JPH10330601A - Coating composition for ink receiving layer having improved fixation of ink and water resistance and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a coating composition for ink receiving layers, having improved ink fixation in ink-jet printing and water resistance and excellent transparency and clarity of recorded image. SOLUTION: This composition comprises a graft urethane resin (1) prepared by grafting (C) 100-60 wt.% of a hydrophilic radically polymerizable vinyl monomer with 0-40 wt.% of another copolymerizable vinyl monomer in an aqueous solution or a water dispersion in which (A) an aqueous urethane resin is mixed with (B) a polyvinyl alcohol having 75-100% saponification degree and 500-5,000 polymerization degree and a modified cationic polymer (2) obtained by compounding (D) a copolymer composed of 10-160 wt.% of a radically polymerizable vinyl monomer having a cationic quaternary ammonium base at the side chain and 90-10 wt.% of another copolymerizable vinyl monomer with (E) a polyvinyl alcohol hating 75-100% saponification degree and 500-5,000 polymerization degree.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating composition for an ink receiving layer having improved fixability and water resistance of an ink, and a method for producing the same. More specifically, the present invention is applied to a base material such as a plastic film, synthetic paper, knitted fabric, nonwoven fabric, paper, metal, etc., so that the ink has good printability and good ink fixability and water resistance in ink jet printing. It is intended to provide a coating composition for a receptor layer and a method for producing the same.

[0002]

2. Description of the Related Art An ink jet recording system is capable of high-speed recording, has a low impact noise due to non-contact with a printing base material, and can use various types of printing base materials including plain paper. In recent years, it has been widely used because of its advantages such as color recording. Printed images are required to be clear images with high contrast and no bleeding. For this reason, when a plastic film other than paper or synthetic paper is used as a printing substrate, an ink receiving layer is applied to the substrate surface. The method has been taken. The ink receiving layer is required to quickly absorb the ink, fix the absorbed ink, and impart water resistance to the printed surface.

In order to satisfy this demand, an ink receiving layer containing a cationic compound as an ink fixing agent has been proposed. For example, Japanese Patent Application Laid-Open No. Hei 7-61113 discloses a recording medium containing a polyvinyl acetal resin and a cationic compound as essential components. However, JP-A-7-68926 discloses that a mixture of polyvinyl alcohol, polyvinyl pyrrolidone, vinyl acetate homopolymer and / or vinyl acetate copolymer is used.
An ink receiving layer containing a grade ammonium compound has been proposed.

However, in the above method, problems such as bleeding due to insufficient adhesion to the printing substrate and insufficient water resistance of the film have not yet been solved, and a satisfactory ink drying property can be obtained. It is not at present.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems and to provide a coating for an ink-receiving layer for ink-jet recording which has good transparency, good ink absorption, good ink fixability and water resistance. It is to obtain a composition.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above problems, and as a result, have accomplished the present invention. That is, the present invention provides (A) an aqueous urethane resin, (B) a saponification degree of 75 to 100%, and a polymerization degree of 500 to 5
(C) 100 to 60% by weight of a hydrophilic radically polymerizable vinyl monomer and 0 to 40% by weight of another copolymerizable vinyl monomer are graft-polymerized in an aqueous solution or an aqueous dispersion in which 2,000 polyvinyl alcohols are mixed. The obtained graft urethane resin (1) is mixed with (D) 10 to 100% by weight of a radical polymerizable vinyl monomer having a cationic quaternary ammonium base in a side chain thereof and 90 to 0% by weight of another copolymerizable vinyl monomer. The modified cationic polymer (2) obtained by mixing the copolymer with (E) polyvinyl alcohol having a degree of saponification of 75 to 100% and a degree of polymerization of 500 to 5,000. An image without bleeding is obtained and ink fixability,
An ink receiving layer coating composition having excellent water resistance and a method for producing the same are disclosed.

Hereinafter, the present invention will be described in detail. The aqueous urethane resin used in the present invention is obtained by dissolving or dispersing a polyurethane resin synthesized from a polyhydroxy compound, a diisocyanate and a low molecular weight chain extender containing at least two hydrogen atoms that react with the diisocyanate in water. And synthesized by a known method. It refers to a compound having an anionic group such as a carboxyl group in a molecule as a hydrophilic group for dissolving or dispersing in water.

[0008] The polyhydroxyl compounds used in the production of the urethane resin described above include phthalic acid, adipic acid,
Organic acids such as dimerized linoleic acid and maleic acid, and glycols such as ethylene glycol, propylene glycol, butylene glycol, and diethyl glycol, and trimethylolpropane, hexanetriol, glycerin, trimethylolethane, and pentaerythritol are subjected to a dehydration condensation reaction. The resulting polyester polyol, polyoxypropylene glycol, polyoxybutylene glycol, polytetramethylene glycol, polyoxypropylene triol, polyoxyethylene polyoxypropylene triol, sorbitol, pentaerythritol, sucrose, starch, inorganic acids such as phosphoric acid Initiators such as polyoxypropylene polyols, polyoxypropylene polyoxyethylene polyols and other polyether polyols Le, an acrylic polyol, a derivative of castor oil, tall oil derivatives, other hydroxyl compounds.

As the diisocyanate, for example, 2,
4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-
Phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, trimethyl hexamethylene diisocyanate, 1,4-cyclohexylene diisocyanate,
4,4'-dicyclohexylmethane diisocyanate,
3,3'-dimethyl-4,4'-biphenylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenylene diisocyanate, 3,3'-dichloro-4,4 '
-Biphenylene diisocyanate, 1,5-naphthalene diisocyanate, 1,5-tetrahydronaphthalene diisocyanate and the like.

As the chain extender, ethylene glycol,
1,4 butanediol, trimethylolpropane, triisopropanolamine, N, N-bis (2-hydroxypropyl) aniline, hydroquinone-bis (β-hydroxyethyl) ether, resorcinol-bis (β-
Polyols such as hydroxyethyl) ether, ethylenediamine, propylenediamine, hexamethylenediamine, phenylenediamine, tolylenediamine, diphenyldiamine, diaminodiphenylmethane, diaminodiphenylmethane, diaminodicyclohexylmethane, piperazine, isophoronediamine, diethylenetriamine,
Polyamines such as dipropylene triamine, hydrazines, and water.

The polyvinyl alcohol used in the present invention is generally obtained by saponifying polyvinyl acetate by an acid saponification method or an alkali saponification method, and has a saponification degree of 75 to 100%. Are suitable. The polyvinyl acetate mentioned here may be a copolymer with 5% or less of another copolymerizable monomer. The polymerization degree is preferably from 500 to 5,000, and those having different degrees of polymerization and saponification may be used as a mixture.

As the hydrophilic radically polymerizable vinyl monomer used in the present invention, a monomer having a hydrophilic group represented by the following chemical formula is used.

[0013]

Embedded image

Specific examples of the hydrophilic radical polymerizable vinyl monomer used in the present invention include hydroxyacrylates such as hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and hydroxypropyl methacrylate; Glycol esters such as glycol acrylate, ethylene glycol methacrylate, polyethylene glycol acrylate and polyethylene glycol methacrylate, acrylamide compounds such as acrylamide, methacrylamide, methylol acrylamide and methoxymethylol acrylamide, and glycidyl acrylate compounds such as glycidyl acrylate and glycidyl methacrylate , Vinylpyridine, vinylimidazole, vinylpyrrolidone, etc. Sulfonyl compounds, acrylic acid, methacrylic acid, maleic acid anhydride, itaconic acid, unsaturated acids and salts thereof such as crotonic acid, amino alkyl acrylate, methacrylic acid aminoalkyl ester can be exemplified.

The above-mentioned hydrophilic radical polymerizable monomers may be used alone or in combination of several kinds.
Furthermore, other copolymerizable vinyl monomers can be used in combination with these hydrophilic monomers.

Other copolymerizable vinyl monomers include vinyl esters such as vinyl acetate and vinyl propionate;
Vinyl chloride, vinyl halides such as vinyl bromide, unsaturated carboxylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, dimethyl vinyl methoxy silane, γ- Vinyl silane such as methacryloxypropyl trimethoxy silane, ethylene, propylene,
Examples thereof include olefins such as styrene and butadiene, and diolefin compounds.

The graft urethane resin in the present invention is obtained by graft-polymerizing the aqueous urethane resin and polyvinyl alcohol with 100 to 60% by weight of a hydrophilic radically polymerizable vinyl monomer and 0 to 40% by weight of another copolymerizable vinyl monomer. can get. When the content of the hydrophilic vinyl monomer is 60% by weight or less, the ink absorbency deteriorates, which is not preferable.

As a polymerization method for obtaining the graft urethane resin, a conventionally known method can be used. For example, a polymerization initiator and, if necessary, a small amount of an emulsifying dispersant are added to the aqueous dispersion of the aqueous urethane resin and polyvinyl alcohol, and the radical polymerizable vinyl monomer is gradually added while stirring at 70 to 80 ° C. And then 2
A method of aging for 5 hours to complete the polymerization to obtain the graft urethane resin of the present invention. Since the radically polymerizable vinyl monomer is graft-polymerized to the aqueous urethane resin and polyvinyl alcohol, this component has excellent ink absorbency and adhesiveness, which is a characteristic of the urethane resin.
It also has properties such as water resistance and toughness.

As the polymerization initiator, general radical polymerization initiators such as potassium persulfate, ammonium persulfate,
Water-soluble peroxides such as hydrogen peroxide, oil-soluble peroxides such as benzoyl peroxide and t-butyl hydroperoxide, and azo compounds such as azodiisobutyronitrile can be used.

The ratio of the aqueous urethane resin, polyvinyl alcohol and the radical polymerizable vinyl monomer is 10 to 500 parts by weight, preferably 20 to 3 parts by weight, based on 100 parts by weight of the aqueous urethane resin in terms of solid content.
00 parts by weight, and 1 radical polymerizable vinyl monomer
0 to 500 parts by weight, preferably 20 to 300 parts by weight.

When the content of polyvinyl alcohol is 10 parts by weight or less, the sharpness of the image and the ink absorbency become poor.
If the amount is more than the weight part, the water resistance becomes poor. When the amount of the radical polymerizable vinyl monomer is less than 10 parts by weight, the ink absorbency is poor, and when it is more than 500 parts by weight, water resistance and blocking resistance are poor.

The radical polymerizable vinyl monomer having a cationic quaternary ammonium base in the side chain used in the present invention includes quaternized aminoalkyl acrylates and aminoalkyl methacrylates,
For example, quaternized products of dimethylaminoethyl methacrylate with methyl chloride or dimethyl sulfate, quaternized products of dimethylaminopropyl (meth) acrylamide with methyl chloride, dimethyl sulfate, benzyl chloride, monochloroacetic acid, etc., acrylamido-3-methylbutyldimethylamine And monomers having a quaternary ammonium base, such as a quaternary compound, a vinylbenzylammonium salt and a diallylammonium salt.

As the other vinyl monomer copolymerizable with the radically polymerizable vinyl monomer having a cationic quaternary ammonium salt in the side chain, those described above can be used.

Radical polymerizable vinyl monomer having a cationic quaternary ammonium salt in the side chain
In a copolymer of 100% by weight and 90 to 0% of another copolymerizable vinyl monomer (hereinafter referred to as a cationic copolymer), a radical polymerizable vinyl monomer having a cationic quaternary ammonium salt in a side chain is 10%. When the content is less than the weight%, the fixing property of the ink and the ink absorbency become poor.

As a specific method for obtaining the cationic copolymer, a conventionally known method can be used. For example, while a polymerization initiator and water in which a small amount of an emulsifying dispersant is dissolved as necessary are kept at 70 to 80 ° C., a radically polymerizable vinyl monomer is gradually added dropwise with stirring, and then ripened for 2 to 5 hours to polymerize. And a cationic copolymer can be obtained.

As the polymerization initiator, benzoyl peroxide, t
Peroxides such as -butyl hydroperoxide and hydrogen peroxide, and azo compounds such as azodiisobutyronitrile and 2,2'-azobis- (amidinopropane) dihydrochloride can be used. Initiators that generate an anionic group such as potassium persulfate and ammonium persulfate are not preferred because they cause a complex with a cationic monomer.

The cationic copolymer of the present invention has excellent film-forming properties, and forms a transparent film by drying at a temperature of 0 ° C. or higher. Further, it is excellent in performance of forming an ion complex with an anionic dye in the ink and fixing the ink.

The modified cationic polymer used in the present invention can be obtained by mixing the above cationic copolymer with polyvinyl alcohol. Polyvinyl alcohol has a saponification degree of 75 to 100% and a polymerization degree of 500 to 5 as described above.
000 can be used. When the cationic copolymer is mixed with polyvinyl alcohol, the cationic copolymer and the anionic graft urethane resin of the present invention can be stably present without easily forming an ion complex.

The mixing ratio of the cationic copolymer to polyvinyl alcohol is 5 to 200 parts by weight of polyvinyl alcohol based on 100 parts by weight of the cationic copolymer in terms of solid content. If the amount of polyvinyl alcohol is 5 parts by weight or less, mixing with the graft urethane resin becomes impossible, and if the amount of polyvinyl alcohol is 200 parts by weight or more, the fixing property of the ink and the adhesion to the substrate become poor.

The coating composition for an ink receiving layer of the present invention is obtained by mixing the above graft urethane resin and a modified cationic polymer. The method of mixing is not particularly limited, but the most stable coating liquid can be prepared by a method of gradually dropping the aqueous graft urethane resin dispersion into the aqueous modified cationic polymer dispersion. In the coating liquid produced by this method, the anionic graft urethane resin and the cationic polymer can stably exist without forming an ion complex and aggregating. The reason is that the anionic urethane resin particles are protected by the graft polymer, and the cationic copolymer is also wrapped in polyvinyl alcohol. It seems that they coexist with fine particles. And drying,
It is considered that the ink-fixing cationic component is present as a fine sea-island structure in the ink-absorbing component even after film formation.
It can be understood that the adhesion to the substrate and the water resistance of the film are remarkably improved as compared with the water resistance of the film formed individually.

The mixing ratio between the graft urethane resin and the modified cationic polymer is 50:50 to 95: 5 in terms of solids weight ratio.
It is. When the proportion of the modified cationic polymer is 50% by weight or more, not only poor printability but also poor water resistance and fixability of the ink in printing with a dye type ink, and a substrate such as a polyester film curls after drying. Cause. 5% by weight of modified cationic polymer
Below, the fixability of the ink is insufficient, resulting in poor water resistance.

The coating composition for an ink receiving layer of the present invention obtained as described above may optionally contain a resin component such as an epoxy resin, an amino resin, an acrylic resin, a polyester resin, a urethane resin, and an isocyanate resin. Compounds, epoxy compounds, carbodiimides, crosslinkers such as silane coupling agents, inorganic fillers such as silica, alumina, talc, kaolin clay, calcium carbonate, mica, and polymethyl acrylate, polystyrene, and polyacrylonitrile porous fine particles Organic fillers, titanium and chromium inorganic pigments and organic pigments, film forming aids, thickeners, leveling agents, antiblocking agents, antistatic agents, ultraviolet absorbers, antioxidants and other conventionally known additives are added. can do.

The coating composition for an ink receiving layer of the present invention is applied to a substrate described below and dried. As the base material, a molded article such as a plastic film or a printing paper such as a synthetic paper can be used. As plastic films, polyester, polyethylene, polypropylene, PVC,
Polycarbonate, nylon, polystyrene, cellophane, triacetate and the like, and synthetic papers such as polypropylene, polyethylene, polystyrene and polyester can be used. Further, it can be applied to paper or a cloth such as a woven or knitted fabric, a nonwoven fabric, a molded product such as a metal, a wood, a ceramic, a ceramic, or the like.

The coating composition for an ink receiving layer of the present invention is usually used as water or a solution or dispersion mainly composed of water, and its concentration is preferably from 10 to 50% by weight. One side or both sides of the printing substrate are coated and dried by a usual roll coater, gravure coater, bar coater, knife coater or the like. The coating amount is usually in the range of 2 to 50 µm, more preferably 5 to 30 µm in film thickness after drying. In the case of cloth or nonwoven fabric, it can be processed by immersion.

As the printing ink for ink-jet printing on the ink receiving layer, aqueous and oily dye inks and pigment inks can be used. In fact, in ink jet printing, ink drops ejected from nozzles land on the present ink receiving layer and are absorbed. The acid dye or pigment in the ink component is fixed by the cationic copolymer in the receiving layer. As a result, the ink-receiving layer obtained as described above has good adhesion to the substrate, good transparency and gloss, excellent ink absorption and drying properties, and the image printed and recorded by the inkjet recording method is It is clear, has no bleeding, has good ink fixability and water resistance, and has good storage stability after printing.

The coating composition of the present invention can be used as a single solution without adding a crosslinking agent or the like. It is useful as a coating composition for an ink receiving layer of the present application.

Hereinafter, the present invention will be described in more detail with reference to examples. Production of Graft Urethane Resin [Production Examples a, b, and cf (Comparative)] An aqueous urethane resin, a polyvinyl alcohol aqueous solution, and water were charged into a reaction vessel equipped with a cooling tube with the composition shown in Table 1 below, and nitrogen gas was supplied for 20 minutes. Deoxygenation was sufficiently performed by blowing. Next, an initiator was added, the temperature was raised to 70 to 80 ° C., the radical polymerizable vinyl monomer was added dropwise over 1 hour, and the mixture was aged at the same temperature for 3 hours to obtain a graft urethane resin.

C is an example of a graft urethane resin containing no polyvinyl alcohol. d is aqueous urethane 100
This is an example of the graft urethane resin in which the ratio of polyvinyl alcohol to the weight part is 500 parts by weight or more. e is an example of a graft urethane resin in which the ratio of the hydrophilic vinyl monomer in the vinyl monomer is 60% by weight or less.

F is an example of the graft urethane resin in which the ratio of the vinyl monomer to 100 parts by weight of the aqueous urethane is 500 parts by weight or more.

[0040]

[Table 1]

[Production Example g (Comparative)] 25 parts by weight of 10% gohsenol GH-17 was blended with 100 parts by weight of the aqueous graft urethane resin dispersion obtained in Production Example c.
(Example when polyvinyl alcohol is mixed after polymerization)

Production of Modified Cationic Polymer [Production Example (a), (b), (c), (d), and (e) (Comparative)] A reaction vessel equipped with a cooling tube was charged with water and an emulsifier in the composition shown in Table 2 below.
Deoxygenation was sufficiently performed by blowing nitrogen gas for 0 minutes. Next, an initiator was added, the temperature was raised to 70 to 80 ° C., the radical polymerizable vinyl monomer was added dropwise over 2 hours, and the mixture was aged at the same temperature for 3 hours, and then cooled. After cooling, an aqueous solution of polyvinyl alcohol was mixed to obtain a modified cationic polymer.

C is an example in which the ratio of the vinyl monomer having a cationic quaternary ammonium salt in the vinyl monomer is 10% by weight or less. D is an example in which the ratio of polyvinyl alcohol to 100 parts by weight of the cationic copolymer is 5 parts by weight or less. (E) is an example in which the ratio of polyvinyl alcohol to 100 parts by weight of the cationic copolymer is 200 parts by weight or more.

[0044]

[Table 2]

Preparation of Coating Agent for Ink Receiving Layer The solid content of the graft urethane resin and the modified cationic polymer was adjusted to 12% by weight with water, and the graft urethane resin and the modified cationic polymer were mixed in the combinations and mixing ratios shown in Table 3. Thus, a coating agent for an ink receiving layer was obtained.
The mixing method was such that a modified cationic polymer was charged into a mixing container, and the graft urethane resin was gradually mixed over 30 minutes with stirring, and after the entire amount was charged, stirring was further continued for 1 hour to obtain a coating agent. However, in Comparative Example 7, aggregation occurred during mixing, and a stable coating liquid could not be produced.
Comparative Example 10 is an example of a graft urethane resin alone.

[0046]

[Table 3]

Examples of Coating Agent Application and Performance Evaluation Example of Coating on Polyester Film The coating agent (Examples 1 to 4 and Comparative Examples 1 to 10) was applied to a 100 μm-thick biaxially stretched polyester film so that the coating thickness after drying was 10 μm.
Dry at 5 ° C. for 5 minutes. About the obtained processed film,
The following tests were performed. 1) Adhesion to polyester film Cross cut tape method (JIS K 5400 8.5.2)
Apply cellophane tape from the processing surface according to
The resin remaining ratio after being immediately peeled off in the 80 ° direction was measured.

〇: Residual rate 100% △: Residual rate 99 to 80% ×: Residual rate 79% or less 2) Blocking resistance A processed surface and an unprocessed surface are superimposed and a load of 1 kg / cm 2 is applied thereto, at 40 ° C. and RH90. % For 24 hours,
The blocking resistance was evaluated from the state at the time of peeling.

Δ: Peeled off without any resistance Δ: Slightly resistant ×: Significantly resistant 3) Transparency Haze on the coated surface was visually judged.

〇: Completely transparent △: Slightly cloudy ×: Completely opaque 4) Image clarity Color inkjet printer BJC manufactured by Canon Inc.
Printing was performed on the processed surface using -400 J, and image bleeding, color tone, and density were visually determined.

〇: No bleeding, clear ×: There is bleeding 5) Penetration / drying of ink The filter paper is pressed onto the printed image under a load of 40 g / cm 2 for 5 seconds until the ink stops transferring to the filter paper. Was measured. 〇: Penetrates within 30 seconds and does not sticky ×: Does not penetrate within 30 seconds, sticky 6) Ink fixability One drop of water is dropped on the image after printing and left for one day with a pipette, and 40 g after 10 seconds / Cm2 was applied to the tissue paper to determine the remaining state of the wiping ink and the film.

Δ: Ink hardly falls off Δ: Ink is removed but film remains ×: Film is removed 7) Presence or absence of curl The processed film was projected with an overhead projector, and it was examined whether the film was curled by heat.

：: no curl ×: curl

Table 4 shows the results. That is, Examples 1-4 showed good performance in all items including the fixing property of the ink. In contrast, Comparative Examples 1 to 10 were insufficient in performance.

[0055]

[Table 4]

2. Example of Coating on Synthetic Paper 2-1 Example of Polypropylene Synthetic Paper Fine seal X-37 (fine silica, manufactured by Tokuyama Soda Co., Ltd., secondary particle diameter: 3.7 μm) was added to the coating agent of Example 1 in terms of solid content weight ratio. Then, 0.2% was added and mixed well, and then applied to YUPO FPG-130 (manufactured by Oji Yuka Synthetic Paper) so that the coating thickness after drying was 10 μm, and dried at 80 ° C. for 3 minutes. A high-grade coated film with good gloss was obtained. When printing was performed with a color ink jet printer DJ850C manufactured by Hewlett-Packard Company, good printability and ink fixability were obtained. 2-2 Polyester synthetic paper The same coating agent as in Example 2-1 was applied to polyester synthetic paper in the same manner as in 2-1. A glossy and curled coating film was obtained. Performance evaluation was performed in the same manner as in 2-1. As a result, good performance was obtained in the same manner as 2-1.

3. Example of coating on paper 3-1 Example of high-grade paper (coated paper) Kallite KT (calcium carbonate manufactured by Shiraishi Kogyo Co., Ltd., secondary particle diameter 2.0 μ) was added to the coating agent of Example 2 in a solid content weight ratio. After adding 0.5% and mixing well, it was coated on high-grade paper so that the coating thickness after drying became 15 μm, and dried at 80 ° C. for 3 minutes. When printing was performed in the photo print mode of Picty 300 (a color inkjet printer manufactured by NEC), clear, high-quality printing without bleeding or repelling was obtained.

3-2 Examples of Other Papers The same coating agent as in 3-1 was applied to information recording paper, paperboard, cardboard, and plain paper in the same manner as in 3-1. Plain paper was also dipped. When printing was performed in the same manner as in the case of 3-1 described above, good printing results were obtained.

4. Example of nonwoven fabric The coating amount of the coating agent of Example 3 on a polyethylene nonwoven fabric and a polyester nonwoven fabric after drying was 12 g / m2.
And dried at 80 ° C. for 3 minutes. Picty 3
When printing was performed in the photo print mode of 00, good printing results were obtained.

5. Examples of Other Films The coating agent of Example 3 was applied to a soft PVC film, a polycarbonate film, and a polystyrene film so that the coating thickness after drying became 8 μm, and dried at 80 ° C. for 2 minutes. For soft PVC, use one of Pesresin A-124S (modified polyester resin made by Takamatsu Oil & Fats) to prevent bleeding of plasticizer.
The coating agent of Example 3 was applied after μ application.
When printing was performed in the photo print mode of the Picty 300, good print results were obtained. The fixability of the ink was also good.

6. Examples of textile products 100% cotton fabric, 100% cotton knitted fabric, polyester / cotton blend (65/35) fabric, 100% polyester as fabric
A woven fabric, a 100% nylon fabric and a 100% wool fabric were used. For the polyester fabric, SR-1000 (a hydrophilic finishing agent for polyester manufactured by Takamatsu Yushi Co., Ltd.) was used, and for the nylon fabric, a hydrophilic fabric processed with Ranogen KRN-6 (a hydrophilic processing agent for nylon manufactured by Takamatsu Yushi Co., Ltd.) was used. .

Each of the base fabrics was knife-coated with the coating agent of Example 1 so that the applied amount after drying was 15 g / m 2.
After drying at 00 ° C. for 5 minutes, a treated cloth was obtained. Next, each fabric was subjected to ink-jet printing and then subjected to a general dyeing process for each dye and fabric to obtain a dyed product. The obtained dyed product had no bleeding, was excellent in color tone and density, and had good washing resistance.

7. Example of an acceptor layer also serving as an anchor coating agent for back printing The coating agent of Example 1 was applied to a 100 μm transparent polyester film so that the film thickness after drying became 3 μm.
Dry at 0 ° C. for 1 minute. A coating agent for back printing (a mixture of an acrylic resin and porous fine particles) was applied thereon so as to have a thickness of 15 μm after drying, and dried at 120 ° C. for 3 minutes to prepare a film for back printing. Separately, a film was prepared by coating the same polyester film with only the back coat coating agent at 15 μm, and the performance was compared. The film coated with the coating agent of the present invention is more adhesive than the film without the anchor coat,
Excellent in water resistance, printability, and light transmittance.

[0064]

As described above, the coating composition of the present invention has good adhesion to a hydrophobic printing material,
In addition, the printability by ink jet printing is good, and the fixability and water resistance of the ink are good without impairing the transparency of the base material.

Therefore, by applying the coating composition of the present invention to a substrate to be printed, it is possible to perform printing with good ink fixability and water resistance without bleeding by ink jet printing, and therefore, it is extremely useful for manufacturing an ink jet recording sheet. It is a suitable composition.

Claims (3)

[Claims] 1. An aqueous urethane resin (A) and (B) a polyvinyl alcohol having a degree of saponification of 75 to 100% and a degree of polymerization of 500 to 5,000 in a mixed aqueous solution or aqueous dispersion of (C) hydrophilicity. Graft urethane resin (1) obtained by graft polymerization of 100 to 60% by weight of a radical polymerizable vinyl monomer and 0 to 40% by weight of another copolymerizable vinyl monomer, and cationic quaternary ammonium on the side chain (D) A copolymer of 10 to 100% by weight of a radical polymerizable vinyl monomer having a base and 90 to 0% by weight of another copolymerizable vinyl monomer has (E) a saponification degree of 75 to
A coating composition for an ink receiving layer, comprising: a modified cationic polymer (2) obtained by mixing 100% of polyvinyl alcohol having a degree of polymerization of 500 to 5000. 2. The coating composition for an ink receiving layer according to claim 1, wherein the hydrophilic radical polymerizable vinyl monomer has a hydrophilic group represented by the following chemical formulas (a) to (f). Embedded image 3. The solid weight ratio of (A) the aqueous urethane resin, (B) polyvinyl alcohol, and (C) the radically polymerizable vinyl monomer according to claim 1 to (A) 100 parts by weight, (B) ) 10-500 parts by weight (C) 10-50
0 parts by weight, (D) a copolymer of a radically polymerizable vinyl monomer having a cationic quaternary ammonium base in a side chain and another copolymerizable vinyl monomer, and (E) a solid content weight of polyvinyl alcohol The ratio is (E) 5 to 200 parts by weight with respect to (D) 100 parts by weight, and (1) the graft urethane resin and (2) the modified cationic polymer are in a solid content ratio of 50:50 to 95: 5. Claims 1 and 2
The coating composition for an ink receiving layer as described in the above.