JPH04184443A - Photosetting resin composition - Google Patents

Abstract

PURPOSE:To obtain a photosetting resin compsn. having high sensitivity to light and alkali developability and giving a cured body having superior moisture and water resistances and adhesion to the base material by incorporating specified amts. of specified resins, a photopolymn. initiator and a catalyst for the reaction of carboxyl and epoxy groups. CONSTITUTION:Carboxylated (meth)acrylate resin (A) and/or carboxylated epoxy resin (B), other epoxy resin (C), a photopolymn. initiator (D) including a cationic photopolymn. initiator and a catalyst (E) for the reaction of carboxyl and epoxy groups are incorporated. The amt. of the resin C is 30-70 wt.% of the total amt. of the resins A-C. The amt. of the initiator D is 0.5-10 pts. wt. per 100 pts. wt., in total, of the resins A-C. The amt. of the catalyst E is 0.01-10 pts.wt. per 100 pts.wt., in total, of the resins A-C. A photosetting resin compsn. giving a cured body having superior moisture and water resistances and adhesion to the base material after alkali development is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention is a resin composition that is cured by irradiation with active energy rays such as ultraviolet rays.

The photocurable resin composition of the present invention can be used as a pattern forming material, and its cured product has excellent adhesion and moisture resistance to glass, ceramics, plastics, glass/epoxy substrates, metals, etc. , excellent water resistance.

<Prior Art> In recent years, photocurable resin compositions have come to be used in various fields as paints, inks, sealing materials, resist materials, pattern forming materials, adhesives, coating agents, etc. .

Examples of such photocurable resin compositions include photocurable acrylate resin compositions (for example, JP-A No. 0F-308415, JP-A-61-291646, etc.), photocurable epoxy resin compositions (for example, JP-A-Heisei 0F-308415, JP-A-61-291646, etc.); 02-113022
JP-A-01-149848, etc.), but paints, inks, sealing materials, resist materials,
A photocurable acrylate resin composition is mainly used as the pattern forming material.

However, most pattern-forming materials composed of conventionally known photocurable acrylate resin compositions use organic solvents during development, which poses problems in terms of environmental hygiene. Since the solvent is expensive, it is economically disadvantageous, and the remaining portion (consisting of the cured product of the photocurable acrylate resin composition) cannot be said to have sufficient solvent resistance or water resistance. Furthermore, the remaining portion was poor in adhesion to the base material (adherent), moisture resistance, and water resistance.

<Problems to be Solved by the Invention> The present invention has characteristics that could not be achieved with conventional photocurable resin compositions, that is, it has high sensitivity to light and is suitable for use in Bakun formation. The purpose of the present invention is to provide a photocurable resin composition that can be developed with a basic aqueous solution instead of an organic solvent, and whose cured product has excellent adhesion to a substrate, moisture resistance, and water resistance.

<Means for solving the problems> The present invention provides carboxylated (meth)acrylate resin (
A) and/or carboxylated epoxy resin (B)
, a carboxylated epoxy resin, an epoxy resin other than (B) (C), a photopolymerization initiator (D) containing a cationic photopolymerization initiator, J, and a reaction catalyst between a carboxyl group and an epoxy group (E). , the content of the resin (C) is 30 to 70% by weight of the total amount of the resin (A), the resin (B), and the resin (C), and the content of the resin (C) is 30 to 70% by weight of the total amount of the resin (A), the resin (B), and the resin (C). The content of the initiator (D) is the same as that of the resin (A).
), total amount of the resin (B) and the resin (C) 10
The content of the reaction catalyst (E) is 0.5 to 10 parts by weight relative to 0 parts by weight.
)! 3 and the resin (C) in a total amount of 0.01 to 10 parts by weight based on 100 parts by weight of the total amount of the resin (C).

The present invention will be explained in detail below.

First, the essential constituent components of the photocurable resin composition of the present invention will be explained.

What is carboxylated (meth)acrylate resin (A)?
It is a compound that has at least one acryloyl group and/or methacryloyl group and one or more carboxyl groups in the same molecule. For example, it is a compound obtained by reacting a reaction product of an epoxy compound and an unsaturated monocarboxylic acid with a saturated or unsaturated polybasic acid anhydride.

Here, carboxylated (meth)acrylate resin (A
) are described below.

The epoxy compound used as one of the raw material compounds of the carboxylated (meth)acrylate resin (A) is -
Any compound having one or more epoxy groups in the molecule may be used, but bisphenol A type epoxy resins, bisphenol F type epoxy resins, novolac type epoxy resins, etc. having two or more epoxy groups in the molecule are suitable. preferable.

Further, unsaturated monocarboxylic acids include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, and the like.

Furthermore, as saturated or unsaturated polybasic acid anhydrides, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, Tribasic acid anhydrides such as endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydrophthalic anhydride:
Aromatic polycarboxylic acid anhydrides such as trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, and other accompanying substances such as 5-(2,
5-dioxytetrahydrofuryl)-3-methyl-3-
Examples include polyhydric carboxylic anhydride derivatives such as cyclohexene-1,2-dicarboxylic anhydride.

The carboxylated epoxy resin (B) is a compound having - or more epoxy groups and carboxyl groups in the same molecule. For example, it is a compound obtained by reacting an epoxy compound with a saturated or unsaturated polybasic acid anhydride.

The epoxy compound and the saturated or unsaturated polybasic acid anhydride, which are the raw material compounds for the carboxylated epoxy resin (B), are as described above.

The photocurable resin composition of the present invention contains a carboxylated (meth)acrylate resin (A) and/or a carboxylated epoxy resin (B).
There are also resins that fall under both meth)acrylate resins (A) and carboxylated epoxy resins (B). That is, an acryloyl group and/or a methacryloyl group, an epoxy group, and a carboxyl group are each contained in the same molecule.
This is a compound obtained by esterifying a portion of the epoxy groups of an epoxy resin with an unsaturated carboxylic acid and then reacting it with a saturated or unsaturated polybasic acid anhydride. Note that one of such compounds is a compound represented by the following formula 1.

Q=O ■ = ■ ○ The carboxylated (meth)acrylate resin (A) and/or carboxylated epoxy resin (B) in the photocurable resin composition of the present invention can be prepared by dissolving the resin composition in a basic aqueous solution. It is important for the purpose of gender.

By measuring the acid value of these compounds,
The solubility of the resin composition in a basic aqueous solution can be determined.

Epoxy resins (C) other than carboxylated epoxy resins (B) include epoxy resins other than carboxylated epoxy resins (B) among epoxy resins.

Epoxy resins corresponding to this include bisphenol A epoxy resins and bisphenol F epoxy resins obtained by reacting bisphenol A, bisphenol F, etc. with epichlorohydrin, epoxy resins hydrogenated with these, and alicyclic epoxy resins. formula epoxy resin, aliphatic epoxy resin, glycidyl ester type epoxy resin, novolac type epoxy resin, epoxy resin having (meth)acryloyl group and epoxy group in the same molecule, urethane-modified epoxy resin having urethane bond, metaxylene diamine, etc. Nitrogen-containing epoxy resin made by epoxidizing hydantoin, etc.
Examples include, but are not limited to, rubber-modified epoxy resins containing polybutadiene or NBR.

Examples of commercially available epoxy resins include 840S and 850S manufactured by Dainippon Ink and Chemicals.

850A, 850P, EXA-85OCR, EXA
-850CRP, 830P.

EXA-830LVP, EXA-830CRP,
N-73OA, N-738A, etc., Sumitomo Chemical's ELA-070, ESCN-100T, etc., Dow Chemical, etc.
Le company 0) QUATREX series (1010,1
410°2010, 2410.3410), TAC
TIX 556 etc., Asahi Denka Kogyo's KRM series (2
199, 2200, 2206゜2410, 2510)
etc., 150ONP of Kyoeisha Yushi Kagaku Kogyo ■ etc.

The epoxy resin (C) other than the carboxylated epoxy resin (B) in the photocurable resin composition of the present invention contributes to the adhesiveness and water resistance of the cured product of the resin composition.

In the present invention, a cationic polymerization initiator is always used as the photopolymerization initiator (D).

The cationic photopolymerization initiator used in the present invention refers to cationic compounds such as aromatic diazonium salts, aromatic iodonium salts, aromatic sulfonium salts, aromatic selenium salts, and metallocene compounds.

All of these photopolymerization initiators are decomposed by ultraviolet light and release Lewis acids, which polymerize epoxy groups.

Among the cationic photopolymerization initiators, the cation moieties of aromatic diazonium salts, aromatic iodonium salts, aromatic sulfonium salts, and aromatic selenium salts are as follows, and the corresponding anions are SbF, -1AsFa, etc.
-1ppa-1BF, -, etc.

More specifically, aromatic diazonium salts, aromatic iodonium salts, aromatic sulfonium salts, and aromatic selenium salts include p-chlorobenzenediazonium hexafluorophosphate, p-methoxybenzenediazonium hexafluorophosphate, Examples include diphenyliodonium hexafluorophosphate, triphenylsulfonium hexafluorophosphate, p-methoxybenzenediazonium hexafluoroantimonate, triphenylsulfonium hexafluoroantimonate.

In addition, as a commercially available cationic photopolymerization initiator, aromatic diazonium salt ULTRASET (manufactured by Asahi Denka Co., Ltd.) is available.
, AMERICURE (manufactured by American Can Co., Ltd.)
etc., aromatic iodonium salt UVI series (manufactured by GE), FC series (manufactured by 3M), etc., aromatic sulfonium salt OPTOMER5P-150゜5P-170 (manufactured by Asahi Denka), UVI series (manufactured by UCC) IRUGACUR of metallocene compounds such as , UVE series (manufactured by GE), FC series and Fx series (manufactured by 3M)
E 261 (manufactured by CIBA-GEIGY) and the like.

In addition, the effective wavelength for the decomposition of these cationic photoinitiators varies mainly depending on the chemical structure of the cationic moiety, and the curing speed mainly depends on the type of anionic moiety that is the counterion and the compound to be cured. Since it varies depending on the type, you can select the appropriate one depending on the purpose.

In the present invention, only a cationic photoinitiator may be used as the photoinitiator (D), but a cationic polymerization initiator and another photoinitiator may be used in combination.

Other photopolymerization initiators include radical photopolymerization initiators.

More specifically, benzoin and its alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-jethoxy-2- Phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenylketone, 2-
Acetophenones such as methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one; 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, l-chloroanthraquinone, 2 -Anthraquinones such as amyl anthraquinone; 2,4-dimethylthioxanthone, 2,4-
diethylthioxanthone, 2-chlorothioxanthone,
Examples of the radical photopolymerization initiator include thioxanthone such as 2.4-diisopropylthioxanthone, ketal such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenone such as benzophenone; and xanthone.

In addition, when using two or more types of compounds together as the photopolymerization initiator (D), it is preferable to combine compounds that act with light of similar wavelengths.

The catalyst (E) for the reaction between a carboxyl group and an epoxy group is not particularly limited as long as it is a compound that catalyzes the reaction between a carboxyl group and an epoxy group. Specific examples include triphenylphosphine and pyridine.

The above are the essential constituent components of the photocurable resin composition of the present invention. Next, the content ratio will be described.

Carboxylated (meth)acrylate resin (A) and/or carboxylated epoxy resin (B), and epoxy resin (C) other than carboxylated epoxy resin (B)
is used so that the resin (C) accounts for 30 to 70% by weight of the total amount of the resin (A), the resin (B), and the resin (C). If the resin (C) is less than 30% by weight, the water-resistant adhesion of the cured product of the photocurable resin composition will be poor, and if it is more than 70% by weight, the developability in a basic aqueous solution (alkaline developability) will be poor. ) becomes defective.

The content of the photopolymerization initiator (D) containing a cationic photopolymerization initiator is 0.5 to 100 parts by weight in total of the resin (A), the resin (B), and the resin (C). The amount is 10 parts by weight, preferably 3 to 5 parts by weight. If the amount is less than 0.5 parts by weight, the effect of adding the photopolymerization initiator cannot be obtained, and 1
If the amount exceeds 0 parts by weight, not only no further improvement in the effect can be obtained, but also disadvantages appear due to unreacted photoinitiator remaining in the cured resin product, and there is also an increase in cost. It will be disadvantageous.

The content of the reaction catalyst (E) between a carboxyl group and an epoxy group is 0.01 to 1OM based on 100 parts by weight of the total amount of the resin (A), the resin (B), and the resin (C).
parts by weight, preferably 0.1 to 5 parts by weight. 0.01
If the amount is less than 1 part by weight, the effect of adding the reaction catalyst (E) cannot be obtained, and as a result, carboxyl groups remain in the cured product of the photocurable resin composition of the present invention, resulting in poor water resistance of the cured product. If the amount exceeds 10 M parts, not only will no further improvement in the effect be obtained, but it will also be disadvantageous in terms of cost.

The essential constituent components of the photocurable resin composition of the present invention are as described above, but in addition, a photopolymerizable monomer (diluent), a silane coupling agent, a leveling agent, as long as the gist of the present invention is not impaired. , a photosensitization aid, a photosensitization accelerator, a thermal polymerization initiator, and further fillers, thickeners, plasticizers, stabilizers, tackifiers, and the like may also be contained.

The photopolymerizable monomer is effective for diluting the photocurable resin composition and making it easy to apply. Photopolymerizable monomers include 2-hydroxyethyl acrylate, 2-
A water-soluble monomer such as hydroxypropyl acrylate, N-vinylpyrrolidone, acryloylmorpholine, methoxytetraethylene glycol acrylate, methoxypolyethylene glycol acrylate, polyethylene glycol diacrylate, or each methacrylate corresponding to the above acrylate, diethylene glycol acrylate, triethylene Glycol diacrylate, propylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, phenoxyethyl acrylate, tetrahydrofurfuryl acrylate, cyclohexyl acrylate,
Trimethylolpropane diacrylate, trimethylolpropane triacrylate, glycerin diglycidyl ether diacrylate, glycerin triglycidyl ether triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, iso borneolyl acrylate, mono- or di-acrylate of cyclopentadiene or methacrylates corresponding to the above acrylates, mono-, di-, tri- or higher polyesters of polybasic acids and hydroxyalkyl (meth)acrylates; Since it has a high water solubility, it may be used as appropriate, taking into consideration the solubility of the photocurable resin composition of the present invention in a basic aqueous solution and the water resistance of the cured product of the resin composition.

Examples of photosensitization aids include 2-chlorothioxanthone, 2,4-diisobubutylthioxanthone, 2,4-dimethylthioxanthone, and benzophenone; examples of photosensitization accelerators include triethylamine, triethanolamine, and 2-chlorothioxanthone; Examples include dimethylaminoethanol, triphenylphosphine, and β-thiodiglycol.

The photocurable resin composition of the present invention can be prepared by stirring its components,
Obtained by mixing. Then, store it in a dark place.

The photocurable resin composition of the present invention is cured using a mercury lamp, a xenon lamp, a carbon arc, a metal halide lamp, sunlight, etc. as an ultraviolet irradiation source.
Intensity 1-100 m W/c including nm ultraviolet rays
It is sufficient to irradiate with a light beam of m'' in air or in an inert gas atmosphere. When irradiating in air, a high-pressure mercury lamp is preferable as the irradiation source.

The photocurable resin composition of the present invention is particularly useful for liquid crystal 0)s edge overcoat parts, and is also suitable as a pattern forming material for printed wiring boards.

An example of how to use the photocurable resin composition of the present invention as a pattern forming material is shown below.

(2) Applying a photocurable resin composition to the substrate.

■Cover with a patterned mask and irradiate with light to perform photopolymerization.

■Remove the mask and perform alkaline development. In this step, the parts that were not irradiated with light melt and are removed from the substrate. Note that the alkaline developing solution is a weakly basic aqueous solution (for example, 1% Na*COs, etc.).

■Perform thermal polymerization (after-cure) if necessary.

This improves the water resistance of the remaining portion (cured product of the photocurable resin composition). The after-cure conditions are preferably 120 to 200°C for about 30 to 60 minutes.

<Example> EXAMPLES The present invention will be specifically explained below with reference to Examples.

(Example) Each photocurable resin composition whose composition is shown in Table 1 was prepared by measuring and mixing the ingredients.

The alkaline developability and water-resistant adhesive properties of these were evaluated using the following methods.

The results are shown in Table 1.

<Test method> 1. Each resin composition was applied to a thickness of 50 μm on an alkali-developable glass plate, and a mask with a line spacing of 1100 μm was applied to lo00 mJ/
cm" of ultraviolet rays to photocure. Next, the mask was removed, and the glass plate was immersed in a 1% NazCOm aqueous solution and developed by shaking. Good developability is indicated by ○,
A state in which development could not be performed was evaluated as ×, and a state in the middle was evaluated as Δ.

2. Adhesion Each resin composition was applied between two glass plates to a thickness of 50 μm and a diameter of 7 mm, and was irradiated with ultraviolet rays of 10,100 O/cm” to photocure. After this, the resin composition was cured at 150°C. After curing for 30 minutes, a sample was obtained.

Each sample was immersed in water at 85°C for 24 hours, and then
A peel test was conducted according to JIS to measure the adhesive strength.

Ladle 50% carboxylated acrylate of cresol novolac type epoxy resin, epoxy equivalent 655, acid value 80.5, manufactured by Shin Nakamura Chemical Industry ■ Umbrella 2 Carboxylated acrylate of cresol novolac type epoxy resin, acid value 80 , manufactured by Shin Nakamura Chemical Co., Ltd. 3 Carboxylated acrylate of phenol novolac type epoxy resin, acid value 80, manufactured by Shin Nakamura Chemical Co., Ltd.*4 Carboxylated acrylate of bisphenol A type epoxy resin, acid value 80 , Shin Nakamura Chemical Co., Ltd. Umbrella 5 50% acrylate of cresol novolac type epoxy resin, epoxy equivalent 498, manufactured by Shin Nakamura Chemical Co., Ltd.*6 50% acrylate of phenol novolac type epoxy resin, epoxy equivalent 422, Shin Nakamura Chemical Co., Ltd. Umbrella 7 50% acrylate of bisphenol A type epoxy resin, epoxy equivalent: 451, manufactured by Shin Nakamura Chemical Co., Ltd. *8 Bisphenol A type epoxy resin, epoxy equivalent: 180, manufactured by Sumitomo Chemical Co., Ltd. *9 Bisphenol A type epoxy resin, epoxy equivalent 475, Kadenka Kogyo ■ Kasa 102-hydroxyethyl acrylate, Kyoeisha Yushi Kagaku Kogyo Co., Ltd. Ill radical photopolymerization initiator, benzyl dimethyl ketal, Ciba Geigy *12 Sulfonium salt-based cationic photopolymerization initiator, electrification Umbrella manufactured by Kogyo 13 Manufactured by Asahi Denka Kogyo ■ 14 γ-Glycidoxyprobyltrimethoxysilane,
As is clear from Table 1, the photocurable resin composition of the present invention has good alkali developability and water-resistant adhesion.
Carboxylated (meth)acrylate resin (A) and/or carboxylated epoxy resin (B), and epoxy resin (C) other than carboxylated epoxy resin (B)
If the proportion of the resin (C) in the total amount exceeds 70% by weight (Comparative Example 1), the alkali developability will be poor;
If it is less than 30% by weight (Comparative Example 2), the water resistant adhesion will be poor.

<Effects of the Invention> The present invention provides a photocurable resin composition that is highly sensitive to light, has alkali developability, and whose cured product has excellent adhesion to a substrate, moisture resistance, and water resistance. will be provided.

Claims (1)

[Claims] (1) Carboxylated (meth)acrylate resin (A)
and/or carboxylated epoxy resin (B), epoxy resin other than carboxylated epoxy resin (B) (
C), a photopolymerization initiator containing a cationic photoinitiator (D
), and reaction catalyst between carboxyl group and epoxy group (
E), the content of the resin (C) is 30 to 70% by weight of the total amount of the resin (A), the resin (B), and the resin (C), and the content is 30 to 70% by weight of the total amount of the resin (A), the resin (B), and the resin (C), and The content of the photopolymerization initiator (D) containing the agent is 0.0 parts by weight based on 100 parts by weight of the total amount of the resin (A), the resin (B), and the resin (C).
5 to 10 parts by weight, and the content of the reaction catalyst (E) is the same as that of the resin (A), the resin (B), and the resin (C
) is 0.01 to 10 parts by weight based on 100 parts by weight of the total amount of the photocurable resin composition.