JPH06256441A - Resin composition and its cured product - Google Patents

Abstract

PURPOSE:To obtain a resin composition excellent in scumming resistance, gloss and curability by using a specified unsaturation-containing polycarboxylic acid resin or a specified unsaturation-containing polycarboxylic acid urethane resin as the component. CONSTITUTION:This resin composition comprises an unsaturation-containing polycarboxylic acid resin which is a reaction product among an epoxy compound having at least two epoxy groups in the molecule, a compound having at least two hydroxyl groups and at least one epoxy-reactive group other than hydroxyl and an unsatpration-containing monocarboxylic acid with a polybasic acid anhydride and a photopolymerization initiator as an optional component. This composition can be cured by applying it to a substrate such as paper, plastic plate, film or wood by e.g. lithography and irradiating it with ultraviolet rays or electron rays.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition suitable for dry lithographic printing ink, which can be cured by ultraviolet rays or electron beams, and a cured product thereof.

[0002]

2. Description of the Related Art At present, as a general printing method, there are letterpress printing, lithographic printing, intaglio printing, etc. Among lithographic printing, in wet offset printing, the printing plate surface consists of a hydrophilic part and a lipophilic part, Is a method in which an image is obtained by transferring only to the lipophilic part. With this printing method, the image is clear, high-quality printed matter can be obtained, the plate making price is low,
The feature is that plate making can be done in a short time. But,
In the printing method according to this method, dampening water is used together with the ink at the time of printing. Therefore, it is necessary to control the dampening water as well as the control of the ink, and the printing work requires a high technique. For this reason, recently, a printing method has been proposed in which lithographic offset printing can be performed without using dampening water. That is, it is a dry lithographic printing method, and printing by this method improves the adverse effects of dampening water, which have been a problem during conventional wet offset printing, such as emulsification of printing ink and transfer failure due to water loss. However, when printing is continued for a long time by this dry lithographic printing method using a normal ink, the temperature on the plate surface rises, and the ink is likely to adhere to the non-image area and stain.

As means for solving this, means for modifying various ink materials with a silicon compound have been proposed. For example, silicone modified alkyd resin (Japanese Patent Publication No. 51
-10124, JP-B-51-22405), silicon-modified phenolic resin (JP-A-52-10)
042, JP-A-52-62506), silicon-modified drying oil (JP-B-52-10041, JP-B-52-10042) Silicon-modified cyclopentadiene resin (JP-A-56-11024) , JP-A-56-110706) Oil-based ink using a solvent of a low aromatic olefin component (JP-A-56-82861).
Issue gazette) etc. Further, the ultraviolet curing ink has the same problem, and therefore, some attempts have been made to improve it. For example,
JP-A-58-13 using silicon oil as an essential component
There is a method proposed in Japanese Patent No. 4165 or the like.

Although these have some effects on stains, they do not have sufficient stain resistance or the background stain resistance is improved, but on the other hand, the gloss of the printed matter deteriorates and the quality of the printed matter deteriorates. There are drawbacks such as doing. On the other hand, the siloxane compound is extremely expensive as compared with a general ink material, and thus has a drawback that the price of the ink also rises.

[0005]

Generally, oily ink takes a long time to dry, and when it is heated and dried, the apparatus becomes large-scale and the energy cost becomes high. UV curable inks have the function of solving these problems, but the UV curable inks that have been developed so far have insufficient resistance to smearing and gloss, as mentioned above. Due to problems, a UV-curable dry lithographic printing ink that is resistant to scumming, has excellent gloss, is inexpensive, and has excellent storage stability is desired.

[0006]

DISCLOSURE OF THE INVENTION As a result of intensive studies to solve the above problems, the present inventors have found that a novel unsaturated group-containing polycarboxylic acid resin (A) or unsaturated group-containing polycarboxylic acid is used. By developing an acid urethane resin (A ') and using it, it is possible to provide a resin composition which is resistant to scumming and is excellent in gloss and curability, which is particularly suitable for dry lithographic printing ink, and a cured product thereof. did.

That is, the present invention includes (1) an epoxy compound (a) having at least two or more epoxy groups in one molecule, and at least two or more hydroxyl groups in one molecule and a hydroxyl group which reacts with an epoxy group. An unsaturated group-containing polycarboxylic acid which is a reaction product of a compound (b) having one reactive group with an unsaturated group-containing monocarboxylic acid (c) (a) and a polybasic acid anhydride (b) Resin (A)
And a photopolymerization initiator (B) as an optional component, and a cured product thereof.

(2) An epoxy compound (a) having at least two or more epoxy groups in one molecule, at least two or more hydroxyl groups in one molecule, and one reactive group other than the hydroxyl group which reacts with the epoxy group. An unsaturated group which is a reaction product of the compound (b) with the unsaturated group-containing monocarboxylic acid (c) (a), a polybasic acid anhydride (b) and an unsaturated group-containing monoisocyanate (c). The present invention relates to a resin composition containing a polycarboxylic acid urethane resin (A ′) and a photopolymerization initiator (B) as an optional component, and a cured product thereof.

The unsaturated group-containing polycarboxylic acid resin (A) used in the present invention comprises an epoxy compound (a) having at least two epoxy groups in one molecule and at least two hydroxyl groups in one molecule. And a reaction product (a) obtained by reacting a compound (b) having one reactive group other than a hydroxyl group that reacts with an epoxy group with an unsaturated group-containing monocarboxylic acid (c) and a polybasic acid anhydride ( ). Specific examples of the epoxy compound (a) having at least two epoxy groups in one molecule include, for example, novolac type epoxy resins (for example, phenols such as phenol, cresol, halogenated phenol and alkylphenol, and formaldehyde). Those obtained by reacting novolaks obtained by reacting under an acidic catalyst with epichlorohydrin and / or methylepichlorohydrin, etc., and commercially available products thereof include Nippon Kayaku Co., Ltd., EOCN-103, and EOCN-
104S, EOCN-1020, EOCN-1027,
EPPN-201, BREN-S; DEN-431, DEN-439 manufactured by Dow Chemical Co., N-730, N-770, N-86 manufactured by Dainippon Ink and Chemicals, Inc.
5, N-665, N-673, VH-4150 and the like. ) Bisphenol type epoxy resins (for example, those obtained by reacting bisphenols such as bisphenol A, bisphenol F, bisphenol S, and tetrabromobisphenol A with epichlorohydrin and / or methyl epichlorohydrin, bisphenol A
And the like obtained by reacting a condensate of the above-mentioned diglycidyl ether with bisphenol with epichlorohydrin and / or methylepichlorohydrin. These commercially available products are manufactured by Yuka Shell Co., Ltd., Epicoat 1004, Epicoat 1002; Dow Chemical Company, DER-33
0, DER-337, etc. ) Trisphenol methane type epoxy resin (for example, trisphenol methane,
Triscresol methane, etc. and epichlorohydrin and /
Alternatively, those obtained by reacting with methylepiclohydrin, such as those commercially available from Nippon Kayaku Co., Ltd., E
There are PPN-501, EPPN-502 and the like. ), Tris (2,3-epoxypropyl) isocyanate, biphenyldiglycidyl ether, and others, Daicel Chemical Industry Co., Ltd., Celoxide 2021; Mitsui Petrochemical Industry Co., Ltd., Epomic VG-3101: oil-based shell epoxy ( Manufactured by E-1031S; Mitsubishi Gas Chemical Co., Inc.
TETRAD-X, TETRAD-C; Nippon Soda Co., Ltd., EPB-13, EPB-27, etc., alicyclic, amino group-containing, or other epoxy resin having a special structure. . Particularly preferred are, for example, cresol novolac type epoxy resin,
Examples thereof include phenol novolac type epoxy resin.

Next, specific examples of the compound (b) having at least two or more hydroxyl groups and one reactive group other than the hydroxyl group which reacts with the epoxy group in one molecule are as follows:
Examples thereof include polyhydroxy-containing monocarboxylic acids such as dimethylolpropionic acid, dimethylolacetic acid, dimethylolbutyric acid, dimethylolvaleric acid, and dimethylolcaproic acid, and dialkanolamines such as diethanolamine and diisopropanolamine. Particularly preferable examples include dimethylolpropionic acid and the like.

Specific examples of the unsaturated group-containing monocarboxylic acid (c) are, for example, acrylic acid, acrylic acid dimer, methacrylic acid, β-styrylacrylic acid, β-furfurylacrylic acid. , Crotonic acid, α-cyanocinnamic acid, cinnamic acid, saturated or unsaturated dibasic acid anhydrides and 1
Half-esters, which are reaction products with (meth) acrylates having one hydroxyl group in the molecule (specifically, succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, Methylhexahydrophthalic anhydride, Methyltetrahydrophthalic anhydride,
Saturated and unsaturated dibasic acid anhydrides such as itaconic anhydride and methylendomethylene tetrahydrophthalic anhydride, and hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) 1 in 1 molecule of acrylate, glycerin di (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, phenylglycidyl ether (meth) acrylate Of half-esters obtained by reacting (meth) acrylates having a hydroxyl group in an equimolar amount), and half-esters which are reaction products of saturated or unsaturated dibasic acids and unsaturated group-containing monoglycidyl compounds , (Specifically, succinic acid, maleic acid, adipic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, itaconic acid, saturated or unsaturated dibasic acid with glycidyl (meth) acrylates such as fumaric acid,

[0012]

[Chemical 1]

[0013]

[Chemical 2]

[0014]

[Chemical 3]

[0015]

[Chemical 4]

Half ester etc. obtained by reacting an unsaturated group-containing monoglycidyl compound such as the above at an equimolar ratio can be used alone or in combination. Particularly preferred is
Acrylic acid and the like.

The reaction between the epoxy compound (a), the compound (b) and the unsaturated group-containing monocarboxylic acid (c) is carried out by the epoxy compound (a) and the compound (b) (or unsaturated group-containing Reacting the monocarboxylic acid (c), then
The first method in which the unsaturated group-containing monocarboxylic acid (c) (or the compound (b) is reacted, and the epoxy compound (a), the compound (b), and the unsaturated group-containing monocarboxylic acid (c) are simultaneously reacted. The second method is preferable, but the second method is preferable, in the reaction between the epoxy compound (a), the compound (b) and the unsaturated group-containing monocarboxylic acid (c), The total amount of the compound (b) and the unsaturated group-containing monocarboxylic acid (c) is about 0.8 to 1.5 with respect to 1 equivalent of the epoxy group of the epoxy compound (a).
The reaction is preferably carried out in a molar ratio, and particularly preferably in a ratio of about 0.9 to 1.1 mol. The proportions of the compound (b) and the unsaturated group-containing monocarboxylic acid (c) used are the same as those of the compound (b) and the unsaturated group-containing monocarboxylic acid (c).
The amount of compound (b) used is 0.0 mol per 1 mol of the total amount of
5 to 0.5 mol is preferable, and 0.1 to 0.5 is particularly preferable.
It is 0.3 mol.

During the reaction, as a diluent, ketones such as ethyl methyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene, glycol ethers such as dipropylene glycol dimethyl ether and dipropylene glycol diethyl ether. , Esters such as ethyl acetate, butyl acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, aliphatic hydrocarbons such as octane and decane, petroleum ethers such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha Organic solvents such as solvents, carbitol (meth) acrylate, phenoxyethyl (meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate Tris (hydroxyethyl) isocyanurate tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, to use reactive monomers etc. Preferred. Further, a catalyst for promoting the reaction (eg, triethylamine, benzyldimethylamine, methyltriethylammonium chloride, benzyltrimethylammonium bromide,
Benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, chromium octanoate, zirconium octanoate, etc.) is preferably used, and the amount of the catalyst is preferably 0.1 to the reaction raw material mixture. It is 10% by weight. In order to prevent polymerization during the reaction, it is preferable to use a polymerization inhibitor (for example, hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol, etc.), and the amount thereof is, relative to the reaction raw material mixture,
It is preferably 0.01 to 1% by weight. The reaction temperature is preferably 60 to 150 ° C. The reaction time is preferably 5 to 60 hours. In this way, the reaction product (a)
Can be obtained.

Next, the reaction product (a) and the polybasic acid anhydride (b) (for example, maleic anhydride, succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride). Acid, methylendomethylenetetrahydrophthalic anhydride, trimellitic acid, pyromellitic acid, etc. are particularly preferable, and tetrahydrophthalic anhydride, succinic anhydride, etc. are particularly preferable. It is preferable that the polybasic acid anhydride (b) is reacted in an amount of 0.05 to 0.9 equivalent per equivalent of the hydroxyl group with respect to the hydroxyl group in the reaction product (a). The reaction temperature is preferably 60 to 150 ° C. The reaction time is preferably 1 to 10 hours.

The unsaturated group-containing polycarboxylic acid urethane resin (A ') used in the present invention comprises the reaction product (a), the polybasic acid anhydride (b) and the unsaturated group-containing monoisocyanate (c). It can be obtained by reacting.
Specific examples of the unsaturated group-containing monoisocyanate (C) include, for example,

[0021]

[Chemical 5]

[0022]

[Chemical 6]

Reacting an organic diisocyanate (for example, tolylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, etc.) with the above-mentioned (meth) acrylates having one hydroxyl group in one molecule in an approximately equimolar amount. And the like. The reaction of the reaction product (a), the polybasic acid anhydride (b) and the unsaturated group-containing monoisocyanate (c) is carried out by reacting the reaction product (a) with the polybasic acid anhydride (b), It is preferable to react the unsaturated group-containing monoisocyanate (c). The reaction of the reaction product (a) and the polybasic acid anhydride (b) can be carried out by carrying out as described above. Then
With respect to the hydroxyl group in the unsaturated group-containing polycarboxylic acid resin (A) which is a reaction product of the reaction product (a) and the polybasic acid anhydride (b), the unsaturated group-containing monoisocyanate ( C) is preferably reacted in an amount of 0.05 to 0.5 equivalent. The reaction temperature is preferably 60 to 100 ° C. During the reaction, it is preferable to add a small amount of a catalyst (eg, dibutyltin laurate), and the reaction time is preferably 5 to 15 hours.

The acid value (mg / KOH / g) of the unsaturated group-containing polycarboxylic acid resin (A) or unsaturated group-containing urethane resin (A ') thus obtained is 20 to 15
0 is preferred.

The amount of the unsaturated group-containing polycarboxylic acid resin (A) or unsaturated group-containing polycarboxylic acid urethane resin (A ') contained in the composition of the present invention is preferably 10 to 80% by weight in the composition. Particularly preferably 15 to 60% by weight.

Next, in the present invention, a photopolymerization initiator (B) is used as an optional component. Specific examples of the photopolymerization initiator (B) include benzoins such as benzoin benzoin methyl ether and benzoin isopropyl ether, acetophenone, 2,2-dimethoxy-2-phenylacetophenone and 2,2-diethoxy-2-. Phenylacetophenone, 1,1-dichloroacetophenone, 1
-Hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, acetophenones such as N, N-dimethylaminoacetophenone, 2-methylanthraquinone, 2- Ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-
Anthraquinones such as amylanthraquinone and 2-aminoanthraquinone, 2,4-dimethylthioxanthone,
2,4-Diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone and other thioxanthones, acetophenone dimethyl ketal, benzyl dimethyl ketal and other ketals, benzophenone, methylbenzophenone, 4,4′-dichlorobenzophenone, 4, Benzophenones such as 4'-bisdiethylaminobenzophenone, Michler's ketone, 4-benzoyl-4'-methyldiphenyl sulfide, 2,4
There are 6-trimethylbenzoyldiphenylphosphine oxide and the like, which can be used alone or in combination of two or more kinds. Further, it may be used together with a photopolymerization initiator such as tertiary amines such as N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine and triethanolamine. These photosensitizers can be used alone or in combination of two or more kinds.

The preferred combination is 2-methyl-1- [4
-(Methylthio) phenyl] -2-morpholinopropan-1-one (Ciba Geigy Co., Irgacure 907) and 2,4-diethylthioxanthone (Nippon Kayaku Co., Ltd., Kayacure DETX) and 2-isopropyl Combination with thioxanthone, 4-benzoyl-4'-methyldiphenyl sulfide and the like. The proportion of the photopolymerization initiator (B) used is 0 to 20% by weight in the composition of the present invention.
Is preferred. The resin composition of the present invention comprises (A) and (B)
In addition to the components, polyurethane (meth) acrylate,
Oligomers such as polyester (meth) acrylate,
Additives such as colorants (eg, color pigments such as yellow, red, indigo, blue, white, etc.), inorganic fillers, defoaming agents, leveling agents and the like can be added.

The composition of the present invention can be obtained by a method in which the above-mentioned components are blended, dissolved and kneaded.

The cured product of the resin composition of the present invention is applied to a paper, a plastic plate, a film, a tree or the like by a conventional method such as lithographic printing, and then cured by irradiating an ultraviolet ray or an electron beam by a conventional method. It can be done.

When the photopolymerization initiator (B) is used,
It can be cured by irradiation with ultraviolet rays.
As a light source for generating such ultraviolet rays, a carbon arc lamp,
A mercury vapor lamp, an ultraviolet fluorescent lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a tungsten lamp, an incandescent lamp, a xenon lamp, an argon glow lamp, etc. can be used.

The resin composition of the present invention is particularly suitable for dry lithographic printing inks, but is also useful for paints, coatings, adhesives and the like.

[0032]

EXAMPLES The present invention will be specifically described below with reference to examples. The parts in the synthesis examples are parts by weight. Synthesis example of unsaturated group-containing polycarboxylic acid resin (A) Synthesis example 1 Bisphenol A type epoxy resin (Yukaka Shell Co., Ltd.)
Made, Epicoat 1001, epoxy equivalent 450) 450
0 part, dimethylolpropionic acid 134 parts, acrylic acid 649 parts, methylhydroquinone 8.1 parts, triphenylphosphine 24.3 parts, and trimethylolpropane triacrylate 3416.6 parts and butyl carbitol acetate as diluents. Prepare 932.3 parts 1
The reaction was carried out at 00 ° C for about 32 hours, and then succinic anhydride 30
0 part was charged and reacted at 95 ° C. for about 6 hours to obtain an unsaturated group-containing polycarboxylic acid resin (A-10-1) having a solid content acid value (excluding diluent) of 30 mg / KOH / g. .

Synthetic Example 2 Phenol / novolak type epoxy resin (Eikato Shell Co., Ltd., Epicoat 154, epoxy equivalent 180) 1
800 parts, dimethylolpropionic acid 402 parts, acrylic acid 504.4 parts, methylhydroquinone 5.4 parts, triphenylphosphine 16.2 parts, and as a diluent, neopentyl glycol diacrylate hydroxypivalate 4975 parts and a solvent. Charge 481 parts of naphtha and react at 100 ° C. for about 32 hours, then charge 304 parts of tetrahydrophthalic anhydride and react at 95 ° C. for about 6 hours to give an acid value (excluding diluent) of solid form 37
mgKOH / g unsaturated group-containing polycarboxylic acid resin (A-30
-2) was obtained.

Synthesis Example 3 Cresol / Novolak type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., EOCN-103, epoxy equivalent 200) 2
000 parts, 268 parts of dimethylolpropionic acid, 576.5 parts of acrylic acid, 7.1 parts of methylhydroquinone, 35.6 parts of triphenylstibine and 4042 parts of ditrimethylolpropane tetraacrylate as a diluent.
Charge 288.7 parts of solvent naphtha and react at 100 ° C. for about 40 hours, then charge 456 parts of tetrahydrophthalic anhydride and react at 95 ° C. for about 6 hours to obtain an acid value (excluding diluent) of the solid form. 50 mg KOH / g of unsaturated group-containing polycarboxylic acid resin (A-20-3) was obtained.

Synthetic Example of Polyuronic Acid Urethane Resin (A ') Containing Unsaturated Group Synthetic Example 4 Cresol / Novolak type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., EOCN-103, epoxy equivalent 200) 2
2,000 parts, dimethylolpropionic acid 268 parts, methacrylic acid 344.2 parts, acrylic acid 288 parts, methylhydroquinone 5.8 parts, triphenylphosphine 17.
Charge 4 parts and, as a diluent, 923.4 parts of tricyclodecane dimethylol diacrylate and 2000 parts of trimethylol propane triacrylate, react at 100 ° C. for about 32 hours, then charge 308 parts of hexahydrophthalic anhydride. After reacting at 95 ° C. for about 6 hours, 156 parts of isocyanate ethyl methacrylate were charged,
After reacting at 50 ° C. for 10 hours, it was confirmed that no isocyanate group remained, and an unsaturated group-containing polycarboxylic acid urethane resin (A′-20-4) having an acid value of 33 was obtained as a solid component.

Examples 1 to 6 The resin composition of the present invention was obtained by heating, dissolving and kneading the blending composition shown in Table 1 (numerical values indicate parts by weight). These resin compositions were printed by using a dry lithographic plate to obtain curability (Examples 1 to 5).
Is the ultraviolet irradiation dose (mJ / cm ² ) until the tack on the surface of the printing surface disappears, and for Example 6,
The electron beam irradiation dose (Mrad) was measured until the tack on the printed surface disappeared). Resistance to scumming (Install a dry lithographic plate with an ink-repellent layer made of silicone rubber on a printing machine modified by installing an electric heater on the plate cylinder to raise the plate surface temperature, without supplying dampening water. The temperature was measured). The results are shown in Table 1.
Shown in. The scum resistance is determined by the scum generation temperature in dry lithographic printing, and if the temperature is less than 25 ° C, "x" is 25 to
30 ° C. “Δ” 30 ° C. or higher is indicated by “◯”.

[0037]

[Table 1] Table 1 Example 1 2 3 4 5 6 unsaturated group-containing polycarboxylic acid resin (A-10-1) 65 60 unsaturated group-containing polycarboxylic acid resin (A-30-2) 75 35 45 Unsaturated group-containing polycarboxylic acid resin (A-20-3) 35 65 Unsaturated group-containing polycarboxylic acid urethane resin (A'-20-4) 20 KAYARAD R-551 * 1 7 10 17 KAYARAD DPHA * 2 17 7 5 7 5 17 Irgacure 907 * 3 3 3 3 3 3 KAYACURE DETX-S * 4 0.5 0.5 0.5 0.5 0.5 Carmine 6 BA * 5 18 18 18 18 18 18 SH-3749 * 6 2.0 Soil resistance ○ ○ ○ ○ △ ○ Curability (mJ / cm ² ) 20 15 15 35 30 − Curability (Mrad) 1

Note * 1 KAYARAD R-551:
Polyethoxydiacrylate of bisphenol A manufactured by Nippon Kayaku Co., Ltd. * 2 KAYARAD DPHA: Nippon Kayaku Co., Ltd.
Made by dipentaerythritol penta and hexaacrylate mixture * 3 Irgacure 907: manufactured by Ciba / Kiggy Co., Ltd., photopolymerization initiator * 4 KAYACURE DETX-S: manufactured by Nippon Kayaku Co., Ltd., photopolymerization initiator * 5 Carmine 6 BA : Toyo Ink Co., Ltd.
Red pigment * 6 SH3749: manufactured by Shin-Etsu Silicone Co., Ltd., silicone oil

As is clear from the evaluation results in Table 1, the resin composition of the present invention has excellent scumming resistance and good curability.

[0040]

INDUSTRIAL APPLICABILITY The resin composition of the present invention is particularly suitable for dry lithographic printing inks, has good resistance to background stains, and has excellent curability with ultraviolet rays and electron beams.

Claims (4)

[Claims] 1. An epoxy compound (a) having at least two or more epoxy groups in one molecule, and at least two or more hydroxyl groups and one reactive group other than hydroxyl groups which react with epoxy groups in one molecule. An unsaturated group-containing polycarboxylic acid resin (A) which is a reaction product of a reaction product (a) of a compound (b) with an unsaturated group-containing monocarboxylic acid (c) and a polybasic acid anhydride (b), and an optional component A resin composition comprising a photopolymerization initiator (B) as the above. 2. A cured product of the composition according to claim 1. 3. An epoxy compound (a) having at least two epoxy groups in one molecule, and at least two hydroxyl groups in one molecule and a reactive group other than hydroxyl groups which reacts with one epoxy group. Containing an unsaturated group which is a reaction product of a compound (b) with an unsaturated group-containing monocarboxylic acid (c) (a), a polybasic acid anhydride (b) and an unsaturated group-containing monoisocyanate (c) A resin composition comprising a polycarboxylic acid urethane resin (A ') and a photopolymerization initiator (B) as an optional component. 4. A cured product of the composition according to claim 3.