JPH1158943A - Ink jet recording material and recording method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve stripe nonuniformity, moisture resistance, and bleeding prevention and the prevention of wounds by applying an application liquid containing nonspherical colloidal silica and a water-dispersive cationic polymer on an ink receiving layer and drying the liquid. SOLUTION: A liquid in which silica particulates are dispersed (generally 5-15%) is added gradually into a polyvinyl alcohol aqueous solution (generally 3-15%) whose pH is kept at about 6-8 and whose temperature is kept at about 40 deg.C with stirring strongly. After the addition, dispersion is done by an ultrasonic dispersion machine, a high speed homogenizer or the like. Next, after various additives being added, viscosity is adjusted to be necessary for application, application on a support and drying are done, and a coat membrane having voids is obtained. A void layer by soft aggregation formation, in order to obtain a high void percentage without deteriorating the fragility of the membrane, a water-soluble binder is preferably crosslinked by a crosslinking agent. The quantity of the membrane applied of an ink receiving layer is more preferably about 10-50 g/m<2> . The solid concentration of an application liquid is especially preferably about 5-20 wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an ink jet recording material and a recording method applicable to various ink jet recording methods.

[0002]

2. Description of the Related Art In recent years, with the spread of personal computers, printers of the ink jet recording system have rapidly spread. In particular, its use has attracted attention in the printing field and design field where high image quality is required.

As a recording material used in the ink jet recording system, a coating layer or an ink receiving layer is provided on a support called an ink jet recording paper or a film in addition to ordinary paper to prevent ink bleeding and overlapping. Improve
High resolution has been realized.

However, in the ink jet recording system, a water-soluble ink is often used to directly eject ink and form an image.
Insufficient fixation of the dye causes problems such as bleeding and an increase in concentration. In particular, this phenomenon becomes remarkable when stored under high humidity environmental conditions. Particularly in recent years, colorization of the ink jet recording method has been rapidly progressing,
In order to approach the high quality output of silver halide photos,
In order to eliminate the roughness of the low-density portion, a printer has been developed by a method of forming an image with two or more types of inks (dark and light inks) of a certain reference color (for example, Y, M, C, and K) having different densities. For example, low-density areas use light-colored inks to reduce roughness, and high-density areas mainly use dark-colored inks to provide a sufficient maximum density. Etc. are known. However, in the case of color printing, the color tone changes if the degree of the above-described blur or density increase differs for each color, and the human eye's detection power is sensitive to the color tone change.
An immediate solution is desired. In addition, there is a problem that unevenness in the shape of a cod is easy to appear, and particularly in the case of glossy paper, it is conspicuous, which is a main factor in lowering image quality.

Further, when a print such as a poster is output, there is a problem that the blur of characters is very conspicuous in an image in which characters are drawn on a color background, and improvement is desired. .

In order to pursue a quality approaching that of silver halide photography, glossy media has been developed and put to practical use in recent years. However, the ink receiving layer may be damaged during transportation of the printer or during handling after printing, and is noticeable on glossy paper.

[0007] That is, the handling environment and application of the conventional ink jet recording material are limited as compared with the printed matter and the electrophotographic copy. For example, when a poster or the like is created using a large-format printer, it is necessary to perform a lamination process to prevent intrusion of humidity.

[0008] In order to solve these problems, pigments have been studied as an approach from ink. However, there are many problems such as nozzle clogging and dispersion techniques. It is.

[0009] In the approach from the recording sheet, in particular, in the field of business use, a method of laminating after printing has been devised, but it is preferable for the user because the number of work steps increases and the cost increases. Was not.

[0010] From the above, the appearance of a recording material for ink jet recording which is excellent in handleability after printing has been desired.

Various studies have been made on the means for solving water resistance and moisture resistance. For example, Japanese Unexamined Patent Publication No.
Japanese Patent No.-64591 discloses that a water-proofing agent is contained to improve the water-resistance, but it has been found that the light-fastness is remarkably deteriorated.

Although the waterproofing agent described in JP-A-61-58788 certainly has a mordant power, it does not exert a sufficient effect on moisture resistance.

On the other hand, it was also found that the water-proofing agent described in JP-A-6-183131 significantly improved the light fastness deterioration, but significantly impaired the ink absorption, and did not provide satisfactory image quality.

In the prior art, moisture resistance, prevention of bleeding,
It was very difficult to solve all of the wound prevention.

[0015]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide an ink jet recording material and a recording method which are excellent in stripe unevenness, moisture resistance, bleeding prevention and scratch prevention.

[0016]

The above objects of the present invention are as follows. In an ink jet recording material having a support and an ink receiving layer provided on the support, the ink receiving layer is obtained by applying and drying a coating liquid containing non-spherical colloidal silica and a water-dispersible cationic polymer. 1. an ink jet recording material, 2. The ink-jet recording material according to the above 1, wherein the non-spherical colloidal silica is amorphous. 3. The ink jet recording material according to the above 1 or 2, wherein the shape of the non-spherical colloidal silica is at least one of a branched shape, a rod shape, a bent shape, and a ring shape. The number average particle diameter of the water-dispersible cationic polymer is 5
4. the ink-jet recording material according to any one of the above items 1 to 3, wherein 5. The inkjet recording material according to any one of the above items 1 to 4, wherein the content of the water-dispersible cationic polymer in the ink receiving layer is 1 to 30% by weight. 6. The ink jet recording material according to any one of the above items 1 to 5, wherein the support has a moisture permeability of 1 to 20 g / m ² · day. 7. The ink jet recording material according to any one of the above items 1 to 6, wherein the support is a polyethylene-coated paper. 8. The ink jet recording material according to any one of the above items 1 to 7, wherein the content of the inorganic particles in the ink receiving layer in the ink receiving layer is 75 to 95% by weight. The ink-jet recording material according to any one of the above items 1 to 8, wherein the water-dispersible cationic polymer contains at least one compound represented by the following general formula (I).

[0017]

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In formula (I), (A) represents a monomer unit obtained by polymerizing a copolymerizable monomer having a quaternary ammonium group, and (B) represents a monomer unit represented by formulas (II) and (II).
It represents a monomer unit obtained by polymerizing a copolymerizable monomer containing at least one of the structures represented by I), (IV) and (V).

[0019]

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In the general formula (II), R ₁ and R ₂ represent an aliphatic group, and in the general formula (III), Z is ＝ C-
Represents a group of non-metallic atoms necessary for forming a 5- or 6-membered ring in cooperation with N = C-. In the general formula (IV), R ₃ and R ₄ represent an aromatic group, a halogen atom, a cyano group, and an oxycarbonyl group. In the general formula (V), R ₅ represents a hydrogen atom and an aliphatic group, and R ₆ represents an aliphatic group.

In the above general formula (I), (C) represents a monomer unit obtained by polymerizing a copolymerizable monomer having at least two ethylenically unsaturated bonding groups, and (D) represents (A), (B) And a monomer unit obtained by polymerizing a copolymerizable monomer other than (C).

K is from 10 to 95 mol%, m is from 0 to 30
Mol%, n is 2 to 20 mol%, p is 0 to 80 mol%
Represents However, k + m + n + p = 100 mol%.

10. A color ink jet recording method, wherein recording is performed on a recording material according to any one of 1 to 9 above, using a recording apparatus that outputs using at least 10.5 different inks. 10. A color ink jet recording method, comprising: recording on at least one reference color using two or more different inks on the recording material according to claim 1. . 12. The color ink jet recording method according to the item 11, wherein the reference color is recorded by a recording device that records with two or more types of inks in which the absorbance of the reference color ink is substantially different. .

[0024]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The details of the present invention will be described below. The water-dispersible cationic polymer in the present invention is a cationic polymer particle which is in a dispersed state using water as a dispersion medium, and is a particle itself insoluble in water.

The water-dispersible cationic polymer of the present invention preferably has a quaternary ammonium group.

The water-dispersible cationic polymer preferably used in the present invention has a unit represented by the following general formula (I).

[0027]

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In formula (I), (A) represents a monomer unit obtained by polymerizing a copolymerizable monomer having a quaternary ammonium group, and (B) represents a monomer unit represented by formulas (II) and (II).
It represents a monomer unit obtained by polymerizing a copolymerizable monomer containing at least one of the structures represented by I), (IV) and (V).

[0029]

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In the general formula (II), R ₁ and R ₂ represent an aliphatic group, and in the general formula (III), Z is ＝ C-
Represents a group of non-metallic atoms necessary for forming a 5- or 6-membered ring in cooperation with N = C-. In the general formula (IV), R ₃ and R ₄ represent an aromatic group, a halogen atom, a cyano group, and an oxycarbonyl group. In the general formula (V), R ₅ represents a hydrogen atom and an aliphatic group, and R ₆ represents an aliphatic group.

In the above general formula (I), (C) represents a monomer unit obtained by polymerizing a copolymerizable monomer having at least two ethylenically unsaturated bonding groups, and (D) represents (A), (B) And a monomer unit obtained by polymerizing a copolymerizable monomer other than (C).

K is from 10 to 95 mol%, and m is from 0 to 30 mol%.
Mol%, n is 2 to 20 mol%, p is 0 to 80 mol%
Represents However, k + m + n + p = 100 mol%.

In the above general formula (I), (A) is represented by the following general formulas (VI), (VII), (VIII) and (I)
The monomer unit represented by X) is preferred.

[0034]

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The above general formulas (VI), (VII) and (VI)
In II) and (IX), R ₇ is a hydrogen atom or an aliphatic group having 1 to 4 carbon atoms (for example, a methyl group, an ethyl group,
n-butyl group etc.). R ₇ is preferably a hydrogen atom or a methyl group.

The above general formulas (VI), (VII) and (VI)
R ₈ , R ₉ , R ₁₀ and R in II) and (IX)
₁₁ represents an aliphatic group having 1 to 10 carbon atoms (for example, a methyl group, an ethyl group, a cyclohexyl group, a benzyl group, etc.). These _{R 8, R 9, R 1} 0 and the substituent represented by R ₁₁ may be independently identical or different from each other, or may be bonded together to form a ring structure together. R ₈ ,
R ₉ , R ₁₀ and R ₁₁ are preferably a methyl group, an ethyl group and a benzyl group, and a methyl group and a benzyl group are particularly preferred.

The above general formulas (VI), (VII) and (VI)
In II) and (IX), X represents an anion, for example, a halogen ion (eg, chloride ion, bromine ion, iodine ion, etc.), an alkyl sulfate ion (eg, methyl sulfate ion, etc.), an alkyl or aryl sulfonate ion (eg, methane ion) Sulfonate ion, p-toluenesulfonic acid ion, etc.), and acetate ion.
Of these, halogen ions and alkyl sulfate ions are particularly preferred. In the general formula (VI), a represents an integer of 1 to 4.

In the general formula (VII), Q represents an oxygen atom or a nitrogen atom. T and W represent a divalent linking group, for example, an ethylene group, a 1,4-cyclohexylene group,
_{-CH 2 CH 2 OCH 2 CH 2} O -, - CH 2 CH (O
H) represents CH ₂ — and a phenylene group. b is 0 or 1
Represents

In the general formulas (VIII) and (IX), R ₁₂ is a hydrogen atom, an aliphatic group (for example, a methyl group, t
-Butyl group, etc.), an aromatic group (eg, a phenyl group), a halogen atom, a cyano group, an acyl group (eg, an acetyl group,
Benzoyl group), an oxycarbonyl group (eg, a methoxycarbonyl group), an aminocarbonyl group (eg, an aminocarbonyl group), and a nitro group.

In the general formula (I), examples of the monomer derived from the monomer unit represented by (A) are shown below.

[0041]

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In the above general formula (I), (B) is preferably a monomer unit represented by the following general formulas (X), (XI) and (XII).

[0043]

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The above general formulas (X), (XI) and (XI)
In I), R ₇ represents a hydrogen atom or an aliphatic group having 1 to 4 carbon atoms (eg, a methyl group, an ethyl group, an n-butyl group, etc.). R ₇ is preferably a hydrogen atom or a methyl group.

In the general formula (X), Q represents an oxygen atom or a nitrogen atom. T and W represent a divalent linking group, for example, ethylene group, 1,4-cyclohexylene group, -CH
_{2 CH 2 OCH 2 CH 2 O} -, - CH 2 CH (OH) C
H ₂ — and a phenylene group. e, f, and g each represent 0 or 1 (however, when e is 1, f and g
Are never 0). R ₁₃ and R ₁₄ represent a hydrogen atom, an alkyl group, and an aryl group. These R
_The alkyl group and the aryl group represented by ₁₃ and R ₁₄ may be bonded to each other to form a cyclic structure.

In the general formula (XI), R ₁₅ represents a halogen atom (eg, a chlorine atom), an aromatic group (eg, a phenyl group), an aryloxy group (eg, a phenoxy group), a hydroxy group, or the like.

In the general formula (XII), R ₁₆ is 2
-Represents a pyridyl group, a 4-pyridyl group, and a 1-imidazole group.

In the above formula (I), examples of the monomer derived from the monomer unit represented by (B) are shown below.

[0049]

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In the above formula (I), examples of the monomer derived from the monomer unit represented by (C) include divinylbenzene, ethylene glycol methacrylate,
Examples include ethylene glycol acrylate, hydroquinone methacrylate, hydroquinone acrylate, ethylene dimethacrylamide, ethylene diacrylamide, and the like.

In the above general formula (I), (C) is preferably a monomer unit represented by the following general formula (XIII).

[0052]

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In the general formula (XIII), R ₇ represents a hydrogen atom or an aliphatic group having 1 to 4 carbon atoms (eg, a methyl group, an ethyl group, an n-butyl group, etc.). R ₇ is preferably a hydrogen atom or a methyl group. V represents a divalent linking group, for example, an arylene group (eg, a phenylene group, a naphthylene group, etc.) and an alkylene group (eg, a methylene group, a 1,4-butylene group, etc.). Y is an ester bond (for example, -C (= O) -O-, -OC (= O)
-), An amide bond (for example, -C (= O) -NH-, -N
H—C (＝ O) —, —SO ₂ —NH—), an ether bond (—O—) or the like, and r represents 0 or 1.

In the above formula (I), examples of the monomer unit represented by (D) include ethylene, propylene, 1-butene, isobutene, styrene, α-methylstyrene, vinyltoluene, acrylic acid and esters thereof, Amide derivatives (eg, methyl acrylate, butyl acrylate, t-butyl acrylamide, etc.), methacrylic acid and its esters or amide derivatives (eg, methyl methacrylate, benzyl methacrylate, n-butyl methacrylamide, etc.), acrylonitrile, methacrylonitrile And the like.

In the above formula (I), (D) is preferably a monomer unit represented by the following formula (XIV).

[0056]

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In the above formula (XIV), R ₇ represents a hydrogen atom or an aliphatic group having 1 to 4 carbon atoms (eg, a methyl group, an ethyl group, an n-butyl group, etc.). R ₇ is preferably a hydrogen atom or a methyl group. R ₁₇ is a hydrogen atom or an aliphatic group having 1 to 6 carbon atoms (for example, a methyl group,
Ethyl group, t-pentyl group, etc.). As R ₁₇ , a hydrogen atom or a methyl group is particularly preferred.

The particle size of the water-dispersible cationic polymer in the present invention is preferably 5 to 400 nm in number average particle size.
More preferably 10 to 200 nm, particularly preferably 3
0 to 180 nm.

The particle size of the water-dispersible cationic polymer in the present invention can be controlled by conditions such as the reaction temperature during the synthesis of the polymer, stirring conditions, the amount of the polymerization initiator, the type and the amount of the surfactant, and the like.

The content of the water-dispersible cationic polymer in the ink receiving layer in the present invention is preferably 1 to 30% by weight, particularly preferably 2 to 20% by weight, and further preferably 3 to 12% by weight. . The content of water-dispersible cationic polymer in the ink receiving layer of the present invention is preferably from 0.1 to 10 g / m ^2, more preferably 0.3 to 5 g / m ^2, particularly preferably 0.5 3g /
m ² .

Specific examples of the water-dispersible cationic polymer used in the ink jet recording material of the present invention are shown below, but the present invention is not limited thereto. The exemplified polymers each contain the following repeating units at the following ratios.

[0062]

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[0063]

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[0064]

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[0065]

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[0066]

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[0067]

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[0068]

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[0069]

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[0070]

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The water-dispersible cationic polymer used in the ink jet recording material of the present invention can be synthesized by a conventionally known method such as solution polymerization, suspension polymerization, or emulsion polymerization. For example, JP-A-51-73440. JP-A-55-58201, JP-A-55-142339, and the like, such as emulsion polymerization and emulsifier-free emulsion polymerization.

The following is a synthesis example of the water-dispersible cationic polymer of the present invention. [Synthesis Example of Exemplary Compound (L-1)] Synthesis of Exemplary Polymer (L-1) (1) Synthesis of Intermediate Amino Monomer In a 1-liter eggplant-shaped flask, 240 ml of ethanol was added.
Take 198.4 g of dimethylamine aqueous solution (40%),
Cool in ice water. To this, chloromethylstyrene was added dropwise so that the internal temperature did not exceed 30 ° C. After the addition, the reaction is carried out in a water bath at 40 ° C. for 4 hours. After completion of the reaction, about 60 ml of the solvent is recovered under reduced pressure. 300 ml of water and 50 of toluene
0 ml is added and the organic layer is separated. The obtained organic layer was washed with water 3
After washing three times with 00 ml, 500 ml of 2N hydrochloric acid was added.
In addition, the aqueous layer is separated.

While cooling the obtained aqueous layer in ice water, 2
550 ml of a specified aqueous sodium hydroxide solution is added for neutralization. To this is added 150 ml of ethyl acetate to extract organic matter. The same extraction operation was further repeated three times, and the obtained organic layer was washed twice with 500 ml of water. After drying the organic layer over anhydrous magnesium sulfate, the solvent is removed under reduced pressure to obtain the desired intermediate amino monomer as a yellow oil. Yield 97.5 g.

(2) Synthesis of Intermediate Polymer 250 ml of degassed water was placed in a 1-liter separable flask.
Surfactant (trade name "TRAX H-45") 8.1m
1), and the intermediate amino monomer (15.5 g) synthesized in the above (1), styrene (10.0 g), divinylbenzene (1.6 g; converted at a purity of 65%) are added thereto (molar ratio: 48). : 48: 4).

Under a nitrogen stream, the mixture was stirred at room temperature for 30 minutes (450 revolutions per minute) to emulsify. After emulsification, 0.63 g of azobiscyanovaleric acid (ACVA) dissolved in 25 ml of degassed water
And 1.2 g of potassium hydroxide were added dropwise, and the mixture was further heated and stirred in a 70 ° C. oil bath under a nitrogen stream for 5 hours;
50 rotations). After the reaction, the mixture was allowed to cool to room temperature, and the solid content was removed through filter paper. Thereafter, the volume was adjusted to 320 ml with pure water to obtain a desired intermediate polymer as a latex polymer.

(3) Synthesis of Exemplified Polymer (L-1) 100 ml of the intermediate polymer synthesized in (2) was
Then, 30 ml of acetonitrile is added dropwise over about 30 minutes with vigorous stirring. Next, 3.0 g of benzyl chloride was added, and the mixture was stirred at room temperature for 30 minutes.
The reaction was performed for 6 hours in a warm water bath at 0 ° C.

After the completion of the reaction, the mixture was allowed to cool to room temperature, and 1 ml of 1-hexanol was added. Further, under reduced pressure, the solvent was
The solution was distilled off, and finally finished to 100 ml with pure water to obtain the intended exemplified polymer (L-1) as a latex polymer.

In the ink jet recording material of the present invention,
Non-spherical colloidal silica is contained in the ink receiving layer.
The term "non-spherical" as used herein means substantially non-spherical, and is preferably a rod-like, branched, annular, bent, or the like. The non-spherical silica is preferably amorphous. The indefinite shape here means that it is not substantially uniform, and includes various forms.For example, if the particle is a branched particle, the position of the branch, the branch and the branch This includes forms including various things such as intervals and the number of branches. Also, branched, rod-shaped, annular,
Blended particles and the like are also included. In addition, when these configurations have a maximum length to thickness ratio of 3
The above-mentioned thing is preferable, and especially preferable thing about 5 times 100 times is more preferable. As a method for synthesizing the non-spherical colloidal silica, for example, a method described in JP-A-1-294515 can be mentioned. Preferred specific examples of such non-spherical silica are commercially available from Nissan Chemical Industries under the trade names such as Snowtex-OUP and Snowtex-UP. As the particle diameter, the long diameter is 4 to 30.
The one with 0 nm is preferred. Here, the major axis is represented by a length corresponding to the diameter of a circumscribed sphere of the particle.

In the present invention, it is also preferable that the ink receiving layer contains inorganic fine particles other than the non-spherical colloidal silica. Examples of such inorganic particles include alumina sol, spherical colloidal silica, oxide particles such as zinc oxide, titanium dioxide, yttrium oxide, magnesium oxide, niobium oxide, and antimony oxide, and various smectite clays such as synthetic hectorite (for example, Clays described in JP-A-81210 and JP-A-6-184998), talc, mica and the like are preferred. These inorganic fine particles preferably have a particle size of 3 to 200 nm in terms of glossiness, and particularly preferably have a particle size of 5 to 70 nm.

The ink receiving layer of the present invention preferably contains one or more water-soluble polymers.

The water-soluble polymer preferably used in the present invention includes, for example, gelatin, polyvinyl alcohols, polyvinylpyrrolidones, polyvinylpyridinium halides, various modified polyvinyl alcohols and other vinylformals and derivatives thereof (JP-A-60-145879).
No. 60-220750, No. 61-143177
Nos. 61-235182 and 61-235183
Nos. 61-237681 and 61-26189), polyacrylamide, polydimethylacrylamide, polydimethylaminoacrylate, sodium polyacrylate, methacrylic acid copolymer salt, polysodium methacrylate, vinyl acrylate Polymers containing acryl groups such as alcohol copolymer salts (Japanese Patent Laid-Open No. 60-16 / 1985)
8651, 62-9988, etc.), starch, oxidized starch, carboxyl starch, dialdehyde starch, cationized starch, dextrin, sodium alginate, gum arabic, casein, pullulan, dextran, methylcellulose, ethylcellulose, carboxymethylcellulose, Natural polymer materials such as hydroxypropylcellulose and derivatives thereof (JP-A-59-174382, JP-A-60-174382)
Nos. -262885, 61-143177, 61-
No. 181679, No. 61-193879, No. 61-2
87782), polyethylene glycol, polypropylene glycol, polyvinyl ether, polyglycerin, alkyl vinyl ether copolymer of maleic acid, maleic acid-N-vinyl pyrrole copolymer, styrene-maleic anhydride copolymer, polyethylene imine, etc. Synthetic polymers (JP-A-61-32787, JP-A-61-2)
37680 and 61-277483). Preferred among these polymers are gelatin, polyvinylpyrrolidones, polyvinyl alcohols, and polyalkylene oxides.

As the gelatin preferably used in the present invention, any gelatin can be used as long as it is a collagen made from animal collagen, but gelatin made from a collagen made from pigskin, cowskin and bovine bone is more preferable. . Further, the kind of gelatin is not particularly limited,
Lime-treated gelatin, acid-treated gelatin, derivative gelatin (for example, JP-B-38-4854 and JP-B-39-5514)
Nos. 40-12237 and 42-26345; U.S. Pat. Nos. 2,525,753 and 2,594,293
Nos. 2,614,928 and 2,763,639
Nos. 3,118,766 and 3,132,945
Nos. 3,186,846 and 3,312,553
Derivative gelatin described in JP-A Nos. 861,414 and 103,189 can be used alone or in combination. When acid-treated gelatin is used,
It is particularly advantageous in terms of water resistance. Further, those having an isoelectric point of 8 or more are preferable, and those having an isoelectric point of 8.5 to 10 are more preferable.

The preferred polyalkylene oxides are polyethylene oxides, and those having an average molecular weight in the range of 10,000 to 500,000 are preferred, and polyethylene glycol (sometimes referred to as PEG) is particularly preferred. With an average molecular weight of 50,
000 to 300,000. The average molecular weight of the polyalkylene oxides is a molecular weight calculated from a hydroxyl value.

The polyvinyl pyrrolidone has a molecular weight of preferably 100,000 or more, particularly preferably 20 to 40.
It is ten thousand.

The polyvinyl alcohol is preferably one having a degree of polymerization of 500 or more, particularly preferably 1,0.
It is at least 00, particularly preferably from 1,500 to 4,000. Further, a saponification degree of 75 to 98 mol% is particularly preferable. Further, various cation-modified, nonionic-modified and anion-modified ones can also be used. Further, it is preferable to use a cationic water-soluble polymer in combination with the cationic latex polymer of the present invention in view of the effect of further improving the water resistance.

The cationic water-soluble polymer preferably used in the present invention refers to a polymer which is water-soluble and mainly shows a cationic property in an aqueous solution.
These are described in JP-A-61-61887, JP-A-61-63477, JP-A-5-104848 and JP-A-5-124329. Polymers containing primary, secondary, tertiary amino groups, and quaternary ammonium salts are exemplified. Any such water-soluble cationic polymer can be used, and the type is not particularly limited,
Examples of the cationic water-soluble polymer more preferably used in the present invention include the following.

A) Polyallylamines b) Dicyandiamide-based condensates c) Polyethyleneimines d) Cation-modified PVA e) Cation-modified PVP f) Ebichlorohydrin derivative g) Amino-substituted nylon h) The following general formula (1) I) a polymer containing a structural unit derived from a monomer unit represented by the following general formula (2) j) a polymer containing a structural unit derived from a monomer unit represented by the following general formula (2) K) A polymer containing a structural unit derived from a monomer unit represented by the following general formula (4)

[0088]

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In the general formulas (1) to (4), R ¹ and R
¹¹ represents a hydrogen atom or a substituted or unsubstituted lower alkyl group, and Q represents an oxygen atom or -NH-. R ^{2 to} R ¹⁰
Each represents a substituted or unsubstituted lower alkyl group, which may be the same or different. X ⁻ is a halogen ion,
Represents a sulfonate anion, an alkyl sulfonate anion, an acetate anion or an alkyl carboxylate anion. n
Represents 2 or 3. X ₁ is a halogen atom (for example, a chlorine atom, a bromine atom, a fluorine atom, an iodine atom, etc.).

The lower alkyl group represented by R ^{1 to} R ¹¹ is preferably a methyl group or an ethyl group. m is 1
Or 2 and l is 0 or 1.

In the present invention, it is preferable to use a crosslinking agent in order to improve water resistance and stickiness. Specific examples of the crosslinking agent include, for example, formaldehyde, aldehyde compounds such as glutaraldehyde, diacetyl,
Ketone compounds such as chloropentanedione, bis (2-
Chloroethyl urea), triazine compounds such as 2-hydroxy-4,6-dichloro-1,3,5-triazine,
U.S. Pat. No. 3,288,775, compounds having a reactive halogen as described in US Pat.
0342 No. carbamoylpyridinium compound,
Compounds having a reactive olefin as described in U.S. Pat. No. 3,635,718, N-methylol compounds described in U.S. Pat. No. 2,732,316, U.S. Pat. No. 3,103,437
Isocyanates as described in U.S. Pat.
Nos. 280 and 2,983,611, aziridine compounds, carbodiimide compounds described in U.S. Pat. No. 3,100,704, epoxy compounds described in U.S. Pat. No. 3,091,537, and mucochloric acid. Organic crosslinking agents such as halogen carboxaldehydes, dioxane derivatives such as dihydroxydioxane, chrome alum,
There are inorganic cross-linking agents such as potassium alum, zirconium sulfate, boric acids and salts thereof, and these can be used alone or in combination of two or more.

The amount of the crosslinking agent varies depending on the type of the water-soluble polymer, the type of the crosslinking agent, the type of the inorganic fine particles, the ratio to the hydrophilic binder, and the like. ~ 100
mg.

When polyvinyl alcohol and / or cation-modified polyvinyl alcohol are used as a particularly preferred water-soluble polymer, it is preferable to use a cross-linking agent selected from boric acid and salts thereof and an epoxy hardener. Most preferred is a crosslinking agent selected from boric acid and its salts.

In the present invention, the boric acid or a salt thereof refers to an oxyacid having a boron atom as a central atom and a salt thereof. Specifically, orthoboric acid, diboric acid, metaboric acid,
Includes tetraborate, pentaborate, and octaborate and their salts.

For the purpose of improving the image quality, it is preferable to add a surfactant to the ink receiving layer as long as the ink absorbency is not impaired. The surfactant used may be any of anionic, cationic, nonionic and betaine types, and low-molecular or high-molecular types or different types may be used in combination. Of these, fluorine surfactants and nonionic surfactants are preferred.

The above-mentioned fluorinated surfactants are described in, for example, US Pat. Nos. 2,559,751, 2,567,011, 2,732,398, 2,764,602 and 2,806, No. 866, No. 2,809,998, No. 2,915,376, No. 2,915,528, No. 2,918,501, No. 2,934,450, No. 2,937,098 No. 2,957,031, No. 3,472,894, No. 3,555,089, British Patent No. 1,143,927, No. 1,130,822,
JP-B-45-37304, JP-A-47-9613,
Nos. 49-134614, 50-117705, 50-117727, 50-112243, and 5
2-41182, 51-12392, British Chemical Society (J. Chem. Soc.), 1950, p. 2789,
1957, pages 2574 and 2640, Journal of the American Chemical Society (J. Amer. Chem. Soc.) 79, 2549
(1957), Oil Chemistry (J. Japan Oil)
Chemists Soc. ), P. 653, J. Org. Chem., Vol. 30, p. 3524 (1965), and the like.

Among these fluorosurfactants, a certain one is trade name of Megafac F from Dainippon Ink and Chemicals, Inc., and Fluorad (trade name) from Minnesota Mining and Manufacturing Company. Fluorad) under the trade name of FC, Imperial Chemical Industry under the trade name of Monflor, E.I.Dupont Nemelas and Company under the trade name of Zonyls, and Farbeberke. Licovet V from Hoechst
Each is marketed under the trade name PF.

Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyethylene glycol fatty acid ester, and the like. For example, a product having the title “Emulgen” from Kao Corporation It is marketed by name. Among them, the surface tension of the 0.01% aqueous solution is 40 dy.
Ne / cm or less is preferable, and particularly preferably 3
It is less than 5 dyne / cm.

A matting agent can be used in the ink receiving layer to prevent sticking. Matting agents are well known in the photographic art and can be defined as discrete solid particles of an inorganic or organic material dispersible in a hydrophilic organic colloid binder. Examples of inorganic matting agents include oxides (eg, silicon dioxide, titanium oxide, magnesium oxide, aluminum oxide, etc.) and alkaline earth metal salts (eg, sulfates and carbonates, specifically, barium sulfate, carbonate Calcium, magnesium sulfate, calcium carbonate, etc., silver halide grains which do not form an image (silver chloride, silver bromide, etc., to which iodine atom may be added as a halogen component even a little) and glass.

Examples of the organic matting agent include starch, cellulose ester (for example, cellulose acetate propionate, etc.), cellulose ether (for example, ethyl cellulose, etc.), and synthetic resin. Examples of synthetic resins include:
Water-insoluble or poorly soluble synthetic polymers such as alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide, vinyl ester (eg, vinyl acetate), acrylonitrile, olefin (eg, ethylene, etc.) ), Styrene, benzoguanamine-formaldehyde condensate alone or in combination, or acrylic acid, methacrylic acid, α, β-unsaturated dicarboxylic acid,
A polymer having a combination of hydroxyalkyl (meth) acrylate, sulfoalkyl (meth) acrylate, styrene sulfonic acid and the like as a monomer component can be used.

Other epoxy resin, nylon, polycarbonate, phenol resin, polyvinyl carbazole,
Polyvinylidene chloride can also be used.

From the viewpoint of transportability, these matting agents preferably have a weight average particle size of 3 to 20 μm, and the total weight (also referred to as an attached amount) in the receiving layer is preferably 10 to 100 mg / m ^2. From the viewpoint of the stability of the coating solution, it is preferable that particles having a particle size of 3 μm or less and particles having a particle size of 20 μm or more are excluded in advance by classification. These matting agents can be used in combination.

The ink-receiving layer further contains a coloring dye, a coloring pigment, an ultraviolet absorber, an antioxidant, a dispersant for the pigment, an antifoaming agent, a leveling agent, a preservative, a fluorescent brightener, a viscosity stabilizer,
Various known additives such as a pH adjuster can also be added.

The support used in the present invention is not limited to a sheet or plate, and can be used in any shape such as a can surface. Further, a transparent support or an opaque support can be used according to the purpose of use.

As the transparent support, any of those conventionally known can be used. For example, materials such as polyester resin, cellulose acetate resin, acrylic resin, polycarbonate resin, polyvinyl chloride resin, polyimide resin, cellophane and celluloid can be used. Film, sheet or plate, or glass plate. Among these, a polyester resin, particularly a polyethylene terephthalate film, is preferred from the viewpoint of the rigidity and transparency of the support.

Examples of the opaque support include uncoated paper such as high quality paper, medium quality paper, super calendered paper, single gloss base paper, and tracing paper, art paper, coated paper, lightweight coated paper, and fine coated paper. Coated paper such as paper and cast-coated paper, plastic film, pigmented opaque film, film such as foamed film, resin-coated paper, resin-impregnated paper, non-woven fabric, cloth, metal film, metal plate, etc., and composites thereof Can be used.

Among these, resin-coated paper and various films are preferable from the viewpoint of glossiness and smoothness, and polyolefin resin-coated paper is used for resin-coated paper and polyester-based film is used for various films from the viewpoint of touch and high quality. More preferred.

As the resin of the resin-coated paper, a polyolefin resin, a resin curable by an electron beam, or the like can be used. Examples of the polyolefin resin include olefin homopolymers such as low-density polyethylene, high-density polyethylene, polypropylene, polybutene and polypentene, and olefins such as ethylene-propylene copolymers.
Copolymers of at least one kind and mixtures thereof are preferable, and various densities and melt viscosity indices (melt indices) are preferred.
Can be used alone or in combination.

Polyethylene is particularly preferred as the polyolefin for covering the front and back surfaces of the base paper, but it is mainly low-density polyethylene (LDPE) and / or high-density polyethylene (HDPE), but other LLDPE and polypropylene may be partially used. Can be.

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 stearic acid amide and arachidic acid amide, zinc stearate, calcium stearate and stearic acid are contained. Aluminum, fatty acid metal salts 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.

[0111] Such resin-coated paper preferably has a thickness of 90 to 90, as is generally known in color photography.
A base paper of 200 μm (about 50 to 200 g in basis weight) coated with polyethylene on both sides is preferable. The thickness of the polyethylene coating layer, on both the ink absorbing layer and the back side,
The thickness is generally 10 to 50 μm, preferably 15 to 40 μm. The polyethylene layer on the ink-absorbing side contains titanium oxide in an amount of 5 to 20% by weight, preferably 7 to 10% by weight, based on polyethylene.
The content of 15% by weight increases the opacity of the support,
It is preferable for achieving high whiteness.

The base paper constituting the resin-coated paper preferably used is not particularly limited, and generally used paper can be used. More preferably, for example, smooth base paper used for a photographic support is used. preferable. 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. The base paper is blended with additives generally used in papermaking, such as a sizing agent, a paper strength enhancer, a filler, an antistatic agent, a fluorescent whitening agent, and a dye.

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 applied to the surface.

The freeness of the pulp used for papermaking is preferably 200 to 500 ml according to the CSF standard, and the fiber length after beating is 24 mesh residual weight% and 42 mesh residual weight specified in JIS-P-8207. 30% by weight
~ 70% is preferred. The weight percentage of the remaining 4 mesh is 2
It is preferably 0% by weight or less.

The basis weight of the base paper is preferably 30 to 250 g.
Particularly, 50 to 200 g is preferable. Base paper thickness is 40-2
50 μm is preferred.

The base paper may be calendered at the papermaking stage or after the papermaking to provide high smoothness. The base paper density is generally 0.7 to 1.2 g / m ² (JIS-P-8118). Further, the rigidity of the base paper is preferably from 20 to 200 g under the conditions specified in JIS-P-8143.

The pH of the base paper is preferably 5 to 9 when measured by the hot water extraction method specified in JIS-P-8113.

The above-mentioned polyolefin-coated paper can be used as glossy paper, or when the polyolefin is melt-extruded onto the surface of the base paper and coated by so-called embossing to obtain a matte surface or silk, which can be obtained by ordinary photographic printing paper. Those having an eye surface can also be used in the present invention.

Further, the polyolefin-coated paper support preferably has the following characteristics. Tensile strength: The strength specified in JIS-P-8113 is preferably 2 to 30 kg in the vertical direction and 1 to 20 kg in the horizontal direction. The tear strength is 10 to 200 g in the vertical direction and 20 to 200 g in the horizontal direction according to the method specified in JIS-P-8116.
Is preferred. Compression elasticity ≧ 103 kgf / cm ² Surface Beck smoothness: 200 seconds or more, particularly 1500 seconds or more, is preferable as a glossy surface under the conditions specified in JIS-P-8119, but it is less than this in so-called molded products. good. Opacity: When measured by the method specified in JIS-P-8138, it is preferably 85% or more, particularly preferably 90% or more.

The support used in the ink jet recording material of the present invention has a taper rigidity of 1 to 15 g · cm according to JIS-P-8125.
It is more preferably used because continuous transportability is improved and the occurrence of stripe unevenness due to transport unevenness is reduced and higher image quality is obtained.

The support used in the ink jet recording material of the present invention, a test temperature of 40.degree.
The moisture permeability defined by the condition of 0% RH is 2.5 to 1
It is preferably 5 g / m ² · day, particularly preferably 3.0 to 10 g / m ² · day. By setting the moisture permeability in this range, moisture resistance and light resistance are improved. Although the reason is not clear, when the moisture permeability is high, after printing, the moisture in the ink moves from the ink receiving layer to the support side from the ink receiving layer. It is conceivable that the increase in concentration due to the diffusion of the dye is suppressed, but when the moisture permeability is too high, when placed in a high humidity environment, the concentration may increase due to moisture entering from the support side. Presumed. Although the effect on light resistance is unknown, it is considered that the decomposition of the dye is accelerated by moisture (moisture) in the film. As means for measuring the moisture permeability, for example, DR.
GEORGES H. It can be measured with a fully automatic water vapor permeability tester L-80-4000 manufactured by LYSSY.

The ink jet recording material of the present invention is preferably of the void type, and the formation of the voids prevents the opacity of the ink absorbing layer from becoming unnecessarily high from the viewpoint of obtaining a high dye concentration and sharpness. preferable.

Particularly preferred in the void-type ink-absorbing layer is a layer in which the ink-absorbing layer forms voids by soft aggregation of ultrafine particles and a hydrophilic binder.

The above-mentioned void formation by soft coagulation is performed by transferring solid coagulation between the hydrophilic binder and the solid fine particles to the solid fine particles having an average particle size of about 200 nm or less when preparing a coating solution containing a hydrophilic binder or forming a film. This is a method of forming voids by forming secondary particles or a three-dimensional structure. The formation of voids by this method has a higher ink absorbing property than the method of using porous fine particles, or the method of forming voids between the fine particles by containing fine particles of solid particles having a volume approximately equal to or greater than the hydrophilic binder. This is a preferable method because a color image with low opacity and high sharpness can be obtained.

The void type ink absorbing layer and the swelling type ink absorbing layer can be used in combination. For example, a method in which a swellable ink-absorbing layer is arranged in the lower layer and a void-type ink-absorbing layer is arranged in the upper layer, or conversely, a method in which a void-type ink-absorbing layer is arranged in the lower layer and a swellable ink-absorbing layer is arranged in the upper layer However, when the void-type ink-absorbing layer is of the soft coagulation type, the latter is preferable.

The method for forming a void structure in a film by forming soft agglomeration, which is preferably used in the present invention, is preferably a method of dispersing an aqueous structure containing a hydrophilic binder in an aqueous solution.
The secondary ultrafine particles are formed via a state where they are aggregated with each other with the contact point relatively restricted.

Such a soft agglomerate structure has a linear or branched form of aggregates dispersed in an aqueous solution, or these aggregates are further aggregated to form a three-dimensional network structure in an aqueous solution. Is included.

In any case, a fine void structure can be formed in the formed film by applying and drying the aqueous solution on the support.

The size of the fine voids in the film obtained in this manner is approximately several times larger than the size of the primary particles, and is characterized by the fine size of the voids. is there.

As a method of forming such a soft aggregation structure, for example, primary particles are hardly aggregated with each other, and the aggregation of particles is accelerated in an aqueous solution containing a hydrophilic binder that can exist stably. It is formed by a method in which a very small amount of a water-soluble polymer is added to form a slight aggregation, or in an aqueous solution having a water-soluble binder capable of weakly bonding to the primary particle surface.

In the present invention, in particular, the latter method is advantageous in that the amount of voids is relatively easy to control and easy to form, that a larger amount of voids can be obtained as compared with the amount of fine particles used, Is preferable because a film having higher glossiness can be obtained. Further, as the fine particles, by using the amorphous colloidal silica of the present invention,
A void layer having a high void ratio can be formed.

Particularly preferred water-soluble polymers for the formation of the void layer are polyvinyl alcohols.

An example of a method for forming a film containing a soft aggregate using polyvinyl alcohol and fine-particle silica will be described below.

A silica fine particle dispersion (generally 5 to 15%) is gradually added to a polyvinyl alcohol aqueous solution (generally 3 to 15%) maintained at a pH of 6 to 8 and a temperature of about 40 ° C. while stirring vigorously. After the addition is completed, the mixture is dispersed with an ultrasonic dispersing machine or a high-speed homogenizer. In this case, it is convenient to use various surfactants and water-miscible organic solvents such as methanol, acetone, and ethyl acetate, if necessary, to prepare a uniform coating solution.

Then, after the addition of various additives, the viscosity is adjusted to a value necessary for coating, and the film is coated on a support by a known method and dried to obtain a film having the above-mentioned voids.

In order to obtain a high porosity without deteriorating the brittleness of the film, the water-soluble binder is preferably crosslinked with the above-described crosslinking agent in the void layer formed by the soft aggregation.

The method for forming the ink receiving layer includes a size press method, a roll coater method, a blade coater method, an air knife coater method, a gate roll coater method, a rod bar coater method, a curtain method, a slide hopper method, and an extrusion method. For example, a commonly used coating method is used.

The coating amount of the ink receiving layer is 5 to 100.
g / m ² , more preferably 10 to 50 g / m ^2
2 .

The coating solution of the present invention has a solid content of 3 to 3%.
30% by weight is preferred, particularly preferably 5 to 20% by weight
It is.

The ink jet recording sheet of the present invention has a maximum ink amount of 20 ml / m ² per 1 m ^{2 of the} recording sheet.
In the ink jet recording method as described above, the effects of the present invention are particularly preferable.

The ink receiving layer is preferably provided on at least one side of the support, and may be provided on both sides of the support.

As the ink jet recording method used in the present invention, for example, it is preferable to use an ink jet recording method of recording on the ink jet recording sheet of the present invention with an ink containing at least 40% by weight of water. An ink jet recording liquid comprising an agent, a liquid medium, and other additives is preferably used. Examples of the colorant include a direct dye, an acid dye, a basic dye, a reactive dye, and a water-soluble dye such as a food colorant.

The solvent of the ink preferably used in the present invention includes water and various water-soluble organic solvents such as methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, and
c-butyl alcohol, tert-butyl alcohol,
Alkyl alcohols having 1 to 4 carbon atoms such as isobutyl alcohol; amides such as dimethylformamide and dimethylacetamide; ketones or ketone alcohols such as acetone and diacetone alcohol; tetrahydrofuran;
Ethers such as dioxane; polyethylene glycol;
Polyalkylene glycols such as polypropylene glycol; ethylene glycol, propylene glycol, butylene glycol, triethylene glycol, 1,2,2
Alkylene glycols having 2 to 6 alkylene groups such as 6-hexanetriol, thiodiglycol, hexylene glycol, diethylene glycol; glycerin, ethylene glycol methyl ether, diethylene glycol methyl (or ethyl) ether, triethylene glycol, monomethyl ether, etc. And pyrrolidinones such as 2H-pyrrolidinone and pyrrolidones such as 1-methyl-2-pyrrolidone and 2-pyrrolidone. Among these many water-soluble organic solvents, polyhydric alcohols such as diethylene glycol, triethylene glycol monomethyl ether,
Preferred are lower alkyl ethers of polyhydric alcohols such as triethylene glycol monoethyl ether and pyrrolidones.

In the present invention, a mixed solvent of water and the above organic solvent is preferably used as a solvent for the ink from the viewpoint of preventing clogging of the ink head nozzle. At this time, the content of water in the ink is 40% by weight or more. Preferably, it is 50 to 90% by weight.

Further, in the present invention, when recording is performed by a recording apparatus using dark and light ink, the effect of the present invention is remarkably exhibited. For example, a conventional color recording apparatus has Y, M, C,
The method of using one kind of ink for each of the four reference colors of K is the mainstream, but for some reference colors, the use of two or more kinds of inks makes it possible to increase the number of gradations and reduce the number of colors. The roughness of the density portion can be improved. In particular, when two or more types of inks (dark and light inks) having different absorbances are used for a certain reference color (for example, Y, M, C, and K), the low-density portion mainly uses light-colored (low-absorbance) inks to give a rough feel. It is known that the high density portion mainly uses a dark color (high absorbance) ink and a sufficient maximum density is obtained. The light color ink and the dark color ink may use the same dye, may use different dyes, or may be a combination of a plurality of different dyes.
As recording apparatuses using dark and light inks for such reference colors, PM-700C (Seiko Epson), Picty 300 (NEC), and Photo Sm
Art (Hewlett-Packard), etc., and in addition to Y, M, C, K, light M, light C
This is characterized in that the output is made with a total of six types of inks. As an example of a recording apparatus of a similar system, BJC-
700J (Cannon) is also included.

[0146]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the scope of the present invention. Note that all “parts” described in the following Examples and Comparative Examples are weight conversion values in a dry state.
In addition, water highly purified by ion exchange treatment was used for adjusting the coating liquid.

Example

Preparation of Examples 1 to 6 and Comparative Examples 1 to 7 One side of 175 g / m ² base paper was coated with a 40 μm polyethylene layer containing 14% by weight of anatase type titanium dioxide (surface side). A polyethylene-coated paper coated with 35 μm of polyethylene on the back side was used as a support, and the front side thereof was subjected to corona discharge treatment.
m ² , a coating liquid having the following composition and treated with an ultrasonic disperser was applied, and dried at 50 ° C. to obtain the ink jet recording materials of Examples 1 to 6 and Comparative Examples 1 to 7 of the present invention. Obtained. The type of inorganic fine particles used in each sample, and
Table 1 shows the types of the cationic latex polymer and the water-soluble cationic polymer.

Coating liquid composition (A) Inorganic fine particles (described in Table 1) 100 parts Cationic latex polymer or water-soluble cationic polymer 5 parts Polyvinyl alcohol (Nippon Synthetic Chemical Co., Gohsenol GH-23) 10 parts Boric acid 0. 2 parts Nonionic surfactant Emulgen 810 (polyoxyethylene octyl phenyl ether) (manufactured by Kao) 0.3 part Adjusted to pH 5.8

Preparation of Examples 7 to 15 and Comparative Example 8 After the same support as in Example 1 was subjected to corona discharge treatment,
A coating liquid having the following composition and having been treated with an ultrasonic disperser was applied so that the dry coating amount was 20 g / m ² , dried at 50 ° C., and then Examples 7 to 15 and Comparative Example 8 of the present invention. Was obtained.

Coating Composition (B) Snowtex OUP (Nissan Chemical Industries) 100 parts Polyvinyl alcohol (Nippon Synthetic Chemical Co., Gohsenol NH-26) 12 parts Cationic latex polymer L-7 Table 2 Boric acid 0.2 Part Adjusted to pH 6.0

Preparation of Examples 16 to 22 and Comparative Example 14 One side of 100 g / m ² base paper was coated with a 40 μm polyethylene layer containing 16% by weight of anatase type titanium dioxide (front side), and the back side. Was subjected to corona discharge treatment on the same support as in Example 1 using a polyethylene-coated paper coated with polyethylene having a thickness of 33 μm, and then an ultrasonic wave having the following composition so that the dry coating amount was 18 g / m ^2. After applying the coating liquid treated by the disperser, the coating liquid was dried at 50 ° C. to obtain the ink jet recording materials of Examples 16 to 22 of the present invention.

Coating liquid composition (C) Snowtex OUP (Nissan Chemical Industries) 100 parts Polyvinyl alcohol AH-26 manufactured by Nippon Synthetic Chemical Co. Added so that the content of inorganic fine particles becomes the value shown in Table 3 Latex polymer L- 14 parts surfactant Emulgen 810 (made by Kao) 0.2 part

Preparation of Examples 23 to 29 The same support as in Example 1 except that the thickness of the polyethylene layer was changed and the support having the moisture permeability shown in Table 4 was subjected to corona discharge treatment, and then dried. An ultrasonic dispersion-treated coating liquid having the following composition was applied so that the coating amount was 22 g / m ² ,
To obtain the ink jet recording materials of Examples 23 to 28 of the present invention. The sample of Example 29 was prepared by changing the support to cast-coated paper.

Coating liquid composition (D) Snowtex OUP 100 parts Polyvinyl alcohol (GH-20, manufactured by Nippon Synthetic Chemical) 15 parts Latex polymer L-33 8 parts Surfactant FK 0.2 parts

[0156]

Embedded image

Preparation of Examples 30 to 36 In the synthesis of (2) the intermediate polymer in the synthesis example of the exemplified compound (L-1), the number of rotations of stirring, the amount of azobiscyanovaleric acid added, the amount of surfactant, Change the reaction temperature,
The exemplified compound (L-
1) A total of seven types were created.

After the same support as in Example 1 was subjected to corona discharge treatment, the support was dried so that the dry coating amount was 20 g / m ² .
A coating liquid having the following composition and treated by an ultrasonic disperser was applied, and dried at 50 ° C. to obtain inkjet recording materials of Examples 30 to 36 of the present invention.

Coating liquid composition (E) Snowtex OUP 100 parts Exemplified compound L-1 (particle size: described in Table 5) 8 parts Polyvinyl alcohol Gohsenol GH-23 10 parts Boric acid 0.3 parts Emulgen 810 0.3 parts Adjusted to pH 6.0

Evaluation The ink-jet recording material samples prepared as described above were evaluated for the following items by outputting them with a PM-700C (Seiko Epson). For the measurement of the reflection density, a Konica densitometer PDA-65 (manufactured by Konica Corporation) was used.

<Image quality> B (blue), G (green),
100%, 80%, 60 for each color of R (red)
A color patch printed on the above sample is created from image data in the form of patches (images filled with uniform density) having three levels of density, and the degree of mottled unevenness of the image (hereinafter abbreviated as mottled unevenness) Was visually evaluated.
The evaluation criteria are shown below.

◎: All patches have no uneven spots and are very good. ○: 1 to 3 types of patches with slightly uneven spots, and none of the patches have noticeable uneven spots. ×: Three or more patches with conspicuous mottle unevenness Δ: Other than ◎, ×, × The order of ◎, △, Δ, × from excellent. <Film Strength> A 100% color patch of B (blue) was printed, and after 5 minutes and 1 hour had passed after printing, the printed portion was rubbed with a pawl, and the way of scratching was visually observed and evaluated. ◎: A level at which no scratch is formed after 5 minutes and 1 hour. ○: A level at which scar is slightly formed after 5 minutes, but not damaged after 1 hour. Δ: A level at which scratch is slightly generated even after 1 hour. Scratch level even after 1 hour

<Lightfastness> After measuring the reflection density of a sample on which a color patch having the highest density of M (magenta) was printed, the sample was irradiated with a xenon fade meter for 70,000 lux for one week and then re-measured. %). Concentration residual rate (%) = (concentration after storage for one week / concentration before storage) × 100

<Moisture resistance> A magenta patch printed sample was prepared from magenta 50% density (halftone) image data, and the reflection density was measured.
After storing for 1 week in a high humidity environment of 0% RH, the measurement was performed again, and the increase in the reflection density was evaluated. The lower the rate of concentration increase, the better the moisture resistance. Concentration increase rate (%) = [(concentration after storage for one week−concentration before storage) / concentration before storage] × 100

<Bleeding> The degree of bleeding of characters was visually evaluated for an image of a sample printed from image data in which black characters were drawn on a background of uniform density of M (magenta). The evaluation criteria are shown below.

◎: Very good without bleeding of characters. ○: Very good level of bleeding when observed carefully. △: Slightly bleeding of characters. Acceptable range x: clearly blurred, practically problematic level The same evaluation was performed with the background color changed to B (blue).

<Change in white background> The reflection density of the unprinted portion of the sample was measured, and the density was measured again after storage for 3 weeks at 50 ° C. and 20% RH, and the density was evaluated based on the rate of increase in the yellow density.

White background change = (yellow density after storage) −
(Yellow density before storage)

Examples 1 to 6 and Comparative Examples 1 to 7 are shown in Table 1, and Examples 7 to 15 and Comparative Example 8 are shown in Table 2.
Table 3 for Examples 16 to 22 and Comparative Example 14
Table 4 shows Examples 23 to 29, and Examples 30 to 29
Table 36 shows the evaluation results for 36.

[0170]

[Table 1]

[0171]

Embedded image

[0172]

[Table 2]

[0173]

[Table 3]

[0174]

[Table 4]

[0175]

[Table 5]

[0176]

According to the present invention, it is possible to provide an ink jet recording material and a recording method which are excellent in suppressing mottle and unevenness, moisture resistance, light resistance, prevention of bleeding and prevention of scratches.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI D21H 27/00 D21H 5/00 Z

Claims (12)

[Claims] An ink jet recording material having a support and an ink receiving layer provided on the support, wherein the ink receiving layer is coated with a coating liquid containing non-spherical colloidal silica and a water-dispersible cationic polymer. And an ink-jet recording material obtained by drying. 2. The ink jet recording material according to claim 1, wherein said non-spherical colloidal silica is amorphous. 3. The ink jet recording material according to claim 1, wherein the shape of the non-spherical colloidal silica is at least one of a branch, a rod, a bend, and a ring. 4. A water-dispersible cationic polymer having a number average particle size of 5 to 400 nm.
4. The ink jet recording material according to any one of claims 1 to 3. 5. The ink jet recording material according to claim 1, wherein the content of the water-dispersible cationic polymer in the ink receiving layer is 1 to 30% by weight. 6. A support having a moisture permeability of 1 to 20 g / m ² ···
The inkjet recording material according to any one of claims 1 to 5, wherein the recording material is day. 7. The ink jet recording material according to claim 1, wherein said support is a polyethylene coated paper. 8. The ink jet recording material according to claim 1, wherein the content of the inorganic particles in the ink receiving layer is 75 to 95% by weight. 9. The ink jet recording material according to claim 1, wherein the water-dispersible cationic polymer contains at least one compound represented by the following general formula (I). . Embedded image In the general formula (I), (A) represents a monomer unit obtained by polymerizing a copolymerizable monomer having a quaternary ammonium group, and (B) represents a general unit (II), (III) or (IV).
And a monomer unit obtained by polymerizing a copolymerizable monomer containing at least one of the structures represented by (V). Embedded image In the general formula (II), R ₁ and R ₂ represent an aliphatic group, and in the general formula (III), Z is necessary for forming a 5- or 6-membered ring together with -CN = C-. Represents a non-metallic atomic group. In the general formula (IV), R ₃ and R ₄ represent an aromatic group, a halogen atom, a cyano group, and an oxycarbonyl group. In the general formula (V), R ₅ represents a hydrogen atom and an aliphatic group, and R ₆ represents an aliphatic group. In the above general formula (I), (C) represents a monomer unit obtained by polymerizing a copolymerizable monomer having at least two ethylenically unsaturated bonding groups, and (D) represents (A), (B) and (C). )
Represents a monomer unit obtained by polymerizing a copolymerizable monomer other than the above. k represents 10 to 95 mol%, m represents 0 to 30 mol%, n represents 2 to 20 mol%, and p represents 0 to 80 mol%. However, k + m + n + p = 100 mol%. 10. A color ink jet recording method for recording on a recording material according to any one of claims 1 to 9, using a recording device for outputting using five or more different inks. 11. A recording apparatus for recording on at least one reference color using two or more different inks, wherein the recording is performed on the recording material according to any one of claims 1 to 9. Ink jet recording method. 12. A color ink jet recording method according to claim 11, wherein said reference color is recorded by a recording apparatus for recording with two or more kinds of inks whose absorbance of said reference color ink is substantially different.