JPH11208100A - Porous recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To form porous recording materials having superior image vividness, a quick drying property, and water resistance. SOLUTION: At least one of layers on carrier is made up of a porous film containing silica of 5-50 pts.wt. and a binder (e.g. a nitric ester group of carboxylic alkyl cellulose having the substitutional degree of a nitric ester group 0.2-2.95 and the substitutional degree of a carboxylic alkyl either group of 0.05-2.8) of 50-95 pts.wt., and also the binder consists of anionic resin and cationic resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a porous recording material, and more particularly, to a porous recording material having excellent image clarity, quick drying, and water resistance.

[0002]

2. Description of the Related Art Conventionally, various recording methods such as a wire dot recording method, a thermosensitive coloring recording method, a thermosensitive thermal transfer recording method, a thermosensitive sublimation transfer recording method, an electrophotographic recording method and an ink jet recording method have been used. There is. Among them, the ink jet system has the features that plain paper can be used as a recording sheet, printing cost is low, the apparatus is compact, there is no noise, high-speed recording, and color printing is easy. In recent years, demand for printed media such as large-sized posters, displays, flyers, and the like has been rapidly increasing.

In particular, in recent years, high image quality and high speed printing have been demanded, and accordingly, the ink ejection amount per unit area and per unit time has been increased. As a conventional technique, there is known a recording sheet in which an ink receiving layer made of a water-soluble resin such as polyvinylpyrrolidone or polyvinyl alcohol is provided on a base material such as paper, plastic film or glass plate (for example, JP-A-55-146786). JP, JP-A-56-99692, JP-A-59-1
No. 74381). However, a recording sheet comprising only a water-soluble resin has low water resistance of the coating film.

Further, a recording sheet having fine voids using alumina hydrate having a pseudo-boehmite structure (for example, Japanese Patent Application Laid-Open No. 2-276670) has been proposed. Inconveniences such as a decrease in workability occur.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a porous recording material having excellent image clarity, quick drying property and water resistance.

[0006]

Means for Solving the Problems The present inventor has found that anionic resins and cationic resins are useful as silica binders in order to solve the above problems, and have completed the present invention. . That is, the present invention is as described below in 1 and further includes the following 2 to 6 embodiments.

1) At least one layer on the support is composed of a porous membrane containing 5 to 50 parts by weight of silica and 50 to 95 parts by weight of a binder, and the binder is made of an anionic resin or a cationic resin. A porous recording material, comprising: 2) a nitric acid ester of carboxyalkylcellulose in which the anionic resin has a degree of substitution of nitric acid ester groups per anhydrous glucose unit of 0.2 to 2.95 and a degree of substitution of carboxyalkyl ether groups of 0.05 to 2.8; 2. The porous recording material as described in 1 above, wherein the cationic resin comprises cationically modified polyvinyl alcohol.

(3) The porous recording material as described in (1) or (2) above, wherein the composition of the binder is 3 to 80 parts by weight of the anionic resin and 20 to 97 parts by weight of the cationic resin. 4) Silica has an average particle size of 0.1 to 20 μm, a pore volume of 0.2 to 5 cc / g, a pore radius of 1 to 20 nm, and a specific surface area of 50 to 900 m ² / g. 4. The porous recording material according to the above 1, 2 or 3.

5) When the silica is colloidal silica dispersed in water or an organic solvent, the particle diameter is 5 nm to 2 nm.
5. The porous recording material as described in 1, 2, 3 or 4, wherein the dispersion of colloidal silica has a pH of 7 or more. (6) The porous recording material as described in any one of (1) to (5) above, which is a recording material for inkjet recording.

Hereinafter, the present invention will be described in detail. The support used in the present invention includes a synthetic resin film or paper. Examples of the synthetic resin film include polyester, polyolefin, polyamide, polyesteramide, polyether, polyimide, polyamideimide, polystyrene, polycarbonate, poly-P-phenylene sulfide, polyetherester, polyvinyl chloride, polyvinyl acetate, and poly ( A (meth) acrylic acid ester or the like can be used. Further, a copolymer, a blend thereof, a further cross-linked product, a film made opaque by kneading a pigment, a foamed film, a gloss film, and the like can also be used. Among the above-mentioned supports, polyester, preferably polyethylene terephthalate, is preferable in terms of mechanical properties, workability, and the like.

Examples of paper include high-quality paper, medium-quality paper, art paper, bond paper, copy paper, baryta paper, cast-coated paper, corrugated paper, coated paper, synthetic paper, glossy paper, and resin-coated paper. Etc. can be used. Synthetic resin film,
In addition to paper, cloth such as cotton, rayon, acrylic, and polyester, glass plate, metal, and the like can be used according to the purpose.

The silica used in the present invention has an average particle size of 0.1 to 20 μm, a pore volume of 0.2 to 5 cc / g, a pore radius of 1 to 20 nm, and a specific surface area of 50 to 900 m ² / g.
g is preferable. Furthermore, the average particle size is 0.1
１５15 μm, pore volume 1-5 cc / g, pore radius 2
More preferably, the specific surface area is from 400 to 700 m ² / g. If the average particle diameter, the pore volume, the pore radius, and the specific surface area are outside these ranges, the ink absorbency is not always improved.

Further, depending on the application, silica can be dispersed in water or an organic solvent and used as colloidal silica. Generally, silica having a particle diameter of 5 to 200 nm dispersed in water or an organic solvent can be suitably used. Preferably it is in the range of 20 to 100 nm, more preferably 40 to 80 nm. If the particle diameter of the colloidal silica is less than 5 nm, the film formability is insufficient, and if it exceeds 200 nm, the gloss of the coating film may be reduced, but it is possible to use them properly depending on the application.

The pH of the colloidal silica is preferably 5 or more, more preferably 7 to 12. pH 5
If it is less than 3, the viscosity of the coating liquid may increase and the workability may decrease. The binder used in the present invention comprises an anionic resin and a cationic resin.

The anionic resin is a resin containing an anionic group such as a carboxylic acid group, a sulfonic acid group and a phosphoric acid group, or a salt thereof. For example, phthalic acid, maleic acid, gelatin derivatives reacted with anhydrides of dibasic acids such as fumaric acid, carboxy-modified starch derivatives, carboxymethyl cellulose, carboxymethyl ethyl cellulose, alkyl carboxymethyl cellulose, nitrates of carboxyalkyl cellulose, etc. Cellulose derivatives, polyacrylic acid, polymethacrylic acid,
These salts, copolymers of methacrylic acid, carboxy-modified polyvinyl alcohol and the like can be mentioned. Among them, nitrates of carboxyalkyl cellulose are preferred.

The nitrates of carboxyalkylcellulose are those having a degree of substitution of nitrate groups of 0.2 to 2.95 and a degree of substitution of carboxyalkyl ether groups of 0.05 to 2.8 contained in carboxyalkylcellulose. For details, see JP-A-5-39301 and JP-A-5-301301.
It refers to an aqueous cellulose derivative disclosed in JP 39302. If the nitrate ester group substitution degree is less than 0.2, the water resistance of the coating film is insufficient, and if it exceeds 2.95, the hydrophilicity tends to be insufficient. If the degree of carboxyalkyl ether group substitution is less than 0.05, the solubility in water becomes insufficient, and the ink absorbency of the coating becomes insufficient. If it exceeds 2.8, the water resistance of the coating becomes poor. Tends to be sufficient. The preferred range of the degree of substitution of the nitrate group of the nitrates of the carboxyalkyl cellulose is 0.2 or more and 2.2 or less, and the preferred range of the degree of substitution of the carboxyalkyl ether group is 0.05 or more and 1.5 or less. .

Examples of the cationic resin include polyvinylpyrrolidone, a cation-modified cellulose derivative, a cation-modified starch, a cation-modified guar gum, a diallyl quaternary ammonium salt polymer, a copolymer of a diallyl quaternary ammonium salt and acrylamide, an aniline resin, Examples thereof include polythiourea, polyethyleneimine, polyvinylpyridines, cationized polyacrylamide, polyallylamine, copolymers thereof, and cation-modified polyvinyl alcohol. Among them, cation-modified polyvinyl alcohol is preferable.

The cationically modified polyvinyl alcohol is
Amide group, imide group, primary amino group, secondary amino group, 3
It is a polyvinyl alcohol containing at least one cationic group selected from a primary amino group, a primary ammonium base, a secondary ammonium base, a tertiary ammonium base, and a quaternary ammonium base. Further, the amount of cation conversion refers to polyvinyl alcohol containing 0.01 mol% or more. The preferred range of the cation conversion amount is 0.1 to 30 mol%. Furthermore, 0.1 to 15 mol% is preferable.
If the modification amount of the cationic group is less than 0.01 mol%, the water resistance of the coating film tends to be insufficient. As the average degree of saponification,
40 to 100 mol% is preferred. If the saponification degree is less than 40 mol%, the ink absorption tends to be insufficient. The average degree of polymerization is preferably from 100 to 5,000, and more preferably from 200 to 3,000. If the average degree of polymerization is less than 100, the water resistance of the coating film is reduced, and if it exceeds 5,000, the solution viscosity is too high, and the workability such as resin mixing and coating on a support tends to be reduced.

As a combination of the above-mentioned anionic resin and cationic resin, a combination of nitric acid esters of carboxyalkyl cellulose and modified polyvinyl alcohol is preferably used. The porous film constituting the porous recording material of the present invention is a coating film having a space capable of substantially absorbing ink. A preferred embodiment of the porous film has a structure having not only fine cracks inside the porous film but also many very fine voids inside the silica particles. The ink absorption speed and absorption amount are much higher than that of a dense non-porous coating consisting of only ordinary water-soluble resins, and as a result, clear images can be obtained even when a large amount of ink is required as in photographic images. Is obtained.

Known binders can be added to the binder used in the present invention. Known binders include, for example, nonionic resins such as methylcellulose, hydroxypropylcellulose, and hydroxypropylmethylcellulose, and ester compounds of anionic resins such as polyhydroxyethyl methacrylate and copolymers thereof. These can be used alone or in combination.

The mixing ratio of silica and binder used in the present invention is preferably 5 to 50 parts by weight of silica and 50 to 95 parts by weight of binder in terms of solid content. If the amount of silica is less than 5 parts by weight, the ink absorbency cannot be said to be sufficient. If the amount of silica exceeds 50 parts by weight, the water resistance is not necessarily sufficient. The mixing ratio of the anionic resin and the cationic resin used in the present invention can be arbitrarily selected depending on the compatibility of the resins used, but is preferably an equivalent amount for neutralizing the ionicity. Examples of the mixing ratio include 3-80 parts by weight of nitrates of carboxyalkyl cellulose and 20-97 parts by weight of cation-modified polyvinyl alcohol. If the nitric acid ester of carboxyalkylcellulose is less than 3 parts by weight, the water resistance of the coating film becomes insufficient, and if it exceeds 80 parts by weight, the film-forming property tends to decrease.

Further, surfactants such as anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants can be added for the purpose of improving image sharpness. . Examples of anionic surfactants include fatty acid soaps, N-acyl amino acids and salts thereof, alkyl ether carboxylates, carboxylates such as acylated peptides, sulfated oils, higher alcohol sulfates, alkyl ether sulfates, Polyoxyethylene alkyl phenyl ether sulfate, sulfate such as fatty acid alkylol amide sulfate, alkyl benzene sulfonate, alkyl naphthalene sulfonate, dialkyl sulfosuccinate, alkyl sulfo acetate, α-olefin sulfonic acid Sulfonates such as salts, phosphates such as alkyl ether phosphates and alkyl phosphates, and the like.

Examples of the cationic surfactant include aliphatic primary amine salts, secondary amine salts, tertiary amine salts, quaternary ammonium salts, benzalkonium salts, benzenetonium chloride, and pyridinium. Salts, imidazolinium salts and the like. Examples of the amphoteric surfactant include a carboxybetaine type, an aminocarboxylic acid type, an imidazolinium betaine type, and a lecithin type.

Examples of the nonionic surfactant include polyoxyethylene alkyl ether type, polyoxyethylene alkyl phenyl ether type, polyoxyethylene sterol ether type, polyoxyethylene lanolin derivative type, polyoxyethylene glycerin fatty acid ester type,
Polyoxyethylene sorbitan fatty acid ester type, polyoxyethylene sorbitol fatty acid ester type, polyethylene glycol fatty acid ester type, fatty acid glyceride type, polyglycerin fatty acid ester type, sorbitan fatty acid ester type, propylene glycol fatty acid ester type, fatty acid alkanolamide type, polyoxy Examples thereof include an ethylene fatty acid amide type, a polyoxyethylene alkylamine type, and an alkylamine oxide type.

Of these, nonionic surfactants are preferable, and sorbitan ester ethers such as polyoxyethylene sorbitan fatty acid ester type and polyoxyethylene sorbitol fatty acid ester type are particularly preferable.
The preferable addition amount is 20 parts by weight or less based on the solid content of the entire coating liquid. More preferably, it is 10 parts by weight or less. If the amount is more than 20 parts by weight, repelling of ink may occur and image clarity may decrease.

For the purpose of improving the water resistance of the coating film, a hydroxyl group crosslinking agent such as an aldehyde compound, a melamine resin, an activated vinyl compound, an acid anhydride, an isocyanate compound, an activated vinyl compound and a compound containing a polyvalent metal is added. I can do things. Among these, a melamine resin is preferable, and a methylol melamine derivative such as methylated methylol melamine etherified with a lower alcohol is more preferably used. The preferable addition amount of the hydroxyl group crosslinking agent is 0.1 to 20 parts by weight based on the binder. If the amount is less than 0.1 part by weight, the water resistance may not be sufficiently exhibited, and if the amount is more than 20 parts by weight, repelling of the ink may occur, and the image clarity may decrease.

In addition, matting agents such as calcium carbonate, basic magnesium carbonate and crystalline cellulose, defoamers,
Examples include coating property improvers, thickeners, antistatic agents, antioxidants, ultraviolet absorbers, dyes, light fastness improvers, preservability improvers, and printability improvers such as alumina sol. These are 2
More than one species can be used in combination. In the recording sheet of the present invention, the thickness of the coating layer provided on the substrate,
It is 0.5 to 100 μm, preferably 2 to 50 μm.
When the thickness is less than 0.5 μm, the ink absorbency is insufficient and drying takes a long time. When the thickness is more than 100 μm, the drying property, coating property and curling property during coating tend to be insufficient.

The nitrates of carboxyalkyl cellulose used in the present invention can be dissolved in water and / or an organic solvent containing water as a main component. In order to increase the solubility in these solvents, the carboxyl groups contained in the carboxyalkyl cellulose nitrates may be partially or entirely neutralized. For neutralization, one of cations such as alkali metal ions, alkaline earth metal ions, ammonium ions, and organic amines is used.
Species or two or more species can be used. In this case, the degree of neutralization is arbitrarily determined according to the composition of the target solution such as water and an organic solvent. Generally, 50% or more of the carboxyl groups contained are neutralized. Is preferred. Neutralizing the carboxyalkylcellulose nitrates lowers the viscosity of the solution and improves the coatability of the support.

The organic solvent which can be used for dissolving the carboxyalkyl cellulose nitrates used in the present invention includes alcohols, polyhydric alcohols, derivatives of polyhydric alcohols, ketones, esters, carbonates and the like. Solvents comprising one or a combination of two or more selected from among them. As alcohols, methanol, ethanol, n-propanol, n-butanol, n-pentanol, n-hexanol, n-heptanol, n-octanol, n-nonyl alcohol,
Examples include n-decanol, n-undecanol or isomers thereof, cyclopentanol, cyclohexanol and the like. Preferred are alcohols having 1 to 6 alkyl carbon atoms.

The polyhydric alcohols include ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 2-cyclohexanediol, 1,7
-Heptanediol, 1,8-octanediol, 1,
Examples include 9-nonanediol, 1,10-decanediol, glycerin, pentaerythritol and the like.

Examples of the polyhydric alcohol derivatives include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol isopropyl ether, ethylene glycol monobutyl ether, ethylene glycol isobutyl ether, propylene glycol monomethyl ether, and propylene. Glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, cellosolve acetate, etc., or a solvent pocket book edited by the Society of Synthetic Organic Chemistry, Japan (Ohm, September 20, 1990).
Polyhydric alcohols and their derivatives described on pages 79 to 574;

Examples of the ketones include acetone, methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, diisopropyl ketone, cyclopentanone, cyclohexanone and the like. As the esters, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, amyl acetate, lactate ester, butyrate ester, dibutyl phthalate, dioctyl phthalate, and cyclic esters such as ε-caprolactone and ε-caprolactam Esters are mentioned.

As ethers, diethyl ether,
Examples include isopropyl ether, n-butyl ether, tetrahydrofuran, tetrahydropyran, 1,4-dioxane and the like. Examples of the carbonates include dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethylene carbonate and the like.

In the porous recording material of the present invention, a method of forming a coating film that absorbs ink includes an air doctor coater, a rod coater, a knife coater, a reverse roll coater, a transfer roll coater, a kiss coater, a cast coating, a spray coater, and a slot. Orifice coater, calendar coater, blade coater,
Known methods such as a gravure coater, a curtain coater, and a roll coater can be applied.

At this time, if necessary, a known surface treatment such as a corona discharge treatment or a primer treatment in the air or another atmosphere is applied to the support before coating, so that the coatability is improved. Not only can it be improved, but it can be firmly formed on the film surface. If necessary, a binder may be applied to both sides of the support, or an ink absorbing layer having different physical properties may be laminated on the support. The concentration of the coating solution and the conditions for drying the coating film are not particularly limited, but the drying conditions for the coating film are desirably in a range that does not adversely affect the properties of the substrate.

The porous recording material of the present invention has good image clarity, quick drying property and water resistance by using a coating liquid comprising silica, an anionic resin and a cationic resin.

[0037]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be further described below with reference to examples. In addition, the measuring method of various characteristics in the present invention is as follows. [Evaluation Method of Image Clearness] Solid printing is performed on a porous recording material by an ink jet printer (BJ-420J, glossy film mode; manufactured by Canon Inc.). The sharpness after recording and the degree of bleeding were visually judged.

：: good, Δ: slightly poor, ×: poor [Evaluation Method of Quick Drying Property] Solid printing was performed on a porous recording material, and immediately after that, the printed portion was rubbed with a finger to evaluate the degree of ink transfer. ：: No transfer, Δ: Slight transfer, X: Transfer [Evaluation method of print water resistance] A solid printed porous recording material was immersed in water at 25 ° C. for 1 minute, dried at room temperature, and printed. The degree of blurring or bleeding was visually determined.

○: almost no change, Δ: slightly blurred,
×: Ink spilled

[0040]

[Production Example 1] Carboxymethylcellulose (Cellogen 5
A; manufactured by Daiichi Kogyo Seiyaku Co., Ltd .; carboxymethyl ether group substitution degree = 0.7), 100 g of sulfuric acid / nitric acid / water (= 5)
5000 g of a mixed acid (9/20/21 parts by weight) is placed in a 5-liter reaction vessel, and a nitrification reaction is carried out at 5 to 10 ° C. for 60 minutes while stirring.

The reaction product is deacidified by centrifugation and immediately washed with a large amount of water. Further, the reaction product was made into a 10% slurry in an autoclave, treated at 140 ° C. for 30 minutes, and then separated by a Buchner funnel to collect the reaction product. The reaction product was dried at 80 ° C. for 2 hours to obtain 120 g of carboxymethyl cellulose nitrate. The nitrate ester substitution degree per anhydroglucose unit of this nitrate ester is the carboxymethyl ether group substitution degree (0.7) of carboxymethyl cellulose and CHN
Measurement of the nitrogen content by a coder gave 1.9.

Next, 100 g of carboxymethyl cellulose nitrate having a degree of substitution of 1.9 and a degree of substitution of carboxymethyl ether of 0.7 per unit of anhydrous glucose unit obtained above per anhydrous glucose unit were added to 100 g of ion-exchanged water. 5
42.8 g and 300 g of isopropyl alcohol were put into a closed mixer and stirred. Furthermore, 1
57.2 g of 0% aqueous ammonia was added. The solution was completely dissolved with heating to obtain a solution having a solid content of 10% (this is referred to as a binder solution A).

[0043]

Example 1 Cation-modified polyvinyl alcohol (CM)
318: Kuraray Co., Ltd.) 100 g, ion-exchanged water 800
g, 100 g of isopropyl alcohol in a mixer,
Stirring was performed until complete dissolution, and a solution having a solid content of 10% was obtained (this is referred to as a binder liquid B).

A binder liquid C was prepared by mixing the binder liquid A and the binder liquid B at a weight ratio of 20:80. Silica (Carplex BS304N, average particle size 7
-10 μm, pore volume 1.08 cc / g, specific surface area 41
8 m ² / g, pore radius 4.1 nm: manufactured by Shionogi Pharmaceutical Co., Ltd.)
And the binder liquid C were mixed at a ratio of 10 to 90 in terms of solid content to prepare a coating liquid.

The coating solution was applied to a 100 μm-thick transparent polyethylene terephthalate film (Melinex D53).
5: manufactured by ICI Japan Co., Ltd.)
m with a rod coater and at 80 ° C for 15
After drying for a minute, a porous recording material was obtained. Table 1 shows the evaluation results.
Shown in

[0046]

Example 2 Silica and binder liquid C were converted to solid content of 3%.
Example 1 except that the coating liquid was adjusted by mixing at 0:70.
In the same manner as in the above, a porous recording material was obtained. Table 1 shows the evaluation results.
Shown in

[0047]

Example 3 Silica and binder liquid C were converted to solid content of 5%.
Example 1 except that the coating liquid was adjusted by mixing at 0:50.
In the same manner as in the above, a porous recording material was obtained. Table 1 shows the evaluation results.
Shown in

[0048]

Example 4 A transparent polyethylene terephthalate film having a thickness of 100 μm (Melinex D535: I)
Example 2 except for the change to CI Japan Co., Ltd.)
In the same manner as in the above, a porous recording material was obtained. Table 1 shows the evaluation results.
Shown in

[0049]

Example 5 A porous recording material was obtained in the same manner as in Example 2 except that the support was changed to copy paper. Table 1 shows the evaluation results.

[0050]

Example 6 Silica prepared separately (average particle size 10 μm, pore volume 1.4 cc / g, specific surface area 670 m)
² / g, pore radius 2.1 nm), except that the porous recording material was obtained in the same manner as in Example 2. Table 1 shows the evaluation results.

[0051]

Example 7 100 g of carboxymethylethylcellulose (carboxymethyl group content 12.8%, ethyl ether group content 40%: manufactured by Freund Corporation), ion-exchanged water 684.1 g, isopropyl alcohol 200 g, 2 g
15.9 g of 8% aqueous ammonia was put into a mixer and stirred until completely dissolved to obtain a solution having a solid content of 10% (this is referred to as a binder liquid D).

A binder liquid E was prepared by mixing the binder liquid B and the binder liquid D at a weight ratio of 20:80. A porous recording material was obtained in the same manner as in Example 2, except that the binder liquid C was changed to the binder liquid E. Table 1 shows the evaluation results.

[0053]

Example 8 100 g of anion-modified polyvinyl alcohol (carboxy-modified 1 mol%) and 800 ion-exchanged water
g and 100 g of isopropyl alcohol were placed in a mixer and stirred until completely dissolved to obtain a solution having a solid content of 10% (this is referred to as a binder liquid F).

The binder liquid G was prepared by mixing the binder liquid B and the binder liquid F at a weight ratio of 20:80. A porous recording material was obtained in the same manner as in Example 2, except that the binder liquid C was changed to the binder liquid G. Table 1 shows the evaluation results.

[0055]

Example 9 Cation-modified polyvinyl alcohol (K2
10: Nippon Synthetic Chemical Company) 100 g, ion-exchanged water 80
0 g and 100 g of isopropyl alcohol were placed in a mixer and stirred until completely dissolved to obtain a solution having a solid content of 10% (this is referred to as a binder liquid L).

The binder liquid M was prepared by mixing the binder liquid A and the binder liquid L at a weight ratio of 20:80. Silica and binder liquid M are 30 to 70 in terms of solid content.
A porous recording material was obtained in the same manner as in Example 1 except that the coating liquid was adjusted by mixing in the above. Table 1 shows the evaluation results.

[0057]

Comparative Example 1 A 100 μm thick transparent polyethylene terephthalate film (Melinex D)
535: manufactured by ICI Japan Co., Ltd.)
Coating was performed with a rod coater so that the thickness became 0 μm, and the coating was dried at 80 ° C. for 15 minutes to obtain a porous recording material. Table 1 shows the evaluation results.

[0058]

Comparative Example 2 100 g of unmodified polyvinyl alcohol, 800 g of ion-exchanged water, 100 g of isopropyl alcohol
Into a mixer and stirred until it is completely dissolved.
% Solution (this is referred to as a binder liquid J). The binder liquid B and the binder liquid J are converted to a weight ratio of 20 to 80.
To prepare a binder liquid K.

A porous recording material was obtained in the same manner as in Example 2, except that the binder liquid C was changed to the binder liquid K.
Table 1 shows the evaluation results.

[0060]

Comparative Example 3 A porous recording material was obtained in the same manner as in Example 2 except that the binder liquid C was changed to the binder liquid J.
Table 1 shows the evaluation results.

[0061]

[Table 1]

[0062]

By using the porous recording material of the present invention, a printed matter having excellent image clarity, quick drying property and water resistance can be obtained. Further, in the present invention, the degree of substitution of the nitrate ester group per anhydroglucose unit is 0.2 to 2.9.
5, the carboxyalkyl ether group substitution degree is 0.05 to
By using a binder comprising a combination of 2.8 carboxyalkylcellulose nitrates and a cation-modified polyvinyl alcohol, high image clarity can be exhibited by the ink absorption of the binder itself even in a range where the amount of silica used is small. In addition, the water resistance of the coating film can be exhibited by the high water resistance of the binder. Further, since the binder itself has excellent gloss, it is possible to obtain a highly glossy coating film by selecting the particle size of silica.

The porous recording material of the present invention can be used as glossy paper, glossy film, matte film, OHP sheets, calendars, stickers (stickers, etc.), cards (business cards, etc.) posters, and digital camera image output. It can be used for applications such as recording sheets. Further, by using it as the outermost layer among the coating layers laminated on the transparent support, it can be used for a back coat film or the like in which a printed image is viewed from the support direction.

With the porous recording material of the present invention, a clear image can be obtained regardless of whether the ink used in the printer is a dye or a pigment.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI // C08J 7/04 C08J 7/04 Z C08L 29:00

Claims (1)

[Claims] 1. The method according to claim 1, wherein at least one layer on the support comprises silica 5
A porous recording material comprising a porous film containing 50 to 95 parts by weight of a binder and 50 to 95 parts by weight of a binder, wherein the binder comprises an anionic resin and a cationic resin.