JPH10251316A - Energy beam-curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition excellent as a coating agent, printing ink binder or a solder resist for manufacturing printing plates by including a resin formed by reaction of a specific compound with an epoxy resin-(meth) acrylate, and a photopolymerization initiator. SOLUTION: This composition excellent in developability, dilutive with water and developable with water is obtained by incorporating (A) 100 pts.wt. of a resin formed by reaction of an epoxy resin-(meth)acrylate prepared by reaction between (i) an epoxy resin bearing two or more epoxy groups and (ii) a (meth) acryloyl-bearing compound with (iii) a cyclic compound having at least two N atoms and bearing at least one active hydrogen on the N atom with (B) 1-30 pts.wt. of a photopolymerization initiator and (C) 0-50 pts.wt. of a epoxy compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an energy ray-curable resin composition. More specifically, the present invention relates to an energy ray-curable resin composition which is excellent as various coating agents, binders for printing inks, and solder resists for producing printing plates.

[0002]

2. Description of the Related Art In recent years, radiation curable resins curable by ultraviolet rays or electron beams have been widely used in the fields of printing, paints, and adhesives from the viewpoint of resource saving and energy saving. In the field of electronic devices such as printed wiring boards, solder resists are used to protect circuit boards after components are mounted for a long period of time, but those using an alkaline aqueous solution as a developing solution are mainly used.
These satisfy the performance as solder resist,
In use, it must be diluted with a large amount of volatile organic solvent, and there are problems such as environmental pollution and ignition, and there is a strong demand for water-based systems.

In order to solve such a problem, a water dilution type and / or water dispersion type liquid photo solder resist has been proposed. For example, JP-A-4-294352 discloses that a reaction product obtained by (a) reacting an aromatic epoxy resin with an unsaturated monocarboxylic acid and then reacting with an unsaturated polybasic acid anhydride is reacted with an amine. Japanese Patent Application Laid-Open No. 4-294354 discloses a photosensitive resin composition in which (b) a thermosetting compound, (c) a photopolymerization initiator, and (d) a reactive diluent are added to the aqueous dispersion of the photosensitive oligomer thus obtained. In the official gazette, (a) a copolymer of (meth) acrylic acid ester and (meth) acrylic acid and a photosensitive oligomer obtained by neutralizing an epoxy group-containing mono (meth) acrylic acid ester reactant with an amine are dispersed in water. A photosensitive resin composition that can be developed with an aqueous alkali solution, in which (b) a photopolymerization initiator and (d) a reactive diluent are added to the resulting dispersion, is disclosed. In the drying process to obtain There amine or volatilized used for neutralization, there is a problem that the developability decreases (thermal head).

[0004] Also, Japanese Patent Application Laid-Open No. Hei 5-3433837 discloses that
(A) an amine value obtained by adding a secondary amine to some of the ethylenically unsaturated bonds of a compound having two or more ethylenically unsaturated bonds has an amine value of 35 to 150 mgKOH /
g having an ethylenically unsaturated bond in one molecule
A salt obtained by neutralizing a tertiary amine compound with a monocarboxylic acid such as acrylic acid, (b) a photopolymerization initiator, (c) a diluent, and (d) an epoxy resin; 2 to 1 equivalents of the carboxylic acid used for the neutralization
Japanese Patent Application Laid-Open No. 5-339330 discloses a water-dilutable and water-washable liquid photo solder resist ink composition which is developed by using a dilute aqueous acid solution and which can be washed with water. An epoxy compound having an epoxy group of, and a part of the unsaturated double bond of a compound derived from a compound having an unsaturated double bond such as acrylic acid,
A compound having an amino group having at least one or more active hydrogens (eg, imidazole, diethanolamine) is added thereto, and then the resulting compound is neutralized with an acid such as lactic acid or acetic acid. An energy ray-curable resin composition containing a polymerization initiator has been proposed.

[0005] These can be diluted with water, but have a high water absorption after curing, and have the drawback that the coating film swells and whitens during development. Further, JP-A-7-261385 discloses that a radically polymerizable secondary amine is added to one equivalent of an acryloyl group of epoxy (meth) acrylate, which is a reaction product of (a) an equivalent reaction of a polyfunctional epoxy compound and (meth) acrylic acid. The reaction of x equivalents (0 <x <1) and non-radical polymerizable secondary amines with y equivalents (0 ≦ y <1) in the range of 0 <x + y ≦ 1 results in radical polymerizability in one molecule. Group and 3
A compound (b) photopolymerization initiator containing a secondary amino group,
(C) a water-soluble compound having a hydroxyl group or an ether bond in one molecule and containing two or more carboxyl groups, and (d) an epoxy resin, a melamine resin and a blocked polyisocyanate compound. Although a solder resist ink composition containing a compound as an essential component and developable with water is disclosed, this composition also has a disadvantage that the drying time is long.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a water-dilutable, water-developable energy ray-curable resin composition having excellent drying and developing properties.

[0007]

Means for Solving the Problems The present invention comprises: A) an epoxy resin obtained by reacting an epoxy resin (a) having two or more epoxy groups with a compound (b) having a (meth) acryloyl group. -A resin which is a cyclic compound having at least two or more nitrogen atoms on an acrylate and obtained by reacting a compound (c) having one or more active hydrogens on the nitrogen atoms. B) Component: photopolymerization initiator An object of the present invention is to provide an energy ray-curable resin composition containing the components A) and B).

[Action] A compound (c) as a raw material constituting the resin of the component (A) is a cyclic compound having at least two or more nitrogen atoms and having at least one active hydrogen on the nitrogen atom. By using the resin, the energy ray-curable resin composition which can be diluted and dispersed in water and has excellent developability without neutralizing the resin of the component (A) with an acid can be obtained.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Component (A): Component (A) serves as a matrix of a cured film, and comprises an epoxy resin (a) having two or more epoxy groups and a (meth) acryloyl group. A compound having at least one (meth) acryloyl group in the molecule obtained by reacting the compound (b) with the compound (b), and a cyclic compound having at least two or more nitrogen atoms, wherein 1 It is a resin obtained by subjecting compound (c) having at least two active hydrogens to an addition reaction.

Epoxy resin (a): The epoxy resin (a) used in the synthesis of the resin (A) includes bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, and biphenyl epoxy resin. Epoxy resin, bixylenol type epoxy resin,
N-glycidyl type epoxy resin; triglycidyl isocyanurate, phenol novolak resin, cresol novolak resin, ethylphenol novolak resin, isopropylphenol novolak resin, tert-butylphenol novolak resin, 3,5-xylenol novolak resin, bromphenol novolak resin, bisphenol A Novolak resin, naphthalene novolak resin, glycidyl compound such as polyvinylphenol: an epoxy resin such as an epoxy compound obtained by reacting a condensate of a phenol and an aromatic aldehyde having a phenolic hydroxyl group with epichlorohydrin or methylepichlorohydrin alone or Two or more kinds can be used in combination.

Compound (b) having a (meth) acryloyl group: The compound having an acryloyl group and / or the compound having a methacryloyl group of the component (b) is collectively referred to as a compound having a (meth) acryloyl group. (A) The compound (b) having a (meth) acryloyl group used in the synthesis of the resin includes (meth) acrylic acid,
2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, glycerin di (meth) acrylate, (meth) acryloyloxyethyl-2-
Hydroxypropyl phthalate, dimethylaminoethyl (meth) acrylate quaternary, diethylaminoethyl (meth) acrylate quaternary, 2- (meth) acryloyloxyethylsuccinic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- ( (Meth) acryloyloxyethyl hexahydrophthalic acid, mono-2- (meth) acryloyloxyethyl acid phosphate, trimethylolpropane tri (meth) acrylate, tetramethylol methane tri (meth) acrylate, (meth)
(Meth) acrylic acid or (meth) acrylic acid ester such as acryloyl isocyanate and 2-isocyanateethyl (meth) acrylate can be used alone or in combination of two or more. These compounds are
It is preferable to use an amount that causes the carboxyl group to react in an amount of 0.5 to 1 equivalent to the sum of the epoxy group and the hydroxyl group in the epoxy resin of the component (a).

A cyclic compound having at least two nitrogen atoms and having one or more active hydrogen atoms on the nitrogen atom (c): a cyclic compound having at least two or more nitrogen atoms of the component (c) Wherein the compound having one or more active hydrogens on the nitrogen atom includes imidazole, 2-methylimidazole, 4-methylimidazole, 4-methyl-5-imidazolecarboxaldehyde, 4-methyl-5-imidazole Methanol, 2-phenylimidazole, 2-methyl-5-nitroimidazole, 2-benzimidazole acetonitrile, 2-methyl-5-nitrobenzimidazole, 4-azabenzimidazole, imidazoline, 2-methyl-2-imidazoline, 7- Azaindole, 1-methylhydantoin, pyrazole, 3 Methylpyrazole, 4-methylpyrazole, 1,2,3-triazole, 1,2,4-triazole, 1,2,4-triazole-3-thiol, 1,2,3-triazole [4,5-b] Pyridine, pyrimidone and the like can be used.

The compound (c) can be used alone or in combination of two or more. A compound having a nitrogen atom having a structure other than the component (c) having the structure described above, such as morpholine or diethanolamine, can be used in a range that does not impair the object of the present invention (less than 50 mol%). These amino compounds are prepared by reacting the epoxy resin of the component (a) with the compound having a (meth) acryloyloxy group of the component (b). Active hydrogen is 0.1 to the sum of heavy bonds.
The reaction is preferably carried out in an amount of 1 to 0.9 equivalent, preferably 0.2 to 0.5 equivalent. When the amount of the amine compound is 0.
If it is less than 1 equivalent, the water solubility of the resin (A) is insufficient, and if it exceeds 0.9 equivalent, the curability (drying time) after irradiation with energy rays is insufficient.

(A) It is preferable to use a solvent during the synthesis reaction of the resin. Examples of the solvent include ketones such as methyl ethyl ketone, aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene, glycol ethers such as methyl cellosolve, methyl carbitol and diethylene glycol dimethyl ether, ethyl acetate and acetate esters of the above glycol ethers. Esters such as compounds, alcohols such as ethylene glycol and propylene glycol, aliphatic hydrocarbons such as octane, petroleum solvents such as petroleum naphtha and solvent naphtha, and water. These solvents may be used alone or as a mixture of two or more kinds. A suitable range of the amount to be used is 5 to 1,000 parts by weight based on 100 parts by weight of the epoxy compound.

Photopolymerization initiator (B): Examples of the photopolymerization initiator (B) include benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether, and their alkyl ethers; acetophenone, 2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone,
-Hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1- Acetophenones such as butanone; anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone and 2-amylanthraquinone;
Thioxanthones such as dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone and 2,4-diisopropylthioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone and xanthones; These can be used alone or in combination of two or more.

The photopolymerization initiator can be used in combination with one or more known and commonly used photopolymerization accelerators such as benzoic acid or tertiary amine.
The usage ratio of these photopolymerization initiators is 1 to 30 parts by weight, preferably 5 to 25 parts by weight, based on 100 parts by weight of the energy ray-curable resin (A). When the use amount of the photopolymerization initiator is less than the above range, the photocurability is deteriorated, and when the use amount is more than the above range, the properties as the solder resist deteriorate.

Optional components: The energy ray-curable resin composition of the present invention comprises, in addition to the resin (A) and the photopolymerization initiator (B), an epoxy compound (C) and a reactive diluent ( D), a protective colloid agent, an inorganic fine powder, a coloring pigment, a thermal polymerization inhibitor, a thickener, an antifoaming agent, a leveling agent, a coupling agent and the like can be used. Further, if necessary, a melamine resin which is a thermosetting resin, a blocked isocyanate,
An oxazoline resin or the like can be added as long as the developability is not reduced. Further, compounds such as adenine, vinyltriazine, dicyandiamide, orthotolylbiguanide, and melamine can be used for the purpose of preventing the oxidation of copper in the circuit of the printed wiring board.

The epoxy compound (C) is added in order to obtain a sufficiently tough film after the post-curing of the curable resin composition. As the epoxy compound used for this purpose, a polyfunctional epoxy compound containing two or more epoxy groups is used. For example, bisphenol A epoxy resin, bisphenol F epoxy resin,
Bisphenol S type epoxy resin, biphenyl type epoxy resin, bixylenol type epoxy resin, N-glycidyl type epoxy resin, triglycidyl isocyanurate,
Phenol novolak resin, cresol novolak resin, ethylphenol novolak resin, isopropylphenol novolak resin, tert-butylphenol novolak resin, 3,5-xylenol novolak resin, bromphenol novolak resin, bisphenol A novolak resin, naphthalene novolak resin, glycidyl of polyvinylphenol Compounds, epoxy compounds of phenols and condensates of aromatic aldehydes having a phenolic hydroxyl group, etc., polyethylene glycol diglycidyl ethers such as ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, propylene glycol Diglycidyl ether, dipropylene glycol diglycidide Ethers, polypropylene glycol diglycidyl ethers such as tripropylene glycol diglycidyl ether, polyglycerol polyglycidyl ethers such as glycerol polyglycidyl ether, diglycerol polyglycidyl ether, sorbitol polyglycidyl ether, sorbitan polyglycidyl ether, pentaerythritol polyglycidyl Ether, trimethylolpropane polyglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether,
Known and commonly used epoxy compounds such as triglycidyl tris (2-hydroxyethyl) isocyanate and diglycidyl adipate can be used alone or in combination of two or more. The epoxy compound may be water-soluble, water-dispersible, or water-insoluble, but a water-soluble compound or a water-dispersible compound is more preferable because of its good compatibility. The epoxy compound (C) is 50 parts by weight based on 100 parts by weight of the resin (A).
Used in parts by weight or less.

The reactive diluent (D) further enhances the photocuring of the energy ray-curable resin, and provides water resistance, heat resistance,
A compound used to obtain a film having alkali resistance and having at least two double bonds. For example, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate,
Polypropylene glycol di (meth) acrylate, neopentyl glycol adipate di (meth) acrylate, neopentyl glycol di (meth) acrylate hydroxypivalate, dicyclopentanyl di (meth)
Acrylate, caprolactone-modified dicyclopentenyl di (meth) acrylate, ethylene oxide-modified bisphenol A di (meth) acrylate, ethylene oxide-modified di (meth) acrylate phosphate, allylated cyclohexyl di (meth) acrylate, isocyanurate di (meth) Acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol penta ( (Meth) acrylate, propionic acid-modified dipentaerythritol tri (meth) acrylate, propylene oxide-modified trimethylol Entry (meth) acrylate, tris (acryloyloxyethyl) isocyanurate,
Reactive diluents such as propionic acid-modified dipentaerythritol tetra (meth) acrylate, propionic acid-modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and caprolactone-modified dipentaerythritol hexa (meth) acrylate No. The above bifunctional, trifunctional,
The tetrafunctional, pentafunctional, and hexafunctional polyfunctional reactive diluents can be used alone or in a mixed system. This reactive diluent may be either an aqueous solution or water-insoluble, but is preferably water-soluble because it has good compatibility with the resin (A).

Examples of the inorganic fine powder include silica, alumina, talc, clay, calcium carbonate and barium sulfate. Examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tertiary butyl catechol, and phenothiazine. . The energy ray-curable resin composition of the present invention has high sensitivity and can be dissolved in water or an organic solvent before curing, and after curing, a cured product (film) having excellent water resistance, solvent resistance and the like can be obtained. give.

In the present invention, energy rays are a general term for various types of ionizing radiation and light such as electron beams, α rays, β rays, γ rays, X rays, neutron rays or ultraviolet rays. The energy ray-curable resin composition of the present invention, depending on the application, aluminum, stainless steel, such as a metal plate,
It is applied on a screen mesh, paper, wood, synthetic resin, semiconductor substrate, or any other substrate, dried, and then irradiated with energy rays for use. The composition of the present invention can be used as a solder resist, a plating resist, various insulating materials, a surface coating agent, a paint, an adhesive and the like.

[0022]

Next, the present invention will be described with reference to examples. (A) Production Example of Resin: (Synthesis Example 1) In a flask provided with a thermometer, a stirrer, and a reflux condenser, an epoxy resin (cresol novolac type epoxy resin manufactured by Yuka Shell Epoxy Co., Ltd .: Epicoat 18)
0S75 (trade name), epoxy equivalent is 217) 217 g
And 124.5 g of diethylene glycol dimethyl ether
And stirred to dissolve, then hydroquinone 0.3
g, 73.5 g of acrylic acid and 2.9 g of tetramethylammonium bromide were added and reacted at 110 ° C. until the acid value became 2 or less. Then, imidazole 34
g and 200 g of water were added and reacted at 80 ° C. for 4 hours to obtain a reaction product solution. This photosensitive resin solution had a nonvolatile component content of about 50%. Hereinafter, this compound is referred to as A-1.

(Synthesis Example 2) The amount of imidazole used was 1
An experiment was performed in the same manner as in Synthesis Example 1, except that 3.6 g and 200 g of water were changed to a mixture of 90 g of water and 90 g of isopropyl alcohol. This photosensitive resin solution contains about 5 nonvolatile components.
It was 0%. Hereinafter, this compound is referred to as A-2. (Synthesis Example 3) In a flask equipped with a thermometer, a stirrer, and a reflux condenser, an epoxy resin (cresol novolak type epoxy resin manufactured by Yuka Shell Epoxy Co., Ltd .: Epicoat 18)
0S65 (trade name), epoxy equivalent is 214) 214g
And 124.5 g of diethylene glycol dimethyl ether
And stirred to dissolve, then hydroquinone 0.3
g and 73.5 g of acrylic acid and 2.9 g of triphenylphosphine, and add 11 g until the acid value becomes 2 or less.
After reacting at 0 ° C., 34 g of pyrazole and 20
0 g was added, and the mixture was reacted at 80 ° C. for 4 hours to obtain a reaction product solution. This photosensitive resin solution had a nonvolatile component content of about 50%. Hereinafter, this compound is referred to as A-3.

(Synthesis Example 4) In a flask equipped with a thermometer, a stirrer and a reflux condenser, an epoxy resin (cresol novolac type epoxy resin manufactured by Yuka Shell Epoxy Co., Ltd .: Epicoat 1031S (trade name), epoxy equivalent: 20)
4) 204 g and 124.5 g of methyl ethyl ketone were added and dissolved by stirring. Then, 0.3 g of hydroquinone, 73.5 g of acrylic acid and dimethylbenzylamine were added.
9 g, and reacted at 110 ° C. until the acid value becomes 2 or less. Then, 34.5 g of 1,2,4-triazole and 200 g of water were added and reacted at 80 ° C. for 4 hours to obtain a reaction product solution. I got This photosensitive resin solution had a nonvolatile component content of about 50%. Hereinafter, this compound is referred to as A-4. (Synthesis Example 5) (for Comparative Example) An experiment was performed in the same manner as in Synthesis Example 1 except that 52.6 g of diethanolamine and 218 g of isopropyl alcohol were used instead of 34 g of imidazole and 200 g of water. This photosensitive resin solution had a nonvolatile component content of about 50%. Hereinafter, this compound is referred to as B-1.

(Synthesis Example 6) (for Comparative Example) Instead of 34 g of imidazole and 200 g of water, 33.5 g of pyrrole and 200 g of isopropyl alcohol were used.
An experiment was performed in the same manner as in Synthesis Example 1 except that the compound was used. This photosensitive resin solution had a nonvolatile component content of about 50%. Less than,
This compound is designated as B-2. (Synthesis Example 7) (for Comparative Example) Epicron N- of cresol novolak type epoxy resin
220 parts of 695 (manufactured by Dainippon Ink and Chemicals, Inc., epoxy equivalent is 220) was placed in a four-necked flask equipped with a stirrer and a reflux condenser, and 168 parts of dipropylene glycol monomethyl ether was added and dissolved by heating. 35 parts of diethanolamine is gradually dropped into this resin solution,
The reaction was carried out at ７０70 ° C. for 3 hours. To this reaction product, 0.05 part of hydroquinone was added as a polymerization inhibitor. This mixture was heated to 85 to 95 ° C., and 48 parts of acrylic acid was gradually added dropwise and reacted for 5 hours to obtain a photosensitive resin solution having a nonvolatile content of 64% and an amine value of a solid content of 62 mgKOH / g. Hereinafter, this is referred to as a resin solution (B-3).

Example 1 The resin solution (A) obtained in Synthesis Example 1
-1) To 100 parts by weight, 5 parts by weight of benzyldimethyl ketal (trade name: Irgacure 651 manufactured by Ciba Geigy) as a photopolymerization initiator was mixed and dispersed to obtain a photocurable resin composition (paint). The performance of this paint was evaluated as follows.

Dryness to the touch: 20 μm of paint on tin plate
And dried in warm air of 80 ° C. for 30 minutes, and then touched with a finger to determine the presence or absence of tack of the coating film. ：: No tack was observed at all. 指紋: Fingerprints remained slightly. ：: Ink adhered to fingers. Water resolubility: A tinplate coated with a paint having a thickness of 20 μm was dried in warm air at 80 ° C. for 30 minutes. After that, the film was immersed in ion-exchanged water for 5 minutes to visually determine the dissolution state of the coating film. ：: Little paint film left on tin plate △: Some paint film left on tin plate ×: Paint film left on tin plate

Curability: A tin plate coated with a coating material having a thickness of 30 μm was dried in warm air at 80 ° C. for 30 minutes, taken out, and the coating film was irradiated with 500 mJ of ultraviolet light using a high-pressure mercury lamp.
/ Cm ² . Next, the film was immersed in ion-exchanged water for 5 minutes to visually determine the state of the coating film. ：: No change in the coating film. Δ: The coating film was whitened. ×: The coating film was dissolved. In addition, as for the one in which the coating film was whitened (Comparative Example 3 to be described later), it was determined that the amount of ultraviolet irradiation was small, and the irradiation amount of ultraviolet light was increased to obtain a transparent one in which the coating film was not whitened. The amount of UV irradiation up to this point is given. Table 1 shows the results.

(Example 2) The procedure of Example 1 was repeated, except that the resin solution (A-2) obtained in Synthesis Example 2 was used instead of the resin solution (A-1). (Example 3) The same operation as in Example 1 was performed except that the resin solution (A-3) obtained in Synthesis Example 3 was used instead of the resin solution (A-1). (Example 4) The same operation as in Example 1 was performed except that the resin solution (A-4) obtained in Synthesis Example 4 was used instead of the resin solution (A-1).

Example 5 The resin solution obtained in Synthesis Example 1 (A
-1) 100 parts by weight of an epoxy compound (product name: EPI REZ6006, manufactured by Yuka Shell Epoxy) 2
0 parts by weight and 5 parts by weight of benzyl dimethyl ketal (trade name: Irgacure 651 manufactured by Ciba Geigy) were mixed and dispersed to obtain a paint. Table 1 shows the performance evaluation test results of the obtained coating films.

Comparative Example 1 The resin solution obtained in Synthesis Example 1 (A
-1) in place of the resin solution (B-
1) The procedure was performed in the same manner as in Example 1 except that 100 parts by weight was used. (Comparative Example 2) The same operation as in Example 1 was performed except that 100 parts by weight of the resin solution (B-2) obtained in Synthesis Example 6 was used instead of the resin solution (A-1) obtained in Synthesis Example 1. did. (Comparative Example 3) The same operation as in Example 1 was performed except that 100 parts by weight of the resin solution (B-3) obtained in Synthesis Example 6 was used instead of the resin solution (A-1) obtained in Synthesis Example 1. did. Table 1 shows the results.

[0032]

[Table 1] ^{* The} amount of UV irradiation before whitening does not reach 2,000 mJ
/ Cm ² .

[0033]

The present invention is an energy ray-curable resin composition which is excellent in developability and can be diluted with water and developed with water.

Claims (2)

[Claims] 1. Component (A): an epoxy resin obtained by reacting an epoxy resin (a) having two or more epoxy groups with a compound (b) having a (meth) acryloyl group.
(Meth) acrylate is a cyclic compound having at least two or more nitrogen atoms, and a resin obtained by reacting compound (c) having one or more active hydrogens on the nitrogen atom. B) Component: photopolymerization Initiator An energy ray-curable resin composition containing the above components A) and B). 2. A component: an epoxy resin (meth) acrylate obtained by reacting an epoxy resin (a) having two or more epoxy groups with a compound (b) having a (meth) acryloyl group, A cyclic compound having at least two or more nitrogen atoms, and a resin obtained by reacting a compound (c) having one or more active hydrogen atoms with the nitrogen atoms 100 parts by weight B) Component: Photopolymerization initiator 1 ３０30 parts by weight C) Component: epoxy compound 0-50 parts by weight An energy ray-curable resin composition containing the above components A), B) and C).