JPH1077309A - Photosensitive resin composition and medium to be recorded using cured product thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition excellent in curl resistance, carrying property and water resistance and useful as an ink receiving layer by including an ethylenically unsaturated group-containing compound, etc., as essential components. SOLUTION: This photosensitive resin composition contains (A) an ethylenically unsaturated group-containing compound, preferably a hydrophilic monomer, (B) saccharides, preferably chitosan, especially preferably a salt of the chitosan with an organic acid, having 200-100,000 average molecular weight, in an amount of 1-50wt.% (C) a photopolymerization initiator and (D) a filler as essential components and further preferably contains (E) a polymer containing tertiary nitrogen, especially polydimethyl acrylamide or polyvinylpyrrolidone.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photosensitive resin composition, a cured product and an article. The cured film of the photosensitive resin composition of the present invention is particularly suitable for an ink receiving layer of an inkjet recording medium.

[0002]

2. Description of the Related Art In recent years, ink-jet recording methods include various ink (recording liquid) discharging methods, for example, an electrostatic suction method, a method of applying mechanical vibration or displacement to ink by using a piezoelectric element, and a method of heating ink to foam. In this method, ink droplets are generated and ejected by a method that uses the pressure, etc., and a part or all of them is attached to a recording medium such as paper to perform recording. Application to various facsimile machines and printers is rapidly spreading because of the fact that high-speed recording is possible, full-color printing is easy, hard copy is easily obtained, and color printing can be performed at low cost. As a recording medium suitable for the ink jet recording system, a recording medium coated with a pigment such as silica on a paper surface to form a porous layer, or a resin that absorbs ink by dissolution or swelling of a plastic substrate (for example, polyester, poly Examples thereof include coating or printing applied to a molded product or a film of methyl methacrylate, polycarbonate, or the like), for example, an OHP (overhead projector) film for inkjet, a disk-shaped electronic recording medium, and the like.

By the way, on the surface of the disk-shaped electronic recording medium, an ink absorbing layer made of a hydrophilic resin coated with a hydrophilic ultraviolet-curing or thermosetting resin is provided in order to print its contents by, for example, an ink jet method. is there. In this case, the printing surface is non-porous, and a transparent image can be obtained. However, usually, the absorption layer made of such a hydrophilic resin is often soluble in water, and the image is easily destroyed when the image is exposed to water. In addition, even when the ink absorbing layer itself does not dissolve in water, if the image is immersed in water, the ink absorbing layer swells, and the dye forming the image easily escapes into water, and the image has water resistance. However, there was a drawback that it could not be obtained.

In order to solve such disadvantages, a direct dye or an acidic dye is often used as a dye of an ink for ink-jet printing, and thus a cationic dye fixing agent or the like is contained in an ink receiving layer. Has been proposed (Japanese Patent Laid-Open No. 61-261889). However, the dye fixing agent that can be contained in the water-soluble resin is itself water-soluble, and the portion bonded to the dye becomes insoluble, but the other portions are water-soluble.
It is difficult to obtain water resistance of the film of the ink receiving layer. JP-A-61-10438 discloses an ink-receiving layer obtained by cationically modifying polyvinyl alcohol as a water-soluble polymer (hereinafter referred to as "cationic PVA").
Alternatively, it has been proposed to include a crosslinked product thereof. In this case, simply containing cationic PVA does not provide the water resistance of the ink receiving layer itself, as in the case of the cationic dye fixing agent. On the other hand, when a crosslinked product of cationic PVA is used, the ink receiving layer cannot be used. However, it is necessary to use cationic PVA as the water-soluble resin, although the water resistance of both the image and the image can be obtained. In addition to a narrow range of material selection, it is necessary to increase the proportion of the cationic group in the ink receiving layer. It is difficult to obtain sufficient ink dryness and water resistance in full-color printing or the like where the amount of ink used for recording is large. Further, Japanese Patent Application Laid-Open No. 61-141584 proposes to improve the absorption of ink by adding amorphous silica to a water-soluble resin. In addition, inorganic pigment particles such as porous materials, for example, clay, talc, diatomaceous earth, calcium carbonate, calcium sulfate, barium sulfate, aluminum silicate, synthetic zeolite, alumina, zinc oxide, lithobon, and titanium white have been proposed. (Japanese Patent Application Laid-Open No. 61-22898)
No. 4, JP-B-4-1706, etc.). However, although the ink absorbency is improved, it is still insufficient for full color.

[0005]

DISCLOSURE OF THE INVENTION The present invention relates to an ink which is excellent in curling resistance and transportability, has a high ink absorption speed, is excellent in water resistance, and has a sharp ink dot shape and is excellent in ink coloring. It is intended to develop a photosensitive resin composition suitable for the receiving layer.

[0006]

Means for Solving the Problems The present invention comprises (1) an ethylenically unsaturated group-containing compound (A), a saccharide (B), a photopolymerization initiator (C), and a filler (D) as essential components. A photosensitive resin composition comprising: (2) The photosensitive resin composition according to (1), wherein the ethylenically unsaturated group-containing compound (A) is a hydrophilic monomer. (3) The photosensitive resin composition according to (1), wherein the saccharide (B) is chitosan. (4) The photosensitive resin composition according to (3), wherein the chitosan is a salt with an acid. (5) The photosensitive resin composition according to (4), wherein the acid is an organic acid.

(6) Chitosan having an average molecular weight of 200 to 1
The photosensitive resin composition according to any one of (3) to (5), wherein the composition is 00000. (7) The photosensitive resin composition according to (1), wherein the content of the saccharide (B) is 1 to 50% by weight. (8) The photosensitive resin composition according to any one of (1) to (7), which contains a polymer (E) containing a tertiary nitrogen. (9) The photosensitive resin composition according to (8), wherein the tertiary nitrogen-containing polymer (E) is a homopolymer. (10) The photosensitive resin composition according to (9), wherein the homopolymer is polydimethylacrylamide or polyvinylpyrrolidone. (11) A cured product of the photosensitive resin composition according to any one of (1) to (10). (12) An article having on its surface a thin film of the cured product according to (11). (13) The article according to (12), wherein the thickness of the thin film of the cured product is 1 to 100 μm. (14) The article is a recording medium (12) or (1)
3) The article according to the above. (15) The article according to (14), wherein the recording medium is an inkjet paper or a disc-shaped electronic recording medium. About.

The ethylenically unsaturated group-containing compound (A) used in the present invention includes, for example, a photopolymerizable monomer and a photopolymerizable oligomer. Photopolymerizable monomers are classified into monofunctional monomers, difunctional monomers, and polyfunctional monomers. As the monofunctional monomer, for example, 2-
Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-ethylhexyl (meth)
Acrylate, 2-ethylhexyl polyethoxy (meth) acrylate, carbitol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate,
N, N-dimethylaminoethyl (meth) acrylate,
N, N-diethylaminoethyl (meth) acrylate,
3- (N, N-dimethylamino) propyl (meth) acrylate, 3- (N, N-dimethylamino) propyl (meth) acrylamide, N, N-diethylaminoethyl vinyl ether, 4-vinylpyridine, (meth) acrylamide, N-vinylpyrrolidone, N-vinylcaprolactam, acrylic monophorin, N, N-dimethylamino (meth) acrylate, N, N-dimethyl (meth) acrylamide, N-vinylcaprolactam, dicyclopentenyl (meth) acrylate, dicyclo Pentenyloxyethyl (meth) acrylate, hydrogenated dicyclopentenyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexane-1,4-dimethylol mono (meth) acrylate, o-phenylphenyloxyethyl (meth) acyl Rate, o- phenyl-phenyloxyethyl oxyethyl (meth) acrylate, phenyl (meth) acrylate, tribromophenyl oxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate and the like.

As the bifunctional monomer, for example, 1,6
-Hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, neopentyl glycol polypropoxydi (meth) acrylate, neopentyl glycol di (hydroxypivalate) di (meth) acrylate ) Acrylate, bisphenol A polyethoxydi (meth) acrylate, bisphenol F polyethoxydi (meth)
Acrylate, polyethylene glycol di (meth) acrylate, bis [(meth) acryloyloxyethyl]
Hydroxyethyl isocyanurate;

Examples of the polyfunctional monomer include trimethylolpropane tri (meth) acrylate, trimethyloloctanetri (meth) acrylate, trimethylolpropane polyethoxytri (meth) acrylate,
Trimethylolpropane polyproxy tri (meth) acrylate, tris [(meth) acryloyloxyethyl]
Isocyanurate, pentaerythritol tri (meta)
Acrylate, pentaerythritol polyethoxytetra (meth) acrylate, pentaerythritol polypropoxytetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropanetetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipenta Erythritol hexa (meth) acrylate, caprolactone-modified tris [(meth) acryloyloxyethyl] isocyanurate and the like can be mentioned.

The photopolymerizable oligomer includes, for example, epoxy (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate and the like. Examples of the epoxy (meth) acrylate include a reaction product of an epoxy resin and an unsaturated group-containing compound having one carboxylic acid in a molecule, and a reaction product of this reaction product and polyhydrochloric anhydride. Examples of epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, trisphenol methane type epoxy resin, biphenyl type epoxy resin, aliphatic glycidyl ether, and alicyclic type. Epoxy resins and the like can be mentioned. Examples of the unsaturated group-containing compound having one carboxylic acid in the molecule include (meth) acrylic acid and (meth) acrylic acid.
Acrylic acid dimer and the like can be mentioned. Examples of the polybasic acid in the polybasic anhydride include, for example, maleic acid, succinic acid, adipic acid, phthalic acid, terephthalic acid, isophthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methyl-tetrahydrophthalic acid and the like. Can be

As urethane (meth) acrylate,
For example, polyol (a) ethylene glycol, propylene glycol, diethylene glycol, neopentyl glycol, neopentyl glycol, 1,6-hexanediol, 1,4-butanediol, polytetramethylene glycol, polybutadiene diol, bisphenol A polyethoxydiol, tri Polyol (a) such as methylolpropane, polyol (a) and polybasic acid (for example, maleic acid, succinic acid, adipic acid, phthalic acid, terephthalic acid, isophthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methyl-tetrahydro Phthalic acid or the like, or a polyester polyol (a-1) which is a reaction product with an acid anhydride thereof, a polyol (a) and ε-caprolactone, or a polyol (a) and the above-mentioned polybasic acid or its acid anhydride. Polyols such as polycaprolactone polyol (a-2), polycarbonate polyol (a-3) and organic polyisocyanates (for example, tolylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, Bis (4-isocyanatophenyl) methylene, xylylene diisocyanate, hexamethylene diisocyanate, trimers of hexamethylene diisocyanate, etc.) and hydroxyl group-containing (meth) acrylates (for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (Meth) acrylate, 4
-Hydroxybutyl (meth) acrylate, pentaerythritol (meth) acrylate, dipentaerythritol penta (meth) acrylate, etc.) or the above-mentioned organic polyisocyanate and the above-mentioned hydroxyl-containing (meth) acrylate Urethane acrylate. The polyester polyol (a-1)
(Meth) acrylate unsaturated polyester silicon (meth) acrylate, polybutadiene poly (meth) acrylate and the like.

Examples of the polyester (meth) acrylate include M-6100, M-6200 and M-625.
0, M-6400, M-6500, M-7100, M-
8030, M-8060, M-8100, M-853
0, M-8560, and M-9050 (all manufactured by Toa Gosei Co., Ltd.).

In the present invention, it is preferable to use a hydrophilic monomer as the ethylenically unsaturated group-containing compound (A). Specific examples thereof include acrylmonophorin, N-vinylpyrrolidone, N-vinylcaprolactam, 2-hydroxyethyl (meth) acrylate, 2-
Hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, phenoxyethyl (meth)
Acrylate, (meth) acrylamide, dimethyl (meth) acrylamide, diethylamino (meth) acrylate, dimethylaminopropyl (meth) acrylamide, dimethylaminoethyl (meth) acrylate, dimethylamino (meth) acrylate, N, N-diethylaminoethyl (meth) ) Acrylate, 3- (N, N-dimethylamino) propyl (meth) acrylate, N, N-
Diethylaminoethyl vinyl ether, 4-vinylpyridine, bis [(meth) acryloyloxyethyl] hydroxyethyl isocyanurate, tris [(meth) acryloyloxyethyl] isocyanurate, caprolactone-modified tris [(meth) acryloyloxyethyl]
Isocyanurate, polyethylene glycol di (meth)
Examples thereof include acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane polyethoxytri (meth) acrylate, and pentaerythritol polyethoxytetra (meth) acrylate. These can be used alone or in combination of two or more. Further, these hydrophilic monomers and non-hydrophilic monomers may be used in combination.

In the present invention, by adding and dispersing the saccharide (B) in the resin, the absorptivity, drying property and sticking property of the ink for inkjet to the ink receiving layer can be improved.

The saccharide (B) used in the present invention includes, for example, glucosamine, chitin, chitosan, starch derivatives, cellulose derivatives, alginic acid derivatives, agar, pectin, carrageenan, konjac, gum arabic, pullulan, dextran, glucose derivatives and the like. And salts thereof. Preferred are chitosan or chitosan hydrochloride, acetate, formate, lactate, malate, adipate and the like, and more preferred is chitosan lactate.

The molecular weight of these saccharides is preferably 20
0 to 100,000, particularly preferably 200 to 50.
000. If the molecular weight is too large, it is difficult to disperse, and the viscosity of the photosensitive resin composition is high, and the coatability is difficult. When chitosan is used, its molecular weight is 200-5.
A low molecular weight of 0000, preferably 5000 to 40000, more preferably 5000 to 30000 is preferred.

The content of the saccharide is preferably 1 to 50% by weight, preferably 10 to 3% by weight, based on the total amount of the photosensitive resin composition.
0% by weight, particularly preferably 20 to 30% by weight. By providing a cured product film of a photosensitive resin composition containing a saccharide in such a range, writing with an inkjet ink containing a water-soluble dye is possible, the printing drying speed is high, and the ink dye to be further used. Is fixed by an intermolecular force, so that a recording medium having higher water resistance of printing can be obtained. If the content is too large, the cured product film of the photosensitive resin composition tends to swell and become brittle, and the durability tends to decrease. Further, the viscosity of the coating film becomes too high, and uniform coating becomes difficult. If too little,
Writing with an ink containing a water-soluble dye becomes difficult, the drying speed of the print decreases, and the water resistance of the print deteriorates.

A filler (D) is added to the photosensitive resin composition of the present invention. Porous particles conventionally used as the filler (D), for example, silica, clay, talc,
Diatomaceous earth, calcium carbonate, calcium sulfate, barium sulfate, aluminum silicate, synthetic zeolites, smectites, montmorillonite group minerals, alumina, etc., and inorganic pigment particles such as zinc oxide, titanium white, etc. may also be used in combination.

Further, for the recording medium of the present invention, a polymer (E) containing at least tertiary nitrogen can be used. The tertiary nitrogen-containing polymer (E) may be a homopolymer of the tertiary nitrogen-containing monofunctional monomer (a), and the monomer (a) and the hydrophilic monomer (b) and / or Although a copolymer with the hydrophilic monomer (c) may be used, a homopolymer of the tertiary nitrogen-containing monofunctional monomer (a) or a copolymer of the monomer (a) and the hydrophilic monomer (b) is preferable, and more preferably. It is a homopolymer of a monofunctional monomer (a) containing a tertiary nitrogen.

Monofunctional monomer containing tertiary nitrogen (a)
Are, for example, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, 3- (N, N-dimethylamino) propyl (meth) acrylate, 3- (N , N-dimethylamino) propyl (meth) acrylamide, N,
Examples include N-diethylaminoethyl vinyl ether, 4-vinylpyridine, N-vinylpyrrolidone, N-vinylcaprolactam, acrylmonophorin, N, N-dimethylamino (meth) acrylate, N, N-dimethyl (meth) acrylamide and the like. (Meth) acrylamide-based monomers are preferred from the viewpoint of stability and the like, and these can be used alone or in combination of two or more.

As the hydrophilic monomer (b), for example, 2
-Hydroxy (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, (meth) acrylamide, methylamino (meth) acrylamide and the like. These may be used alone or in combination of two or more. As the non-hydrophilic monomer (c), for example, methyl (meth)
Examples include acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) acrylic acid, styrene, p-methylstyrene, and the like.

The mixing ratio of the components (a), (b) and (c) is such that the component (a) is 20 to 100% by weight, preferably 25 to 100% by weight, and the component (b) is 0 to 60% by weight. %,
It is preferable that the content is preferably 0 to 50% by weight, and the component (c) is 0 to 50% by weight, preferably 0 to 40% by weight.

These components (a), (b) and (c) can be synthesized by using a conventionally known solution polymerization method. For example, the components (a), (b) and (c) are prepared by using a polymerization initiator (eg, azobisisobutylnitrile) in a solvent (eg, a suitable organic solvent such as isopropyl alcohol, methyl cellosolve, methyl ethyl ketone, dioxane). It can be obtained by reacting at a reaction temperature of 60 to 100 ° C. in a nitrogen gas stream.

In the photosensitive resin composition of the present invention, as a hydrophilic polymer other than the tertiary nitrogen-containing polymer (E), polyethylene glycol having a molecular weight of 1,000 to 50,000 can be used.

Specific examples of the photopolymerization initiator (C) used in the present invention may be any known photopolymerization initiator, for example, 2-hydroxy-2-methylpropiophenone, -Isopropyl-2-hydroxy-2-methylpropiophenone, benzyldimethyl ketal, 1
-Hydroxycyclohexylphenyl ketone, benzophenone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1,2,4,6-trimethylbenzoylphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) ) -2,4,4-trimethylpentylphosphinoxide and the like. These photopolymerization initiators can be used in combination with a polymerization initiation auxiliary such as tertiary amines.

The proportion of each component of the photosensitive resin composition of the present invention is such that the content of the ethylenically unsaturated group-containing compound (A) is 5 to 60% by weight, preferably 20 to 60% by weight.
Particularly preferably, 30 to 60% by weight, the saccharide (B) component is
1 to 50% by weight, preferably 10 to 30% by weight, particularly preferably 20 to 30% by weight, and the photopolymerization initiator (C) component is 0.01 to 10% by weight, preferably 1 to 5% by weight;
Particularly preferably 2 to 5% by weight, and the filler (D) is 1 to 6% by weight.
0% by weight, preferably 1 to 30% by weight, particularly preferably 1 to 20% by weight, and the polymer (E) component is 0 to 50% by weight, preferably 0 to 40% by weight, particularly preferably 0 to 3% by weight.
0% by weight.

If necessary, additives such as an antioxidant, an antifoaming agent, a leveling agent, a light stabilizer and a polymerization inhibitor may be added to the photosensitive resin composition of the present invention. it can. As an antioxidant, for example, BHT Suwanox (manufactured by Seiko Chemical), and as an antifoaming agent, for example, KS-
603 (manufactured by Shin-Etsu Chemical Co., Ltd.)
For example, SH-29PA (Toray Dow Silicone)
LA-82 (manufactured by Asahi Denka Kogyo) as a light stabilizer, and Q-1301 as a polymerization inhibitor, for example.
(Manufactured by Wako Pure Chemical Industries).

The photosensitive resin composition of the present invention comprises, for example, the components (A) and (C), and if necessary, the component (E) in an amount of 30 to 80.
Mix under heating at about ° C, and further add the components (B) and (D),
Further, if necessary, for example, it can be obtained by adding additives such as an antioxidant, an antifoaming agent, a leveling agent, a light stabilizer, a polymerization inhibitor and the like, and mixing them uniformly.

The cured product of the present invention can be obtained by irradiating the above-mentioned photosensitive resin composition with energy rays such as ultraviolet rays and visible rays. Examples of the light source include a metahalide lamp and a high-pressure mercury lamp.

The article of the present invention has a thin film of a cured product of the above photosensitive resin composition on the surface. Examples of the article include a recording medium. Examples of the recording medium include inkjet paper such as inkjet paper and OHP sheets, CD-R (write-once compact disc),
Disc-shaped electronic recording media such as VD (Digital Video Disc) can be used. This article was prepared by coating the photosensitive resin composition of the present invention as an ink receiving layer on a substrate of the article with a film thickness of 1.
１００100 μm, applied by a method such as a screen printing method or a bar coder method, and cured by irradiating energy rays such as ultraviolet rays to form an ink receiving layer comprising a thin film of a cured product of the photosensitive resin composition of the present invention. Can be obtained. As the base material of the article, for example, paper, sheet-like or plate-like plastic (material is, for example, polyester, polymethyl methacrylate, polycarbonate, etc.)
Is raised. The paper, sheet-like or plate-like plastic may have a surface on which the ink receiving layer is formed, which is treated with a primer or an overcoat agent.

[0032]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the scope of the Examples. In the following description, “parts” and “%” indicate “parts by weight” and “% by weight”, respectively, unless otherwise specified.

Synthesis Example 1 3- (N, N-dimethylamino) propyl methacrylamide 16 parts, dimethylaminoethyl acrylate 1
After charging 6 parts of 2-hydroxyethyl methacrylate, 16 parts of 2-hydroxyethyl methacrylate, 0.3 part of azobisisobutylnitrile, and 200 parts of methyl cellosolve, passing nitrogen gas for 1 hour, the mixture was heated and stirred at 70 ° C. for 5 hours to perform a polymerization reaction. Was.
After the completion of the reaction, the reaction mixture was poured into a large amount of cyclohexane to precipitate a product. Next, cyclohexane containing the reaction solvent was removed by decantation, and the reaction product was dried under reduced pressure to obtain 40 parts of a polymer (E1).

Synthesis Example 2 N, N-dimethylacrylamide 26 parts, 2-hydroxyethyl methacrylate 10 parts, methyl acrylate 12 parts, azobisisobutylnitrile 0.2 part,
And 200 parts of methyl cellosolve, nitrogen gas was passed for 1 hour, and the mixture was heated and stirred at 70 ° C. for 4 hours to carry out a polymerization reaction. After the completion of the reaction, the reaction mixture was poured into a large amount of cyclohexane to precipitate a product. Next, cyclohexane containing the reaction solvent was removed by decantation,
The reaction product was dried under reduced pressure to obtain polymer (E2) 44
Got a part.

Synthesis Example 3 50 parts of N, N-dimethylacrylamide, 0.3 part of azobisisobutylnitrile, and 200 parts of methyl cellosolve were charged, and nitrogen gas was passed for 1 hour.
The mixture was heated and stirred at 6 ° C. for 6 hours to carry out a polymerization reaction. After the completion of the reaction, the reaction mixture was poured into a large amount of cyclohexane to precipitate a product. Next, cyclohexane containing the reaction solvent was removed by decantation, and the reaction product was dried under reduced pressure to obtain 46 parts of a polymer (E3).

Examples 1 to 5 and Comparative Examples 1 to 3 A photosensitive resin composition was prepared according to Table 1 and had a thickness of 100 μm.
m on a polyethylene terephthalate film having a thickness of 5 to 12 μm after curing by a bar coater method, and irradiating ultraviolet rays to cure the coating to form a recording medium. Various evaluations (ink drying time, water resistance, durability, and curl properties) were performed using the ink.

The composition of the used ink is as follows. Yellow ink: CI Direct Yellow 86 2 parts, diethylene glycol 20 parts, polyethylene glycol # 200 10 parts, water 70 parts Red ink: CI Acid Red 35 2 parts, diethylene glycol 20 parts, polyethylene glycol # 200
10 parts, water 70 parts Blue ink: CI Direct Blue 86 2 parts, diethylene glycol 20 parts, polyethylene glycol # 20
0 10 parts, water 70 parts Black ink: CI Food Black 2 2 parts, diethylene glycol 20 parts, polyethylene glycol # 200
10 parts, water 70 parts

Evaluation method 1) Ink drying property The recording medium printed by the ink jet recording method was left at room temperature (20 ° C., 65% RH), and when the finger touched the printed image, the ink dried and adhered to the finger. The time was measured until it disappeared, and it was determined in the following manner.・ ・ ・: Time required for the ink to dry and no longer adhere to the finger is within 30 seconds. Δ: Time from drying for 30 seconds to 1 minute until ink does not adhere to the finger. ×: 1 minute or more until drying and the ink no longer adheres to the finger.

2) Water Resistance The recording medium printed by the ink jet recording method was left standing in water for 24 hours, and the appearance was observed.・ ・ ・: There is no change in the printed image. Δ: Slight bleeding and fading occurred in the printed image. X: The printed image almost disappeared, and the coating film was ragged.

3) Durability The recording medium printed by the ink jet recording method is 80
After standing at 500 ° C. and 80% RH for 500 hours, the appearance was observed.・ ・ ・: There is no change in the printed image. Δ: Slight bleeding and fading occurred in the printed image. X: The printed image almost disappeared.

4) Conveyability When the recording medium is printed by a printer under the conditions of 35 ° C. and 85% RH, those which adhere to the feed roller of the printer and cannot be conveyed due to stickiness of the surface of the ink receiving layer. "X", "Slightly sticky" on the surface of the ink receiving layer due to slight stickiness, "△";

5) Curling Property The curling state of the recording medium thus prepared was observed.・ ・ ・: There is no curl at all. Δ: Very slightly curled. X: Large curl.

[0043]

Table 1 Example 1 Comparative Example 1 2 3 4 5 1 2 3 (A) Component Acryloylmorpholine 17.9 Component N, N-dimethylacrylamide 40 N, N-dimethylaminopropyl 35.3 8.9 81.4 Acrylamide 2-hydroxyethyl Acry 25.2 28.2 32.2 Rate Bis (acryloyloxy) 10.1 11.3 12.9 6.7 17.6 17.9 81.4 Hydroxyethyl isocyanurate (B) Chitosan lactate 22.7 28.9 13.3 11.8 Component Glucosamine sulfate 25.4 (C) 1-Hydroxycyclohexyl 2.6 2.8 3.2 3.3 2.9 6.3 4.1 4.1 Component Phenyl ketone (D) Silica 2.8 9.6 3.5 16.7 14.7 4.5 2.9 2.9 Component Calcium carbonate 16.6 (E) Polymer obtained in Synthesis example 1 44.6 11.6 Component Polymer obtained in Synthesis example 2 17.6 11.6 Obtained in Synthesis example 3 Polymer 20.2 22.6 20 Polyvinylpyrrolidone 19.3 ─────────────────────────────────イ ン ク Ink drying property ○ △ ○ △ △ △ × △ Water resistance ○ ○ ○ △ △ △ × × Durability ○ ○ ○ △ △ △ × × Transportability ○ ○ ○ ○ ○ △ ○ × Curling ○ ○ ○ ○ ○ ○ × ○

Polyvinylpyrrolidone used in Table 1 above was Rubiscol K-30 manufactured by BASF, and chitosan lactate was Koyo Chitosan SK-2 manufactured by Koyo Chemical Co., Ltd.
Glucosamine sulfate is a glucosamine sulfate manufactured by Koyo Chemical Co., Ltd., and silica is Aerosil R manufactured by Nippon Aerosil Co., Ltd.
-812, calcium carbonate is Shiraishi Kana CC manufactured by Shiraishi Industry Co., Ltd. The numerical values in Table 1 are all by weight.

As is clear from the evaluation results in Table 1, the cured film of the photosensitive resin composition of the present invention is excellent in the drying property, water resistance, durability, transportability and curling properties of the ink.
It is considered that the drying property of this ink is due to the high water absorbing ability of the cured film. Due to this high water absorption capacity and water resistance, the cured film of the photosensitive resin composition of the present invention has antifogging property, antistatic property and antislip property.

[0046]

According to the photosensitive resin composition of the present invention, when the obtained cured product is used for an ink receiving layer of a recording medium of an ink jet recording system, the drying property, water resistance, durability and transportability of the ink are obtained. It has excellent curl properties and is effective as an ink receiving layer of an inkjet recording type recording medium.
Further, since the cured film of the photosensitive resin composition has anti-fogging property, anti-static property and anti-slip property, it imparts anti-fogging property to glass and film, imparts anti-static property to electronic recording medium, It can be used for imparting anti-slip properties to seats and various grips (for example, golf clubs, bats, automobile handles, various tools, etc.).

Claims (15)

[Claims] 1. A photosensitive resin composition comprising, as essential components, an ethylenically unsaturated group-containing compound (A), a saccharide (B), a photopolymerization initiator (C), and a filler (D). Stuff. 2. The photosensitive resin composition according to claim 1, wherein the ethylenically unsaturated group-containing compound (A) is a hydrophilic monomer. 3. The photosensitive resin composition according to claim 1, wherein the saccharide (B) is chitosan. 4. The photosensitive resin composition according to claim 3, wherein the chitosan is a salt with an acid. 5. The photosensitive resin composition according to claim 4, wherein the acid is an organic acid. 6. The chitosan has an average molecular weight of 200 to 1000.
The photosensitive resin composition according to any one of claims 3 to 5, which is 00. 7. The photosensitive resin composition according to claim 1, wherein the content of the saccharide (B) is 1 to 50% by weight. 8. The photosensitive resin composition according to claim 1, comprising a polymer (E) containing a tertiary nitrogen. 9. The photosensitive resin composition according to claim 8, wherein the tertiary nitrogen-containing polymer (E) is a homopolymer. 10. The photosensitive resin composition according to claim 9, wherein the homopolymer is polydimethylacrylamide or polyvinylpyrrolidone. 11. A cured product of the photosensitive resin composition according to claim 1. 12. An article having a thin film of the cured product according to claim 11 on the surface. 13. The article according to claim 12, wherein the thin film of the cured product has a thickness of 1 to 100 μm. 14. The article according to claim 12, wherein the article is a recording medium. 15. The article according to claim 14, wherein the recording medium is an inkjet paper or a disc-shaped electronic recording medium.