JPH10101983A - Composition for printing substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition for printing substrates excellent in ink absorption and also in ink dryability, print clarity, water resistance, and thermal blocking resistance. SOLUTION: This composition comprises 3-80wt.% carboxyalkyl cellulose nitric acid ester having a degree of nitration of 0.2-2.95per glucose anhydride unit and a degree of carboxyalkyl-etherification of 0.05-2.8, 96-10wt.% cation- modified polyvinyl alcohol, and 1-20wt.% cationic polymer. The cationic polymer is desirably a (co)polymer of a diallyl-quat. ammonium salt. A recording material having excellent printability can be obtained by applying the composition to a substrate such as paper or a film and drying the applied composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition for coating a raw material for printing, and more particularly, to a composition having excellent ink absorbency and excellent ink drying properties, print clarity, water resistance, and heat blocking properties. The present invention relates to an excellent printing material composition.

[0002]

2. Description of the Related Art Conventional recording methods include:
There are various recording methods such as a wire dot recording method, a thermosensitive coloring recording method, a heat-melting heat transfer recording method, a heat-sensitive sublimation transfer recording method, an electrophotographic recording method, and an ink jet recording method. Among them, the ink jet system can use plain paper as a recording sheet, the printing cost is low, the device is compact, there is no noise, and high-speed recording is possible.
It has features such as colorization. For this reason, attention has been paid to its use as a printer for outputting image information such as characters and figures created by a computer or the like at high speed and with high character. In addition, since it is easy to colorize and the picture pattern is clear, image information created by a computer is recorded on a transparent recording sheet by an ink jet printer, and this is used as a manuscript for an overhead projector (OHP), and is used for conferences and various conferences. Demands for use in presentations and the like, and demands for using printed matter for design purposes are increasing.

The recording methods of ink jet printers are roughly classified into a continuous method in which continuously ejected ink is selectively landed on paper, and a drop-on-demand method in which ink is selectively ejected. The drop-on-demand method has become mainstream. In the drop-on-demand method, a recording ink is ejected by the pressure of a fine piezoelectric element (piezo element), or the ink is ejected from a nozzle by the pressure of air generated by heating a thermal head and adheres to a recording sheet. In general, a bubble jet method for performing recording is used.

[0004] Ink-jet recording has a simple mechanism in which the process is completed only by discharging ink, which is a color material, directly onto recording paper. Therefore, a great problem is imposed on the recording head and the ink. With respect to ink, it is required to improve ink jetting failure caused by an increase in viscosity due to ink drying. Normally, the ink component is generally obtained by dissolving a dye, a resin, an additive, and the like in water and alcohol.

[0005] Further, it is required for a recording material to be recorded by an ink jet printer to absorb the moisture of the attached ink and to dry and solidify the ink. From such a viewpoint, the following is known as a recording sheet for ink jet in which an ink receiving layer is formed on a recording material to enhance the ink absorbency. Examples of the ink jet recording material having improved ink absorption include a recording sheet in which an ink receiving layer made of a water-soluble resin such as polyvinylpyrrolidone and polyvinyl alcohol is provided on a raw material such as paper, a plastic film, and a glass plate, or silica. Recording sheets provided with an ink receiving layer containing a filler (for example, JP-A-55-146786, JP-A-56-99692, and JP-A-59-1)
74381, JP-A-2-276670).

This type of recording sheet has good absorbability and fixability of aqueous ink, but has a drawback that the ink receiving layer has poor water resistance and is easily peeled off when exposed to water. Furthermore, when a filler such as silica is contained, if the content of the filler is high, the ink adsorbing force is too strong, so that an appropriate dot spread cannot be obtained and a thin image is formed. That is, the required image cannot be obtained. On the other hand, if the content of the filler is low, there is a problem that the ink cannot be sufficiently dried, and blocking and image disorder occur. Also, the addition of the filler causes fine cracks on the surface of the recording sheet,
There is also a problem that the flexibility of the ink receiving layer is impaired.

[0007] In some cases, use of a cationic resin has been proposed for the purpose of improving the adsorptivity of the dye (for example, Japanese Patent Application Laid-Open No. Hei 4-263984). In this case,
Although the adsorptivity between the ink receiving layer and the dye is improved, there is a problem that water resistance is insufficient and the ink receiving layer easily flows with water. Further, it has been proposed to use a pseudo-boehmite structure alumina hydrate as a receiving layer having excellent print clarity and water resistance (for example, US Pat. No. 4,879,879).
166, U.S. Pat. No. 5,104,730,
JP-A-2-276670, JP-A-5-32037
No.). Further, it has been proposed to form an ink receiving layer having a laminated structure using the alumina material or the silica material (for example, U.S. Pat. No. 5,104,730, U.S. Pat. No. 4,780,356, and Japanese Patent Laid-Open No. 4-3).
73576, JP-A-4-37576, JP-A-3-281384). However, when the amount of ink increases, the ink cannot be absorbed sufficiently, and bleeding occurs. In addition, since a void such as an alumina material is used, when the void is closed by moisture or the like, there is a problem that the ink absorption becomes insufficient. Further, there is also a disadvantage such as a decrease in workability due to an increase in viscosity of the coating liquid over time.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide a composition for a printing raw material which has good ink absorption, fixability and drying properties, and has good water resistance and blocking resistance. It is.

[0009]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a composition using a specific carboxyalkylcellulose nitrate, a cation-modified polyvinyl alcohol and a cation polymer in combination is provided.
It has been found that an excellent recording material can be obtained by coating at least one side of the raw material, and the present invention has been completed.

That is, according to the present invention, the degree of substitution of nitrate ester groups per anhydrous glucose unit is 0.2 to 2.95, and the degree of substitution of carboxyalkyl ether groups is 0.05 to 2.8.
3 to 80% by weight of carboxyalkyl cellulose nitrates, cationically modified polyvinyl alcohol 9
The present invention relates to a composition for a raw material for printing, comprising 6 to 10% by weight and 1 to 20% by weight of a cationic polymer.

The raw material used in the present invention is a support on which the composition of the present invention is applied, and includes, for example, a transparent plastic film, a pigmented opaque film, a foamed film, a high quality paper, a medium paper, Conventional paper such as art paper, bond paper, copy paper, baryta paper, cast coated paper, corrugated paper, coated paper, synthetic paper, resin-coated paper, glass, cotton, rayon, acrylic, polyester, etc. cloth, metal Any known one can be used.

Examples of transparent plastic films include polyester, polyolefin, polyamide, polyesteramide, polyether, polyimide, polyamideimide, polystyrene, polycarbonate, poly-P-phenylene sulfide, polyetherester, polyvinyl chloride, and poly (meth). Acrylic sun esters and the like can be used. Further, these copolymers, blends, and further crosslinked products can also be used.

The raw material is appropriately selected from the above-mentioned substrates in accordance with various conditions such as the purpose of recording the recording medium, the use of the recorded image, and the adhesion to the composition coated on the recording medium. The carboxyalkyl cellulose nitrate used in the present invention is a carboxyalkyl cellulose having a nitrate ester substitution degree of 0.2 to 2.95,
Carboxyalkyl ether group substitution degree is 0.05-2.
8, specifically the aqueous cellulose derivatives disclosed in JP-A-5-39301 and JP-A-5-39302.

If the nitrate ester group substitution degree is less than 0.2, the water resistance is insufficient, and if it exceeds 2.95, the hydrophilicity becomes insufficient. A preferred range of the nitrate ester group substitution degree is 0.2 or more and 2.2 or less. If the degree of carboxyalkyl ether group substitution is less than 0.05, the solubility in water is insufficient, and the ink absorbency is insufficient. If it exceeds 2.8, the water resistance of the coated surface is insufficient. The preferred range of the degree of substitution of the carboxyalkyl ether group is 0.05 or more,
1.5 or less.

The cation-modified polyvinyl alcohol used in the present invention is a polyvinyl alcohol having a cation modification amount of 0.01 mol% or more. For example, the cation modifying group is selected from an amide group, an imide group, a primary amino group, a secondary amino group, a tertiary amino group, a primary ammonium base, a secondary ammonium base, a tertiary ammonium base, and a quaternary ammonium base. Preferred are those containing at least one cationic group.

The cation modification amount is preferably 0.1 to 30 mol%. Furthermore, 0.1 to 15 mol% is preferable. If the amount of modification of the cationic group is less than 0.1 mol%, the water resistance of the ink absorbing layer is not always sufficient. The average degree of saponification is preferably from 40 to 100 mol%. Saponification degree 40
If it is less than mol%, the ink absorbency tends to decrease. The average degree of polymerization is preferably from 100 to 5000. Further, 200 to 3000 is preferable. Average degree of polymerization is 100
If it is less than 5,000, the water resistance of the ink absorbing layer will be reduced. If it exceeds 5,000, the solution viscosity will be high and the workability may be reduced.

The cationic polymer used in the present invention is:
Water-soluble cationized polymers other than the above-mentioned cation-modified polyvinyl alcohol, such as cationized cellulose, cationized starch, cationized guar gum, diallyl quaternary ammonium salt polymer, diallyl quaternary ammonium salt / acrylamide copolymer and the like. . Among these, a polymer / copolymer of diallyl quaternary ammonium salt is preferred from the viewpoint of printing water resistance.

The mixing ratio of the carboxyalkyl cellulose nitrate to the cation-modified polyvinyl alcohol and the cation polymer used in the present invention is based on the weight of the solid content of the carboxyalkyl cellulose nitrate.
10 to 96% by weight of cation-modified polyvinyl alcohol and 1 to 20% by weight of cationic polymer with respect to 80% by weight
Is preferred. This mixing ratio can be arbitrarily selected depending on the balance between the nitric acid ester groups of the nitric acid esters of the carboxyalkyl cellulose and the carboxyalkyl groups.

In the present invention, the thickness of the coating layer provided on the raw fabric is 1 to 100 μm, preferably 1 to 50 μm,
Further, 5 to 30 μm is appropriate. If the thickness is too small, water absorption is insufficient and drying takes time. If the thickness is too large, water resistance may decrease or coating may be difficult. A mixture of a nitric acid ester of carboxyalkylcellulose, a cation-modified polyvinyl alcohol, and a cation polymer used in the present invention with an aqueous polymer for the purpose of improving ink drying properties, film properties of an ink receiving layer, gloss, and image clarity. May be mixed.

Examples of the aqueous polymer include gelatin derivatives such as lime-processed gelatin, acid-processed gelatin, and enzyme-processed gelatin; for example, gelatin reacted with anhydrides of dibasic acids such as phthalic acid, maleic acid, and fumaric acid. Various gelatins, oxidized starch, cationized starch, starches such as etherified starch, cellulose derivatives such as methylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose, hydroxyethylcellulose, polyalkylene oxides and their derivatives, polyacrylic acid , Polymethacrylic acid or its esters, salts and their copolymers, polyhydroxyethyl methacrylate and its copolymers, polyvinylpyrrolidone, polyvinylpyridium , Polyvinyl alcohol of various degrees of saponification, carboxy-modified, amphoteric polyvinyl alcohol, polyethylene glycol, polypropylene glycol, polyvinyl ether, alkyl vinyl ether-maleic anhydride copolymer, styrene-maleic anhydride copolymer, and salts thereof, Synthetic polymers such as polyethyleneimine, conjugated diene copolymer latex such as styrene / butadiene copolymer, methyl methacrylate / butadiene copolymer, polyvinyl acetate, vinyl acetate / maleic ester copolymer, vinyl acetate / acryl Acid ester copolymer, vinyl acetate copolymer latex such as ethylene / vinyl acetate copolymer, acrylate ester polymer, methacrylate ester polymer, ethylene / acrylate ester copolymer, styrene / acrylic acid Latex of an acrylic polymer or copolymer such as an acid ester copolymer, a functional group-modified polymer latex with a functional group-containing monomer such as a vinylidene chloride-based copolymer latex or a carboxyl group of these various polymers, Aqueous adhesives such as thermosetting synthetic resins such as melamine resin and urea resin, and aqueous synthetic resins such as polymethyl methacrylate, polyurethane resin, unsaturated polyester resin, vinyl chloride / vinyl acetate copolymer, polyvinyl butyral, and alkyd resin Can be mentioned. These can be used alone or in combination.

Known additives can be used in the composition for printing raw material of the present invention as long as the properties of the present invention are not impaired. For example, matting agents such as calcium carbonate, basic magnesium carbonate, and crystalline cellulose, antifoaming agents, coating improvers, thickeners, antistatic agents, antioxidants, ultraviolet absorbers, dyes, water resistance agents, light resistance And a printability improving agent such as colloidal silica and alumina sol.

The carboxyalkyl cellulose nitrates used in the present invention may have some or all of the carboxyl groups contained therein neutralized. By being neutralized, the solubility in water and a water-soluble organic solvent containing water as a main component is increased, and handling becomes easy. For neutralization, one or more cations such as an alkali metal ion, an alkaline earth metal ion, an ammonium ion, and an organic amine 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.

Examples of the water-soluble organic solvent which can be used for dissolving the carboxyalkyl cellulose nitrate used in the present invention include alcohols, polyhydric alcohols, derivatives of polyhydric alcohols, ketones, esters, and carbonates. Or a combination of two or more solvents. As alcohols, methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, n-pentanol, n-hexanol, n-heptanol, n-octanol, n-
Nonyl alcohol, n-decanol, n-undecanol or isomers thereof, cyclopentanol, cyclohexanol and the like can be mentioned. 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, diethylene glycol and the like.

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, triethylene glycol butyl ether, etc.
Or solvent pocket book (p4
79-p574; September 20, 1990, issued by Ohmsha) and polyhydric alcohols and derivatives thereof.

Examples of ketones include acetone, methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, diisopropyl ketone, cyclopentanone and cyclohexanone. Esters include methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, amyl acetate, lactate ester, butyrate ester, diisopropyl glutarate, diisopropyl succinate, diisopropyl adipate, dibutyl phthalate, dioctyl phthalate, And ε-
And cyclic esters such as caprolactone and ε-caprolactam.

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

In forming the coating layer of the composition for printing raw material of the present invention, a known method such as an air knife coater, a blade coater, a bar coater, a gravure coater, a curtain coater, a roll coater, or an applicator is applied. Can be. At this time, if the raw material is subjected to a known surface treatment such as a corona discharge treatment or a primer treatment in the air or another atmosphere as necessary before coating, the coatability is only improved. And a coating layer can be firmly formed on the surface of the raw film.

If necessary, the composition may be applied to both sides of the raw material, or ink absorbing layers having different physical properties may be laminated on the raw material. 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. By using a composition containing a carboxyalkyl cellulose nitrate, a cation-modified polyvinyl alcohol, and a cation polymer of the present invention, the ink has good absorbency and fixing property, good drying property, good water resistance and good blocking resistance. A recording material having an ink receiving layer formed thereon is obtained. Also, using a transparent substrate, making the coating layer opaque,
The present invention can be applied to a back coat film or the like in which a printed image is viewed from a raw material direction.

[0030]

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 printability] Inkjet printer (BJ
-600J; manufactured by Canon Inc.) to print solid on the printing material. The sharpness after recording and the degree of bleeding were visually judged. ：: good, や: slightly good, ×: bad [Dryability evaluation method] Printing was performed on the raw material for printing, and after 60 seconds, a copy paper was overlaid on the printed portion and the load was changed to (125 g /
cm ² ), and the degree of transfer to copy paper was evaluated. ○: No transfer, △: Slightly transfer, ×: Very transfer [Water resistance evaluation method] After immersing the solid printed printing material in water for 2 minutes, air dry, and check the ink flow It was visually determined. ：: no change, △: slightly flowing, ×: flowing away [Evaluation method of heat-resistant blocking property] After the recording surfaces of the recording sheets are superimposed on each other and subjected to a load (125 g / cm ² ) and allowed to stand at 60 ° C. for 30 minutes. The blocking state was determined. ○: No resistance, Δ: Resistance, ×: Peeling

[0031]

[Production Example 1] Carboxymethylcellulose (Cellogen 5
A; manufactured by Daiichi Kogyo Seiyaku Co., Ltd .; carboxymethyl ether group substitution degree = 0.7), 100 g, and sulfuric acid / nitric acid / water = 63.
5000 g of an acid mixture consisting of / 25/12% by weight is put into 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 a centrifuge and immediately washed with a large amount of water. Further, the reaction product was made into a 10% slurry in an autoclave,
After treatment at 30 ° C. for 30 minutes, the reaction product was recovered by separation on a Buchner funnel. The reaction product was dried at 80 ° C. for 2 hours to obtain 120 g of carboxymethyl cellulose nitrate. Anhydroglucose unit 1 of this nitrate ester
The nitrate ester group substitution degree per piece is the carboxymethyl ether group substitution degree (0.
7) and the measurement of the nitrogen content by the CHN coder showed that it was 1.9.

Next, 100 g of a 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 anhydroglucose unit obtained per anhydroglucose unit and ion-exchanged water 59
8.6 g and 250 g of butyl cellosolve were put into a closed mixer and stirred. Further, 51.4 g of 10% aqueous ammonia was added as a neutralizing agent. The solution was completely dissolved with heating to obtain a solution having a solid content of 10%. This is the binder solution A
And

[0033]

[Production Example 2] Carboxymethylcellulose (Cellogen 5
A; manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd .; carboxymethyl ether group substitution degree = 0.7), sulfuric acid / nitric acid / water = 59 /
90 g of dried carboxymethylcellulose nitrate was obtained in the same manner as in Production Example 1 except that the content was 20/21% by weight and the treatment was performed in an autoclave at 100 ° C. for 30 minutes. The degree of substitution of the nitric ester group per anhydroglucose unit of this nitrate ester was the degree of substitution of the carboxymethyl ether group of carboxymethyl cellulose (0.
7) and the measurement of the nitrogen content by the CHN coder showed that it was 1.2.

Next, 100 g of carboxymethylcellulose nitrate having a degree of substitution of nitrate ester of 1.2 and a degree of substitution of carboxymethyl ether group of 0.7 per unit of anhydrous glucose unit obtained above and 84 parts of ion-exchanged water were obtained.
2.8 g and 200 g of isopropyl alcohol were put into a closed mixer and stirred. 10% as a neutralizer
57.2 g of aqueous ammonia was added. The solution was completely dissolved with heating to obtain a solution having a solid content of 10%. This is designated as Binder Liquid B.

[0035]

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,
The solution was stirred until it was completely dissolved to obtain a solution having a solid content of 10%. This is designated as binder liquid C.

Binder solution A and binder solution C, diallyl quaternary ammonium salt-based cationic polymer (trade name: ADEKA CATION ACE PD-50; Asahi Denka Kogyo Co., Ltd.)
47.5: 47.5: 5.0 in terms of solid content weight ratio.
To prepare a printing material composition. The composition is
On a polyethylene terephthalate film, coated with a rod coater so that the film thickness after drying is 10 to 25μ,
After drying, a recording sheet was obtained. The obtained sheet was printed solid with an ink jet printer. As a result, physical properties were as follows, and all satisfactory physical properties were obtained. Printability: 、, drying property: 、, water resistance; 、, heat blocking property: ○

[0037]

Example 2 A recording sheet was obtained in the same manner as in Example 1 except that the binder liquid A was changed to the binder liquid B. As a result, physical properties were as follows, and all satisfactory physical properties were obtained. Printability: 、, drying property: 、, water resistance; 、, heat blocking property: ○

[0038]

Example 3 Example 3 was repeated except that the cationic polymer of Example 1 was changed to a diallyl quaternary ammonium salt / acrylamide copolymer (trade name: ADEKA CATION ACE PDA-245; manufactured by Asahi Denka Kogyo KK). A recording sheet was obtained in the same manner as in Example 1. As a result, the physical properties are as follows,
All satisfactory physical properties were obtained. Printability: 、, drying property: 、, water resistance; 、, heat blocking property: ○

[0039]

Example 4 Cation-modified polyvinyl alcohol (K2
10: Nippon Synthetic Chemical Industry Co., Ltd.), 800 g of ion-exchanged water, 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 designated as binder liquid D.

Binder solution A and binder solution D, diallyl quaternary ammonium salt-based cationic polymer (trade name: ADEKA CATION ACE PD-50; Asahi Denka Kogyo Co., Ltd.)
47.5: 47.5: 5 in terms of solid content weight ratio.
0 to prepare a printing material composition. The composition was coated on a polyethylene terephthalate film with a rod coater so that the film thickness after drying was 10 to 25 μm, and dried to obtain a recording sheet. The obtained sheet was printed solid with an ink jet printer. As a result, physical properties were as follows, and all satisfactory physical properties were obtained. Printability: 、, drying property: 、, water resistance; 、, heat blocking property: ○

[0041]

Comparative Example 1 A recording sheet was obtained in the same manner as in Example 1 except that only the binder liquid C of Example 1 was used as the binder liquid. As a result, the physical properties were as follows. ×, drying property; ×, water resistance; ×, heat blocking property; ×

[0042]

Comparative Example 2 A recording sheet was obtained in the same manner as in Example 1 except that only the binder liquid A of Example 1 was used as the binder liquid. As a result, the physical properties were as follows.性, drying property; 水性, water resistance; ×, heat blocking property; か ら From the above results, the recording material obtained by using the printing material composition of the present invention is excellent in ink absorbency and It can be seen that all physical properties such as ink drying property, print clarity, water resistance and heat blocking property are excellent.

[0043]

The recording material obtained by using the composition for a printing material of the present invention is excellent in ink absorption, ink drying, print clarity, water resistance and heat blocking property. Therefore, it can be used for applications such as OHP sheets, calendars, posters, stickers (such as stickers), and cards (such as business cards). Further, by making the coating layer opaque using a transparent raw material, it can be used for a back coat film or the like in which a printed image is viewed from the raw material direction.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI D21H 19/52 D21H 1/30

Claims (2)

[Claims] 1. Nitrate esters 3 of carboxyalkyl cellulose having a degree of substitution of nitric acid ester groups per anhydroglucose unit of 0.2 to 2.95 and a degree of substitution of carboxyalkyl ether groups of 0.05 to 2.8. A composition for a raw material for printing, comprising 80 to 80% by weight, 96 to 10% by weight of a cation-modified polyvinyl alcohol and 1 to 20% by weight of a cationic polymer. 2. The composition according to claim 1, wherein the cationic polymer is a polymer or copolymer of diallyl quaternary ammonium salt.