JP2003119228A - Photo- and/or thermosetting resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photo- and/or thermosetting resin composition which gives a cured coating film excellent in water resistance and electrical characteristics. SOLUTION: The photo- and/or thermosetting resin composition comprises essentially a compound or polymer having structural formula (I) (wherein R<1> is H or a 1-7C hydrocarbon group; and R<2> to R<4> may be the same or different and are each a 1-7C hydrocarbon group).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a light and / or thermosetting resin composition, and a liquid resist comprising the resin composition, a dry film, a color filter used for a liquid crystal display, a pigment such as a black matrix. The present invention relates to a wiring board insulating material such as a resist or buildup, or a coating protective film. More specifically, the present invention relates to a photo- and / or thermosetting resin composition which is capable of easily forming an image by exposure and development with a dilute aqueous alkali solution after forming a film and has excellent water resistance. The light and / or thermosetting resin composition of the present invention is particularly useful as a binder resin for a resist ink such as a printed wiring board relating to electronics, an LSI-related matter, a color filter accompanying a liquid crystal, and a sealing agent. .

[0002]

2. Description of the Related Art In recent years, due to environmental problems, resource saving, energy saving, workability improvement, etc., solvent development has shifted to dilute alkaline aqueous solution development in various fields. In the printed wiring board processing field, the resist ink has been changed from the solvent development type to a dilute alkaline aqueous solution development type for the same reason. In printed wiring boards, solder resist resins are widely used as permanent protective coatings for circuit boards. The solder resist is formed on the entire surface of the base circuit conductor except the portion to be soldered. The main function of the solder resist is to prevent the solder from adhering to unnecessary portions when soldering electronic parts to the printed wiring board, and to prevent oxidation and corrosion of the circuit conductor. Conventionally, when a solder resist film is formed on a printed wiring board, a thermosetting type resist ink is printed by a screen printing method, and a transfer portion is thermoset or UV-cured. However, the screen printing method has a problem that bleeding, bleeding, and sagging occur at the time of printing, and it cannot cope with the recent increase in the density of circuit boards. A photographic method was developed to solve this problem. The photographic method is a method of forming a desired pattern by exposing through a film on which a pattern is formed and then developing. Conventionally, an organic solvent has been used for developing such a photo solder resist ink. However, in recent years, due to the problem of environmental pollution, there is a tendency to shift to a type capable of developing with a dilute alkaline aqueous solution. Such a resist ink can be obtained by adding a polybasic acid anhydride to a reaction product of a novolac type epoxy compound and an unsaturated monocarboxylic acid as described in Japanese Patent Publication No. 1-54390. The compound is used as the main component. The solder resist ink obtained by using this compound as a main component has excellent heat resistance and is still widely used today. Further, JP-A-63-11930 and JP-A-63-20
Japanese Patent No. 564 proposes a composition using a half ester compound of a copolymer of styrene and maleic anhydride.

[0003]

However, the ink using the above compound has (1) a high resin acid value and poor electrical characteristics. Further, (2) it has a drawback that the tack-free property is poor and it takes a very long time to remove the solvent after applying the ink. In order to solve the above problems, JP-A-1-
289820 and JP-A-6-138659 propose a resin composition obtained by adding an alicyclic epoxy-containing unsaturated compound to a poly (meth) acrylic resin. Although the tack-free property has been greatly improved, it is still not sufficient in terms of the water resistance and electric properties of the cured coating film.

[0004]

Therefore, as a result of intensive investigations to solve the above problems, the present inventors have found that the compound having the structure shown in the structural formula (I) or the structural formula (I) is obtained. It has been found that the above problems can be solved by a light and / or thermosetting resin composition containing a polymer having the structure shown in the skeleton as an essential component, and the present invention has been completed.

That is, the present invention relates to the following structural formula (I)

[Chemical 3] And / or thermosetting resin composition (R ¹ is hydrogen or C ₁ ~
Represents a C ₇ hydrocarbon group. R ^{2 to} R ⁴ represent a C _{1 to} C ₇ hydrocarbon group, and they may be the same or different. ) ”,“ The following structural formula (I)

[Chemical 4] (R ¹ represents hydrogen or a C _{1 to} C ₇ hydrocarbon group. R ^{2 to} R ⁴ are
Represents a hydrocarbon group of C ₁ -C _7, they may be be the same or different. A photo- and / or thermosetting resin composition containing, as an essential component, a polymer containing a compound having a) in a resin skeleton and, if necessary, a curable resin. And "a liquid resist, a dry film, a color filter used for a liquid crystal display, a pigment resist, a wiring board insulating material, or a coating protective film, which is composed of the above-mentioned light and / or thermosetting resin composition."

In the present invention, the following structural formula (I)

[Chemical 5] Of a cured product obtained by using a curable resin composition containing as an essential component a compound having the formula or a polymer having the structure represented by the structural formula (I) in the skeleton, and reducing water absorption by improving water resistance. By performing the above, a light and / or thermosetting resin composition having excellent electrical characteristics is provided. In the compound having the structural formula (I), R ¹ is hydrogen or C _1-
Represents a C ₇ hydrocarbon residue. R ^{2 to} R ⁴ represent a C _{1 to} C ₇ hydrocarbon residue, and they may be the same or different. Specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and an alicyclic group such as a cyclohexyl group. Commonly it is a methyl group. A typical example of a specific compound is trimethylcyclohexyl (meth) acrylate.

Next, the polymer used in the photocurable and / or thermosetting composition of the present invention will be described. As the polymer having the structure represented by the structural formula (I) in the skeleton, a copolymer composed of the compound of the structural formula (I) and a (meth) acrylic acid ester (this copolymer has a curable unsaturated bond Or a copolymer of a compound of structural formula (I), a compound having a polymerizable unsaturated group having an acid group, and a (meth) acrylic acid ester (also referred to as an acid group-containing resin) It is a modified copolymer synthesized by adding an epoxy group-containing unsaturated compound to some acid groups in the presence of a catalyst. The molar ratio of the compound represented by the structural formula (I) and the other polymerizable monomer can be arbitrarily changed, but the compound represented by the structural formula (I) / the other polymerizable monomer = 5/95 to 99/1 preferable. More preferably, it is in the range of 5/95 to 50/50. When the molar ratio of the compound represented by the structural formula (I) is less than 5, the water resistance of the entire cured product is significantly reduced. When using the above-mentioned copolymer having no curable unsaturated bond, it is necessary to mix another curable resin having a curable unsaturated bond. Other curable resins include difunctional (meth) acrylic acid esters such as 1,6-hexanediol di (meth) acrylate and trifunctional (meth) acrylic acid esters such as trimethylolpropane tri (meth) acrylate. Examples thereof include tetrafunctional (meth) acrylic acid esters such as pentaerythritol tetra (meth) acrylate, and hexafunctional (meth) acrylic acid esters such as dipentaerythritol hexa (meth) acrylate. Examples of (meth) acrylic acid ester include methyl (meth) acrylate and ethyl (meth)
(Meth) acrylic acid alkyl esters such as acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, adamantyl (meth) acrylate, norbornyl (meth) acrylate, 2- Hydroxyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, caprocactone-modified 2-hydroxyethyl (meth) acrylate, hydroxyadamantyl (meth) acrylate, hydroxynorbornyl (meth) acrylate, etc. Having (meth) acrylic acid esters, methoxydiethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, isooctyl Carboxymethyl diethylene glycol (meth) acrylate, phenoxy triethyleneglycol (meth) acrylate, methoxy triethylene glycol (meth) acrylate, (meth) acrylates such as methoxy polyethylene glycol (meth) acrylate.

As the compound containing an unsaturated group and having at least one or more acid groups, which can be used as necessary,
(Meth) acrylic acid, β-carboxyethyl acrylate, ε-caprolactone-modified (meth) acrylate, vinylphenols and the like can be mentioned. Alternatively, it may be one having two or more carboxyl groups such as maleic acid in the molecule. These may be used alone or in combination.

Next, an epoxy group-containing unsaturated compound is added to the acid group of the copolymer obtained from the above monomer to obtain the modified copolymer having the structure represented by the structural formula (I) in the skeleton. To be The epoxy group-containing unsaturated compound is a compound having one radically polymerizable unsaturated group and an aliphatic or alicyclic epoxy group in one molecule.
Specifically, for example, the following formula or general formula [R ¹ represents a hydrogen atom or a methyl group. R ² represents a divalent saturated aliphatic hydrocarbon group having 1 to 6 carbon atoms, n is an integer of 4 to 8, m is an integer of 0 to 30, and l is an integer of 2 to 10. ] An alicyclic epoxy group-containing unsaturated compound such as [eg, 3,4-epoxycyclohexylmethyl acrylate (Cyclomer A200 manufactured by Daicel Chemical Industries, Ltd.)]. Further, aliphatic-containing unsaturated compounds such as glycidyl methacrylate, β-methylglycidyl methacrylate, and allyl glycidyl ether can be used. These epoxy group-containing unsaturated compounds may be used alone or in combination of two or more.

[0010]

[Chemical 6]

[0011]

[Chemical 7]

The amount of the epoxy group-containing unsaturated compound added is preferably in the range of 5 to 50 mol% with respect to the total monomers constituting the modified copolymer. If the added amount is less than 5%, the ultraviolet curability is poor, and the physical properties of the cured coating are reduced. If it is 50% or more, the storage stability of the resin becomes poor.
The modified copolymer thus obtained has an acid value of 10 to 150 K in order to be soluble in a dilute aqueous alkali solution or water.
It is necessary to be in the range of OH-mg / g. If the acid value is less than 10 KOH-mg / g, it is difficult to remove the uncured film with a dilute aqueous alkali solution or water, and the KO film is 150 KO.
If it exceeds H-mg / g, there is a problem that the water resistance of the cured film and, as a result, the electrical characteristics are poor. The modified copolymer preferably has a weight average molecular weight in the range of 5,000 to 150,000. Weight average molecular weight of 5,000
If it is below, there are problems that (1) the tack-free performance is poor, (2) the moisture resistance of the coating film after exposure is poor, film slippage occurs during development, and the resolution is greatly degraded. If the weight average molecular weight is 150,000 or more, there are problems such as (1) the developability is remarkably deteriorated, and (2) the storage stability is deteriorated.

The catalyst used when the epoxy group-containing unsaturated compound is added to the acid group-containing resin is a tertiary amine such as dimethylbenzylamine, triethylamine, tetramethylethylenediamine, tri-n-octylamine, or tetramethylammonium. Quaternary ammonium salts such as chloride, tetramethylammonium bromide and tetrabutylammonium bromide, alkylureas such as tetramethylurea, alkylguanidines such as tetramethylguanidine, metal compounds typified by cobalt naphthenate, organometallic complexes, tritium Phosphine compounds such as phenylphosphine and salts thereof can be mentioned, but tertiary phosphine typified by triphenylphosphine is preferable. The above catalysts may be used alone or in combination. These catalysts are used in an amount of 0.01 to 10% by weight, preferably 0.5 to 3.0% by weight, based on the epoxy compound. If it is less than 0.01% by weight, the catalytic effect is low and it is not necessary to add an amount exceeding 10% by weight.

The solvent used when the epoxy group-containing unsaturated compound is added to the acid group-containing resin is not particularly limited as long as it can dissolve the raw materials used, and examples thereof include aromatic compounds such as benzene, toluene and xylene. Group hydrocarbons,
Alcohols such as methanol, ethanol, 2-propanol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, ethers such as diethyl ether, dibutyl ether, dioxane, ethyl acetate, isobutyl acetate, ethylene glycol monoacetate, propylene glycol mono Esters such as acetate, 1,3-propanediol monoacetate, dipropylene glycol monoacetate, ethylene glycol monoalkyl ethers, diethylene glycol monoalkyl ethers, propylene glycol monoalkyl ethers, 1,3-propanediol monoalkyl ether , Dipropylene glycol monoalkyl ethers, butylene glycol monoalkyl ethers,
Diethylene glycol dialkyl ethers such as ethylene glycol dialkyl ethers, diethylene glycol dimethyl ether and diethylene glycol diethyl ether, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether acetates, 1,3-propanediol monoalkyl ether acetates, diethylene glycol monoalkyl Amides such as ether acetates, dimethylformamide and dimethylacetamide, and halogenated hydrocarbons such as carbon tetrachloride and chloroform are used. These solvents may be used alone or as a mixture.

The light and / or thermosetting composition of the present invention will be described. Examples of the photopolymerization initiator that can be included in the composition include benzophenone, acetophenone benzyl, benzyl dimethyl ketone, benzoin,
Benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, dimethoxyacetophenone, dimethoxyphenylacetophenone, diethoxyacetophenone, diphenyldisulfite, α
-Hydroxyisobutylphenone or the like is used alone or in combination. These photoinitiators can also contain synergists to enhance the conversion of light absorbed energy into polymerization initiating free radicals, such as tertiary amines. The amount of the photopolymerization initiator added is 0 to 20% by weight, preferably 0 to 10% by weight, and more preferably 0 to 5% with respect to the entire composition.
% By weight. If the addition amount of the photopolymerization initiator is more than 20% by weight, not only the curability is lowered but also the cost is increased, which is not preferable. When the curable resin composition of the present invention is cured by electron beam irradiation, it is not always necessary to add the initiator.

Liquid resist and dry film
When used as a component, it can be cured by heat. The curing conditions may be 100 to 200 ° C. and 1 to 90 minutes. The curing is preferably carried out in an inert gas atmosphere, but it can also be carried out in an air atmosphere. The Tg of the cured coating film obtained from the light and / or thermosetting resin composition obtained as described above is 50 ° C or higher, preferably 50 ° C to 200 ° C. When the Tg of the cured coating film is less than 50 ° C., the tack-free property of the cured coating film is deteriorated, which is not preferable. In particular, since the curable resin composition of the present invention contains the structural formula (I), it is characterized in that the Tg of the cured coating film is improved to 100 ° C to 180 ° C, which is 5 ° C as compared with the case where it is not contained. ~ 50
It can be improved by about 0 ° C.

The diluting monomer or oligomer is a compound having a radical-polymerizable double bond represented by an acrylic ester or methacrylic ester compound, a vinyl aromatic compound such as styrene, an amide unsaturated compound and the like. Typical acrylic acid ester or methacrylic acid ester is as follows. (Meth) acrylic acid alkyl esters such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, 2-hydroxyethyl (Meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, caprocactone-modified 2-hydroxyethyl (meth) acrylate,
Hydroxyl group-containing (meth) acrylates, methoxydiethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, isooctyloxydiethylene glycol (meth) acrylate, phenoxytriethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) Acrylate, methoxy polyethylene glycol # 400-
(Meth) acrylates such as (meth) acrylate,
Bifunctional (meth) acrylic acid esters such as 1,6-hexanediol di (meth) acrylate and neopentyl glycol di (meth) acrylate, trifunctional (meth) such as trimethylolpropane tri (meth) acrylate
Acrylic acid esters are used. Examples of the polymerizable prepolymer include (meth) acrylic acid esters of polyester polyols, (meth) acrylic acid esters of polyether polyols, adducts of polyepoxy and (meth) acrylic acid, and polyols via polyisocyanates. And a resin into which hydroxy (meth) acrylate is introduced. The above-mentioned diluting monomer and oligomer can be blended in a necessary amount with respect to the modified copolymer, for example, in the range of 0 to 300 parts by weight, preferably 0 to 100 parts by weight. When the amount of the diluting monomer and oligomer is more than 300 parts, the characteristics of the photo- and / or thermosetting resin composition of the present invention are reduced.

Examples of the epoxy compound that can be added to the photo and / or thermosetting composition of the present invention include epoxidized polybutadiene, epoxidized butadiene styrene block copolymers and other unsaturated group-containing epoxidized resins. Examples of commercially available products include Epolide PB and ESBS manufactured by Daicel Chemical Industries, Ltd. Alicyclic epoxy resin (for example, Celoxide 2021, E manufactured by Daicel Chemical Industries, Ltd.)
HPE; Epomic VG-310 manufactured by Mitsui Chemicals, Inc.
1: Yuka Shell Epoxy Co., Ltd., E-1031S; Mitsubishi Gas Chemical Co., Inc., TETRAD-X, TETRAD
-C; manufactured by Nippon Soda Co., Ltd., EPB-13, EPB-27
Etc.), a copolymer type epoxy resin (for example, a copolymer of glycidyl methacrylate and styrene, a copolymer of glycidyl methacrylate, styrene, and methyl methacrylate, CP-50M, CP-5 manufactured by NOF CORPORATION).
0S, or a copolymer such as glycidyl methacrylate and cyclohexylmaleimide). Other examples include epoxidized resins having a special structure.
In addition, novolac type epoxy resin (for example, phenol, cresol, halogenated phenol, and alkylphenol, etc., obtained by reacting novolaks and epichlorohydrin and / or methyl epichlorohydrin obtained by reacting formaldehyde with formaldehyde under an acidic catalyst. The commercially available products include EOCN-103, EOCN-104S and EO manufactured by Nippon Kayaku Co., Ltd.
CN-1020, EOCN-1027, EPPN-20
1, BREN-S: Dow Chemical Co., DEN-43
1, DEN-439: manufactured by Dainippon Ink and Chemicals, Inc.
N-73, VH-4150, etc.), bisphenol type epoxy resin (for example, bisphenol A, bisphenol F, bisphenol S, tetrabromobisphenol A, etc. obtained by reacting bisphenol with epichlorohydrin, and bisphenol A Those obtained by reacting a condensate of diglycidyl ether with the above-mentioned bisphenols and epichlorohydrin, etc. As commercially available products thereof, manufactured by Yuka Shell Co., Ltd., Epicoat 1004,
Epicoat 1002; DER-33 manufactured by Dow Chemical Company
0, DER-337, etc.), trisphenol methane, triscresol methane and the like and / or those obtained by reacting with epichlorohydrin and / or methylepichlorohydrin. As its commercial product, Nippon Kayaku Co., Ltd. EPPN-
501, EPPN-502 and the like, tris (2,3-epoxypropyl) isocyanurate, biphenyl diglycidyl ether and the like can also be used. These epoxy resins may be used alone or in combination. These epoxy compounds are added in a necessary amount, for example, 0 to 300 parts based on the modified copolymer. Amount of epoxy compound is 3
When it is more than 00 parts, the characteristics of the light and / or thermosetting resin composition of the present invention are reduced. Further, after the above-mentioned epoxy resin is modified with (meth) acrylic acid, a compound or resin having an unsaturated group and an acid group, to which an acid anhydride is added, can be used in combination.

Further, the photo- and / or thermosetting resin composition of the present invention contains the compound represented by the structural formula (I) in the copolymer without copolymerizing the compound represented by the structural formula (I). It can also be manufactured by mixing with a curable resin that is not included as a copolymerization component. Examples of the curable resin include bifunctional (meth) acrylic acid esters such as 1,6-hexanediol di (meth) acrylate and trifunctional (meth) acrylic acid such as trimethylolpropane tri (meth) acrylate. Esters, tetrafunctional (meth) acrylic acid esters such as pentaerythritol tetra (meth) acrylate, and hexafunctional (meth) acrylic acid esters such as dipentaerythritol hexa (meth) acrylate can be used. In addition, novolac type epoxy resin (for example, phenol, cresol, halogenated phenol, and alkylphenol, etc., obtained by reacting novolaks and epichlorohydrin and / or methyl epichlorohydrin obtained by reacting formaldehyde with formaldehyde under an acidic catalyst. Examples of commercially available products include EOCN-103 manufactured by Nippon Kayaku Co., Ltd.,
EOCN-104S, EOCN-1020, EOCN-
1027, EPPN-201, BREN-S: manufactured by Dow Chemical Co., DEN-431, DEN-439: manufactured by Dainippon Ink and Chemicals, Inc., N-73, VH-4150, etc.), bisphenol type epoxy resin (For example, those obtained by reacting bisphenols such as bisphenol A, bisphenol F, bisphenol S, and tetrabromobisphenol A with epichlorohydrin,
As a commercially available product obtained by reacting a diglycidyl ether of bisphenol A with a condensate of the above bisphenols and epichlorohydrin, Yuka Shell Co., Ltd.
Manufactured by Dow Chemical Co., Ltd. DER-330, DER-337, etc.), trichlorophenol methane, triscresol methane and the like obtained by reacting with epichlorohydrin and / or methyl epichlorohydrin, and the like, commercial products thereof. As Nippon Kayaku Co., Ltd. EPPN-501, EPPN-502, etc.,
A photo and / or thermosetting resin obtained by adding a compound having an acid group and a (meth) acryl group to tris (2,3-epoxypropyl) isocyanurate, biphenyldiglycidyl ether, or the like, and a rare acid obtained by adding an acid anhydride. A light and / or thermosetting resin that can be developed with an alkaline solution can be mixed and used.

The mixing ratio, the acid value of the resin, the amounts of various additives, etc. may be substantially the same as those containing the compound represented by the structural formula (I) as a copolymerization component. However, in this case, the structural formula (I)
Since the compound shown in (1) also plays a role as a solvent for diluting a low molecular weight compound, the molecular weight of the curable resin which does not contain the compound represented by the structural formula (I) as a copolymerization component is slightly higher in consideration of the viscosity of the resin composition during use. It needs to be adjusted higher.

The photocurable and / or thermosetting resin composition of the present invention may further contain a thermal polymerization inhibitor, a surfactant, a light absorber, a thixotropic agent, a dye, a pigment and the like as other additives, if necessary. You can Further, a thermoplastic resin, a thermosetting resin or the like can be blended. The light and / or thermosetting resin composition of the present invention can be cured by applying it as a thin film on a substrate. As a method for forming a thin film, spraying, brushing, roll coating, curtain coating, electrodeposition coating, electrostatic coating, etc. are used. The curing is preferably carried out in an inert gas atmosphere, but it can also be carried out in an air atmosphere.
The curable resin and the curable resin composition according to the present invention are used in various coating fields such as ink, plastic paint, paper printing, film coating, and furniture coating, FRP,
It can be applied to many industrial fields such as linings, insulation varnishes in the electronics field, insulation sheets, laminated plates, printed boards, resist inks, pigment resist inks for color filters, and semiconductor encapsulants.
As a light source for photocuring the light and / or thermosetting resin composition of the present invention, a high pressure mercury lamp, ultraviolet rays, E
Light such as B or a laser beam can be used. The irradiation conditions are, for example, 50 to 1 when using a high pressure mercury lamp.
After drying the coating film at 20 ° C for 5 to 20 minutes, 50 to 20
The irradiation intensity is 0 W / cm, preferably 80 to 150 W / cm, more preferably about 120 W / cm, and the irradiation time is 1 to 10 seconds, preferably 3 to 8 seconds, more preferably about 5 seconds. The thickness of the cured coating film thus obtained is 5 to 50 μm, preferably about 20 μm.

[0022]

EXAMPLES The present invention will be described more specifically below with reference to examples. However, the present invention is not limited to this embodiment. [Synthesis Example of Resin] (Synthesis Example 1) 250 g of dipropylene glycol monomethyl ether (MFDG manufactured by Nippon Emulsifier Co., Ltd.) was introduced into a 2 L separable flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introduction tube. Then, after raising the temperature to 110 ° C,
Methacrylic acid 113.5g, methyl methacrylate 5
2.8 g, trimethylcyclohexyl methacrylate [compound of structural formula (I)] 161.2 g, MFDG20
Both 0 g and 22.0 g of t-butyl peroxy 2-ethylhexanoate (Perbutyl O manufactured by NOF CORPORATION) were added dropwise over 4 hours. After dropping, the mixture was aged for 3 hours to synthesize a trunk polymer having a carboxyl group. Next, 3,4-epoxycyclohexylmethyl acrylate (Cyclomer A200 manufactured by Daicel Chemical Industries, Ltd.) was added to the above trunk polymer solution.
222.4 g, triphenylphosphine 2.2 g, and methyl hydroquinone 1.0 g were added, and the mixture was reacted at 100 ° C. for 10 hours. Reaction is air / nitrogen (10/90% by volume)
Was performed under a mixed atmosphere. This gives an acid value of 10 KOH
A curable resin solution (A-1) having -mg / g, double bond equivalent (resin weight per 1 mol of unsaturated group) 450, and weight average molecular weight 15,000 was obtained. (Synthesis Example 2) 250 g of propylene glycol nomomethyl ether (MMPG manufactured by Daicel Chemical Industries, Ltd.) was introduced into a 2 L separable flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen inlet tube, and heated to 110 ° C. After heating, βCEA (β-carboxyethyl acrylate) 5
7.0 g, methacrylic acid 79.5 g, trimethylcyclohexyl methacrylate 191.0 g, MFDG223
g and t-butyl peroxy 2-ethylhexanoate (Perbutyl O manufactured by NOF CORPORATION) were both added dropwise over 4 hours. After dropping, the mixture was aged for 3 hours to synthesize a trunk polymer having a carboxyl group. Next, 2,4-epoxycyclohexyl methyl acrylate (Cyclomer A200 manufactured by Daicel Chemical Industries, Ltd.) 2 was added to the above trunk polymer solution.
22.4 g, triphenylphosphine 2.0 g, and methyl hydroquinone 1.0 g were added, and the mixture was reacted at 100 ° C. for 10 hours. The reaction was carried out under a mixed atmosphere of air / nitrogen (10/90% by volume). This gives an acid value of 10 KOH-
A curable resin solution (A-2) having a mg / g, a double bond equivalent [resin weight per 1 mol of unsaturated group (g)] of 50 and a weight average molecular weight of 14,000 was obtained. (Synthesis Example 3) 250 g of dipropylene glycol monomethyl ether (MFDG manufactured by Nippon Emulsifier Co., Ltd.) was introduced into a 2 L separable flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen inlet tube, and the temperature was raised to 110 ° C. After warming
Methacrylic acid 113.5g, methyl methacrylate 21
4.0 g, MFDG 200 g, and t-butyl peroxy 2-ethylhexanoate (Perbutyl O manufactured by NOF CORPORATION) 22.0 g were added dropwise over 4 hours. After dropping 3
A trunk polymer having a carboxyl group was synthesized by aging for a time. Next, 222.4 g of 3,4-epoxycyclohexylmethyl acrylate (Cyclomer A200 manufactured by Daicel Chemical Industries, Ltd.), 2.2 g of triphenylphosphine and 1.0 g of methylhydroquinone were added to the above trunk polymer solution, and the mixture was added at 10 ° C. at 10 ° C. Reacted for hours. The reaction is air /
It was carried out under a mixed atmosphere of nitrogen (10/90% by volume). Thereby, a curable resin solution (A-3) having an acid value of 10 KOH-mg / g, a double bond equivalent [resin weight per 1 mol of unsaturated group (g)] 450, and a weight average molecular weight of 15,000.
Got (Synthesis Example 4) 250 g of dipropylene glycol monomethyl ether (MFDG manufactured by Nippon Emulsifier Co., Ltd.) was introduced into a 2 L separable flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introduction tube, and the temperature was raised to 110 ° C. After warming
Methacrylic acid 189.4 g, trimethylcyclohexyl methacrylate 138.1 g, MFDG 200 g and t
22.0 g of -butyl peroxy 2-ethylhexanoate (Perbutyl O manufactured by NOF CORPORATION) was added dropwise over 4 hours. After dropping, the mixture was aged for 3 hours to synthesize a trunk polymer having a carboxyl group. Next, to the above trunk polymer solution,
3,4-epoxycyclohexyl methyl acrylate (Cyclomer A200 manufactured by Daicel Chemical Industries, Ltd.) 22
2.4 g, triphenylphosphine 2.2 g, and methyl hydroquinone 1.0 g were added, and the mixture was reacted at 100 ° C. for 10 hours. The reaction was carried out under a mixed atmosphere of air / nitrogen (10/90% by volume). This gives an acid value of 100 KOH-
A curable resin solution (A-4) having a mg / g, a double bond equivalent [resin weight per 1 mol of unsaturated group (g)] 450 and a weight average molecular weight of 16,000 was obtained. (Synthesis Example 5) 250 g of propylene glycol nomomethyl ether (MMPG manufactured by Daicel Chemical Industries, Ltd.) was introduced into a 2 L separable flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen inlet tube, and heated to 110 ° C. After heating, βCEA (β carboxyethyl acrylate) 2
5.4 g, methacrylic acid 136.3 g, trimethylcyclohexyl methacrylate 165.9 g, MFDG20
Both 0 g and 22.0 g of t-butyl peroxy 2-ethylhexanoate (Perbutyl O manufactured by NOF CORPORATION) were added dropwise over 4 hours. After dropping, the mixture was aged for 3 hours to synthesize a trunk polymer having a carboxyl group. Next, 3,4-epoxycyclohexylmethyl acrylate (Cyclomer A200 manufactured by Daicel Chemical Industries, Ltd.) was added to the above trunk polymer solution.
222.4 g, triphenylphosphine 2.2 g, and methyl hydroquinone 1.0 g were added, and the mixture was reacted at 100 ° C. for 10 hours. Reaction is air / nitrogen (10/90% by volume)
Was performed under a mixed atmosphere. This gives an acid value of 55 KOH
-Mg / g, double bond equivalent [resin weight per 1 mol of unsaturated group (g)] 450, and a curable resin solution (A-5) having a weight average molecular weight of 13,500 were obtained. (Synthesis Example 6) 250 g of propylene glycol nomomethyl ether (MMPG manufactured by Daicel Chemical Industries, Ltd.) was introduced into a 2 L separable flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen inlet tube, and heated to 110 ° C. After heating, β-CEA (β-carboxyethyl acrylate)
95.2 g, methacrylic acid 132.6 g, trimethylcyclohexyl methacrylate 99.870.5 g, MF
200 g of DG and 22.0 g of t-butyl peroxy 2-ethylhexanoate (Perbutyl O manufactured by NOF CORPORATION) were added dropwise over 4 hours. After dropping, the mixture was aged for 3 hours to synthesize a trunk polymer having a carboxyl group. Next, 3,4-epoxycyclohexyl methyl acrylate (manufactured by Daicel Chemical Industries, Ltd., Cyclomer A was added to the above trunk polymer solution.
200) 222.4 g, triphenylphosphine 2.0
g and 1.0 g of methylhydroquinone were added and reacted at 100 ° C. for 10 hours. The reaction is air / nitrogen (10/90
(Volume%). This gives an acid value of 1
00KOH-mg / g, double bond equivalent [unsaturated group 1mo
Resin weight per liter (g)] 450, weight average molecular weight 1
4,000 curable resin solution (A-6) was obtained. (Synthesis Example 7) 250 g of dipropylene glycol monomethyl ether (MFDG manufactured by Nippon Emulsifier Co., Ltd.) was introduced into a 2 L separable flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introduction tube, and the temperature was raised to 110 ° C. After warming
Methacrylic acid 189.4 g, methyl methacrylate 13
8.1 g, MFDG 200 g, and t-butyl peroxy 2-ethylhexanoate (Perbutyl O manufactured by NOF CORPORATION) 22.0 g were added dropwise over 4 hours. After dropping 3
A trunk polymer having a carboxyl group was synthesized by aging for a time. Next, 222.4 g of 3,4-epoxycyclohexyl methyl acrylate (Cyclomer A200 manufactured by Daicel Chemical Industries, Ltd.), 2.2 g of triphenylphosphine and 1.0 g of methylhydroquinone were added to the above trunk polymer solution, and the mixture was added at 10 ° C. at 10 ° C. Reacted for hours. The reaction is air /
It was carried out under a mixed atmosphere of nitrogen (10/90% by volume). Thereby, a curable resin solution (A-7) having an acid value of 100 KOH-mg / g, a double bond equivalent [resin weight per 1 mol of unsaturated group (g)] 450, and a weight average molecular weight of 16,000.
Got (Synthesis Example 8) 1090 g of a cresol novolac type epoxy resin (YDCN-702 manufactured by Tohto Kasei Co., Ltd.) having an epoxy equivalent of 215 was placed in a 2 L separable flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen inlet tube. It was introduced and heated and melted at 100 ° C. Then acrylic acid 3
90 g, 1.5 g of methylhydroquinone and 2 g of dimethylbenzylamine were added and reacted at 110 ° C. for 12 hours. Thereby, an acrylic acid-modified product of a novolac type epoxy compound having an acid value of 3.0 KOH-mg / g was synthesized.
Ethylcarbitol acetate 2 was added to 450 g of this product.
After introducing 50 g and heating to 80 ° C., 0.5 mol of tetraphthalic anhydride is reacted with 1 hydroxyl group equivalent to give an acid value of 58 KOH.
After the acrylic acid modification of -mg / g of the epoxy resin, a curable resin solution (A-8) having an unsaturated group and an acid group added with an acid anhydride was obtained.

<Example 1> 300 parts by weight of the solution of Synthesis Example 1 of unsaturated resin was mixed with 10 parts of α-hydroxyisobutylphenone.
After adding 1 part by weight, the solution was coated on an aluminum plate with a bar coater and dried at 80 ° C. for 15 minutes, and then 1
UV was irradiated with a 20 W / cm high-pressure mercury lamp for 5 seconds to cure. The coating thickness was about 20 μm. The water resistance was evaluated by examining the initial adhesion of this coating film and the adhesion after immersion in water. <Example 2> 10 parts by weight of α-hydroxyisobutylphenone was added to 300 parts by weight of the solution of Synthesis Example 2 of unsaturated resin, and this solution was coated on an aluminum plate with a bar coater and dried at 80 ° C for 15 minutes. 120 W / cm
UV irradiation was carried out for 5 seconds with a high pressure mercury lamp to cure. The coating thickness was about 20 μm. The water resistance was evaluated by examining the initial adhesion of this coating film and the adhesion after immersion in water. <Example 3> To 270 parts by weight of the solution of Synthesis Example 3 of unsaturated resin, 30 parts by weight of trimethylcyclohexyl methacrylate and 10 parts by weight of α-hydroxyisobutylphenone were added, and then the solution was coated on an aluminum plate with a bar coater. 120W / c after drying at 80 ℃ for 15 minutes
UV irradiation was carried out for 5 seconds with a high pressure mercury lamp to cure. The coating thickness was about 20 μm. The water resistance was evaluated by examining the initial adhesion of this coating film and the adhesion after immersion in water.

Comparative Example 1 300 parts by weight of the solution of Synthesis Example 3 of unsaturated resin was mixed with 10 parts of α-hydroxyisobutylphenone.
After adding 1 part by weight, the solution was coated on an aluminum plate with a bar coater and dried at 80 ° C. for 15 minutes, and then 1
UV was irradiated with a 20 W / cm high-pressure mercury lamp for 5 seconds to cure. The coating thickness was about 20 μm. Further, the water resistance was examined by examining the initial adhesion of this coating film and the adhesion after immersion in water.

[0025]

[Table 1]

[Examples 4 to 10 and Comparative Examples 2 to 3] Resin solutions A4 to 8 are 100 parts by weight (solid content) as shown in Table 2.
And 10 parts by weight of TCMMA (Examples 9 to 10)
Only), trimethylolpropane triacrylate 20
20 parts by weight of cresol novolac type epoxy resin (Epicoat 180S70 manufactured by Yuka Shell Epoxy Co., Ltd.) having an epoxy equivalent of 220 parts by weight, benzyl methyl ketal 7
Parts by weight, 2 parts by weight of diethylthioxanthone, 1.5 parts by weight of phthalocyanine green, 5 parts by weight of silica, 20 parts by weight of barium sulfate, 5 parts by weight of dicyandiamide, and then kneaded with a three-roll mill to give a viscous ink composition. Got The ink obtained above was applied on a patterned substrate using a bar coater to a thickness of 20 μm, and 8
It was dried for 20 minutes by a blow dryer at 0 ° C. Then, the negative film was brought into close contact with the film and irradiated with a light amount of 800 mJ / cm ² . Further, it was developed with a 1% sodium carbonate aqueous solution, and the obtained coating film was cured in a 150 ° C. blower oven for 30 minutes to obtain a coating film. Next, similarly to Examples 1 to 3, the water resistance was evaluated by examining the initial adhesion of the coating film and the adhesion after immersion in water.

[0027]

[Table 2]

(Finger touch dryness) After the completion of drying, tackiness by touch with fingers was examined and evaluated according to the following criteria. ◯: No tack. Δ: Some tack. X: Tack (sensitivity). Evaluation was performed using a 21-step step tablet manufactured by Stofer. Adhesion after immersion in water: After immersing the coated plate in warm water at 50 ° C for 1 day, wipe off water on the surface and leave at room temperature for 1 hour, and then at 1 mm intervals on the test piece according to the test method of JIS D-0202. 100 goggles-like cuts were put in, and then peeling was performed with a cellophane adhesive tape, and the number of squares which did not peel was expressed as a molecule, and the original number of squares (100) was expressed as a molecule.

[0029]

As is clear from the above results, the inks of the examples are superior to the comparative examples in adhesiveness after immersion in water. It was also found to be excellent in tack-free property. From the above, it was found that the photocurable resin containing the compound having the structure of formula (I) or the polymer having the structure of formula (I) as an essential component has excellent water resistance.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ identification code FI theme code (reference) C09D 4/00 C09D 4/00 4J038 G03F 7/038 501 G03F 7/038 501 F term (reference) 2H025 AA14 AA20 AB11 AB13 AB15 AC01 AD01 BC13 BC53 BC74 BC82 BC85 CA00 CB13 CB14 CB28 CB29 CB30 CB41 CB51 CC11 FA17 4F071 AA33 AA42 BA02 BC01 4J002 BG071 CD002 FD096 4J027 AA02 AE01 BA07 CA10 CB03 CB10 CD06 CD08 4J036 AA01 AK06 AK08 AK11 DA01 EA03 HA02 JA01 JA07 JA09 KA01 4J038 FA001 FA111 FA252 KA03

Claims (8)

[Claims] 1. The following structural formula (I): (R ¹ represents hydrogen or a C _{1 to} C ₇ hydrocarbon group. R ^{2 to} R ⁴ are
Represents a hydrocarbon group of C ₁ -C _7, they may be be the same or different. And a thermosetting resin composition containing a curable resin as an essential component. 2. The following structural formula (I): (R ¹ represents hydrogen or a C _{1 to} C ₇ hydrocarbon group. R ^{2 to} R ⁴ are
Represents a hydrocarbon group of C ₁ -C _7, they may be be the same or different. A photo- and / or thermosetting resin composition comprising a polymer containing a compound having a) in a resin skeleton and optionally a curable resin as an essential component. 3. The photo- and / or thermosetting resin composition according to claim 1, which contains a photopolymerization initiator and a diluting monomer or oligomer. 4. The acid value is 10 to 150 KOH-mg / g.
The light and / or thermosetting resin composition according to any one of claims 1 to 3, wherein 5. The photo- and / or thermosetting resin composition according to claim 1, which contains an epoxy compound and / or an epoxy resin. 6. The light and / or thermosetting resin composition according to claim 1, which contains a pigment. 7. The light and / or light according to any one of claims 1 to 6, which comprises a novolac or a bisphenol epoxy resin modified with (meth) acrylic acid and then added with an acid anhydride.
Or a thermosetting resin composition. 8. A liquid resist comprising the light and / or thermosetting resin composition according to claim 1, a dry film, a color filter used for a liquid crystal display, a pigment resist, a wiring board insulating material, or Coating protective film.