to 100 ml with pure water.

[Yellow Ink] Direct Yellow 86 2.0 g Diethylene glycol 22.2 g Glycerin 4.5 g Finished to 100 ml with pure water.

[Light Cyan Ink] Direct Blue 199 0.6 g Ethylene glycol 16.01 g Glycerin 9.5 g Finished to 100 ml with pure water.

[Light magenta ink] Direct Red 227 0.5 g Glycerin 3.5 g Diethylene glycol monobutyl ether 21.5 g Finished to 100 ml with pure water.

[0085]

[Table 2] 記録 Recording sheet Ink absorptivity Storage (%) Remarks Lightfastness Gasfastness １ 1 7877 Invention 2 ８２ 82 79 Invention 3 ８１ 81 83 Invention 4 ８７ 87 86 Invention 5 ○ 75 76 Invention 6 ○ 84 82 Invention 7 ○ 85 84 Invention 8 ○ 86 85 Invention 9 ○ 76 74 Invention 10 ○ 77 75 Invention 11 ○ 65 62 Comparison 12 ○ 69 67 Comparison 13 ○ 59 58 Comparison 14 ○ 52 53 Comparison ────────────────────────────

The glossiness of each recording sheet was 60 to 6
5% showed high gloss.

As is evident from the results shown in Table 2, the use of the compound of the present invention improves storage stability while maintaining high ink absorbency, and provides photo-like high gloss.

Example 2 The fumed silica used in Example 1 was replaced with an average primary particle size of 15 n.
The same test was conducted except that m-type and plate-like pseudo-boehmite having an aspect ratio of 5 were used. As a result, almost the same results were obtained in ink absorbency, storage stability, and glossiness.

Example 3 The fumed silica used in Example 1 had an average primary particle size of 13 n.
The same test was performed except that m was replaced with γ-alumina (Aerosil aluminum oxide C, manufactured by Nippon Aerosil Co., Ltd.). As a result, almost the same results were obtained in ink absorbency, storage stability, and glossiness.

[0090]

According to the present invention, a photo-like ink jet recording material having high ink absorption, high gloss and improved storage stability can be obtained.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (Reference) C08L 101/14 B41J 3/04 101Y F term (Reference) 2C056 EA13 FC06 2H086 BA15 BA19 BA33 BA35 BA45 4J002 BE02X BG07W BG13W BJ00W DE146 DJ016 EE017 EE027 EU187 FD147 GS00

Claims (10)

[Claims] 1. An ink jet recording material having an ink receiving layer provided on a support, wherein the ink receiving layer has a repeating structure selected from a hydrazine derivative structure or an acyclic hydroxylamine derivative structure, and a cation different from these. Having a repeating structure for imparting
An ink jet recording material comprising a cationic polymer. 2. The ink jet recording material according to claim 1, wherein the hydrazine derivative structure is a semicarbazide derivative structure or a carbonohydrazide derivative structure. 3. The non-cyclic hydroxylamine derivative structure is an N-acylhydroxylamine derivative structure.
The ink jet recording material according to claim 1. 4. The ink-jet recording material according to claim 1, wherein the repeating structure for imparting cationicity is a repeating structure selected from a tertiary amino group or a quaternary ammonium group. 5. The proportion of a repeating structure selected from a hydrazine derivative structure or an acyclic hydroxylamine derivative structure in the entire cationic polymer is 10 to 50.
The ink-jet recording material according to claim 1, which is mol%. 6. The ink jet recording material according to claim 1, wherein the ink receiving layer contains inorganic fine particles. 7. The ink jet recording material according to claim 6, wherein the inorganic fine particles are fumed silica, alumina, or alumina hydrate having an average primary particle size of 30 nm or less. 8. The ink jet recording material according to claim 6, which comprises 10 to 40% by weight of a hydrophilic binder based on the inorganic fine particles. 9. The ink jet recording material according to claim 1, wherein the ink receiving layer is cross-linked by a cross-linking agent. 10. The support according to claim 1, wherein the support is a water-resistant support.
10. The ink jet recording material according to any one of items 1 to 9.