JPH0583562B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a photopolymerization initiator composition for polymerizing unsaturated compounds. It is well known that monomers, oligomers, and polymers containing unsaturated bonds in their molecules are photopolymerized in the presence of a photoinitiator, and photopolymers are used to create printing plates, printed circuit boards, ICs, etc. It is widely used as a photoresist. [Prior Art] As a highly sensitive photopolymerization initiator used in photopolymers and photoresists, for example,
A photopolymerization initiator consisting of a combination of a benzoylperoxy compound and an aromatic carbonyl compound represented by xanthone in No. 59-20304, and an organic peroxide in JP-A-59-45303 and JP-A-60-76503. There are photopolymerization initiators made of a combination of pyrylium salts and pyrylium salts or thiopyrylium salts. In addition, 4,
A photopolymerizable composition is described that combines 4'-bis(dialkylamino)benzophenone, an aromatic ketone compound, and an organic peroxide. [Problems to be solved by the invention] For practical use in printing plate materials, a strong film is required to print a larger number of copies, and for practical use in photoresist materials, acid resistance is required. This is essential, and for that reason, the strength of the membrane is also important.
As described above, the market needs for photopolymerization initiators include higher sensitivity and higher film strength. However, with the above-mentioned photopolymerization initiator consisting of a combination of an organic peroxide and a visible light absorbing compound, it is possible to obtain a highly sensitive image, but when considering practicality, the strength of the film on which the image is formed is limited. Not enough. An object of the present invention is to provide a photopolymerization initiator composition that is highly sensitive and can provide sufficient photocured film strength. [Means for solving the problem] The present invention provides benzophenone group-containing polyhydric peroxyester represented by the following general formula (I), 4,4'-bis(dialkylamino)benzophenone represented by the general formula (), and the following The present invention provides a photopolymerization initiator composition for polymerizing unsaturated monomers comprising the photosensitizing dye shown in the following.

[In the formula, R ₁ and R′ ₁ each have 4 to 8 carbon atoms]
A tertiary alkyl group or a tertiary aralkyl group having 9 to 12 carbon atoms, R ₂ and R' ₂ are each a hydrogen atom, a tertiary alkoxy group having 4 to 8 carbon atoms, or a tertiary aralkyloxy group having 9 to 12 carbon atoms represents. ]

[However, R represents an alkyl group, a cycloalkyl group, or a hydroxyalkyl group having 1 to 6 carbon atoms. ]

Photosensitizing dyes [benzalacetophenones, pyrylium salts,
One or more selected from thiopyrylium salts, cyanine dyes, merocyanine dyes, xanthene dyes, and thiazole dyes] Examples of the benzophenone group-containing polyhydric peroxyester represented by the general formula (I) used in the present invention are: , for example, 3,3',4,4'-tetra-(t-
butylperoxycarbonyl)benzophenone,
3,3',4,4'-tetra-(t-amylperoxycarbonyl)benzophenone, 3,3',4,
4'-tetra(t-hexylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra(t-octylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra(cumylperoxycarbonyl) benzophenone, 3,3',4,
Examples include 4'-tetra(p-isopropylcumylperoxycarbonyl)benzophenone, and these may be used alone or in combination of two or more. 4 represented by the general formula () used in the present invention,
Examples of 4'-bis(dialkylamino)benzophenone include 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(dicyclohexylamino)benzophenone, Examples include 4,4'-bis(dihydroxyethylamino)benzophenone. Among these, 4,4'-bis(dimethylamino)benzophenone and 4,4'-bis(diethylamino)benzophenone are particularly preferred. Photosensitizing dyes used in the present invention include benzalacetophenones, pyrylium salts, thiopyrylium salts, cyanine dyes, merocyanine dyes,
Compounds that absorb visible light, such as xanthene dyes and thiazole dyes. Examples of the above benzalacetophenones include:
Benzalacetophenone, benzalmethylacetophenone, methylbenzalmethylacetophenone, methylbenzalethylacetophenone, methylbenzalmethoxyacetophenone, ethylbenzalbutoxyacetophenone, methoxybenzalmethoxyaceto Phenone, methoxybenzalethyl acetophenone, ethylbenzalphenoxyacetophenone, butylbenzalmethoxyacetophenone, benzaldimethylaminoacetophenone, dimethylaminobenzaldimethylaminoacetophenone, methoxybenzaldimethylamino Acetophenone, aminobenzalaminoacetophenone, dimethylaminobenzalmethoxyacetophenone, benzaldiethylaminoacetophenone, dimethylaminobenzalacetophenone, butoxybenzaldimethylaminoacetophenone,
Examples include chlorobenzalmethylacetophenone, methylbenzalnitroacetophenone, benzalnitroacetophenone, and nitrobenzalacetophenone. Examples of pyrylium salts and thiopyrylium salts include 2,4,6-triphenylpyrylium perchlorate, 4-(4-methoxyphenyl)-
2,6-diphenylpyrylium perchlorate,
2,6-bis(4-methoxyphenyl)-4-phenylpyrylium perchlorate, 4-(4-butoxyphenyl)-2,6-diphenylpyrylium perchlorate, 4-(4-amyloxyphenyl) )-2,6-bis(4-ethylphenyl)pyrylium perchlorate, 2,4,6-triphenylpyrylium fluoroborate, 2,4,6-triphenylthiapyrylium perchlorate, 2,
6-bis(4-ethylphenyl)-4-(4-amyloxyphenyl)thiopyrylium perchlorate, 4-(4-methoxyphenyl)-2,6-diphenylthiopyrylium perchlorate, 6-( 4
-ethoxyphenyl)-2,4-diphenylthiopyrylium perchlorate, 2,4,6-tri(4-methoxyphenyl)thiopyrylium perchlorate, 4-(4-amyloxyphenyl)-2 ，
6-bis(4-ethylphenyl)thiopyrylium perchlorate, 2,4,6-triphenylthiopyrylium fluoroborate, 2,4,6-triphenylthiopyrylium sulfate, 4-(4
-methoxyphenyl)-2,6-diphenylthiopyrylium fluoroborate, 2-(4-amyloxyphenyl)-4,6-diphenylthiopyrylium fluoroborate, 4-(4-amyloxyphenyl) )-2,6-bis(4-methoxyphenyl)
Thiopyrylium perchlorate, 4-(4-methoxyphenyl)-2,6-bis(4-ethylphenyl)thiopyrylium perchlorate, 4-(2,
4-dichlorophenyl)-2,6-diphenylpyrylium perchlorate, 2-(3,4-dichlorophenyl)-4-(4-methoxyphenyl)-6
-Phenylpyrylium perchlorate, 4-(4
-amyloxyphenyl)-2,6-bis(4-ethylphenyl)pyrylium perchlorate, 2,
6-bis(4-ethylphenyl)-4-(4-methoxyphenyl)pyrylium fluoroborate, 4
-(4-dimethylaminophenyl)-2,6-diphenylpyrylium perchlorate, 2,6-bis(4-ethylphenyl)-4-methoxyphenylthiopyrylium fluoroborate, 4-(4-butoxyphenyl) -2,6-bis(4-dimethoxyphenyl)thiopyrylium fluoroborate,
2,6-bis(4-methoxyphenyl)-4-phenylthiopyrylium perchlorate, 4-(2,
4-dichlorophenyl)-2,6-diphenylthiopyrylium perchlorate, 2,6-bis(4
-amyloxyphenyl)-4-(4-methoxyphenyl)thiopyrylium perchlorate and the like. In addition, cyanine dyes, merocyanine dyes,
Examples of xanthene dyes and thiazole dyes include the following. A: Cyanine dye

[R ₁ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms,
It represents an aryl group, an alkoxy group or a dialkylamino group, _R2 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aryl group, X represents a halogen atom, and n represents an integer from 1 to 3. Y is

【formula】

【formula】

[expression] or

Represents [formula]. ]

[R ₁ and R ₂ represent a hydrogen atom, an alkyl group or an aryl group having 1 to 10 carbon atoms, X represents a halogen atom,

【ceremony

【formula】

【formula】

【formula】

【formula】 or

Represents [formula].

[R ₁ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms,
Represents an aryl group or an alkoxy group, R ₂
represents a hydrogen atom, an alkyl group or an aryl group having 1 to 10 carbon atoms, X represents a halogen atom,
n represents an integer from 1 to 3. ] Y is

【formula】,

【formula】,

【formula】 or

Represents [formula]. B: Merocyanine dye

[R ₁ , R ₂ and R ₃ represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group. ]

[Chemical formula] [R ₁ and R ₂ represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, n represents an integer of 1 to 3, and
teeth

【formula】

【formula】

【formula】

【formula】,

【formula】

【formula】

[expression] or

Represents [formula]. ]

[R ₁ , R ₂ and R ₃ represent a hydrogen atom, an alkyl group or an aryl group having 1 to 6 carbon atoms, and X represents a hydrogen atom or an alkali metal. ]

C: Xanthene dye

[X represents a hydrogen atom or an alkali metal; Y represents a hydrogen atom or a halogen atom. ]

[R ₁ , R ₂ , R ₃ , R ₄ represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group, X represents a halogen atom, and Y represents a hydrogen atom or an alkali metal. D: Thiazole dye

[R represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group, an alkoxy group, a nitro group, or an amino group, and X represents an amino group or a phenylamino group. ]

[R ₁ , R ₂ , R ₃ , R ₄ represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group, and R ₅ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group, or a sulfonic acid group. group, and X represents a halogen atom or a hydroxyl group. ]

The photopolymerization initiator composition of the present invention comprises the above-mentioned (A) benzophenone group-containing polyhydric peroxyester and (B)
It consists of 4,4'-bis(dialkylamino)benzophenone and (C) a photosensitizing dye, and (A) and (B)
The mixing ratio of both (A):(B) is 1:100 to 1:100 by weight.
100:1, more preferably 1:10-30:
It is 1. Also, the blending ratio of both (A) and (C) is 1:
100 to 100:1, more preferably 1:30 to
The ratio is 20:1. Outside this range, excellent photopolymerization initiation performance cannot be obtained. The photoinitiator composition of the present invention can photopolymerize almost all unsaturated compounds, especially unsaturated monomers. That is, unsaturated compounds are monomers, oligomers, or polymers having polymerizable ethylenically unsaturated bonds, such as unsaturated acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid and its anhydrides, and fumaric acid. Methyl (meth)acrylate (meth)ethyl acrylate, butyl (meth)acrylate, glycidyl (meth)acrylate,
Hydroxyethyl (meth)acrylate, dimethyl maleate, diethyl maleate, dimethyl fumarate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate ) Unsaturated acid ester compounds such as acrylate, monomers such as styrene, acrylamide, acrylonitrile, N-vinylpyrrolidone, and vinyl acetate, as well as unsaturated polyesters, unsaturated polyethers, unsaturated polyurethanes, epoxy (meth)acrylate compounds, etc. There is. The photopolymerization initiator composition of the present invention is added to these unsaturated compounds alone or in a mixture of two or more, and if necessary, a binder resin or a suitable diluting solvent is added to prepare a photopolymerizable photosensitive liquid. Use as. At that time, the amount of the photopolymerization initiator composition added is 0.1 to 30 parts by weight, preferably 0.5 to 20 parts by weight, based on 100 parts by weight of the unsaturated compound. The binder resin is used as a coating film forming aid for printing plate materials, photoresists, etc. for the purpose of improving physical properties, and is preferably used in an amount of usually about 50 to 500 parts by weight per 100 parts by weight of the unsaturated compound. Examples of the binder resin include (meth)acrylic acid ester resin, vinylpyrrolidone resin,
There are vinyl alcohol-based resins, etc. In addition, any appropriate diluting solvent can be used as long as it dissolves the photopolymerization initiator composition and unsaturated compound of the present invention, such as water, methanol, ethanol, isopropanol, butanol, acetone,
Methyl ethyl ketone, methyl isobutyl ketone,
Toluene, xylene, ethyl acetate, butyl acetate,
Examples include methyl cellosolve, tetrahydrofuran, dioxane, dichloromethane, chloroform, carbon tetrachloride, trichlorethylene, dimethylformamide, and dimethyl sulfoxide. The photopolymerizable photosensitive liquid thus obtained undergoes a photopolymerization reaction by irradiating it with actinic light such as ultraviolet rays, visible light, or laser light. [Effects of the Invention] The photopolymerization initiator composition of the present invention uses a combination of three components: a benzophenone group-containing polyvalent peroxyester, 4,4'-bis(dialkylamino)benzophenone, and a photosensitizing dye. , has significantly higher sensitivity than conventional photopolymerization initiators, and the resulting image film is also tough, making it possible to obtain a practical image film that is sufficiently sensitive to visible light, making it easy to work with. It is superior in terms of performance and economy. The photopolymerization initiator composition of the present invention can be used in ordinary photopolymerization reactions, and can also be applied to a variety of applications such as photocurable paints, printing inks, adhesives, printing plate materials, and photoresists. be. [Examples] The present invention will be explained in more detail below using Examples and Comparative Examples. Parts in the examples indicate parts by weight. Examples 1 to 10 Copolymer of methyl methacrylate and methacrylic acid as binder resin (molecular weight 80000, acid value 65)
100 parts and pentaerythritol triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.: A-
The photopolymerization initiator composition of the present invention shown in Table 1 was added to 100 parts of TMM-3L) in the proportions shown in Table 1, and this was further uniformly dissolved in 1000 parts of methyl cellosolve solvent to obtain a photosensitive liquid. Ta. These photosensitive solutions were applied onto an anodized aluminum plate using a spinner so that the dry film thickness was 1 μm, and the dried products were used as samples for photosensitive testing. (Photosensitivity test) ●Method A (photocuring with ultraviolet rays) Using the above sample, use an integrated light meter (Co., Ltd.) from a distance of 65cm under vacuum using a 2KW ultra-high pressure mercury lamp.
Manufactured by Oak Seisakusho: UV-330AP-1)
Irradiation was performed at an exposure dose of 10 mJ/cm ² . ●Method B (photocuring using visible light) A colored glass filter (Toshiba Glass Co., Ltd.) was applied to the above sample.
Y-47 (manufactured by Co., Ltd.: cuts light of 470 nm or less), and then the exposure amount is 10 mJ/cm ² using the same light source as method A.
It was irradiated so that The photocured film was evaluated by the gel fraction and solubility test shown below. ●The gel fraction was determined as follows. Gel fraction (%) = W ₂ - W ₀ / W ₁ - W ₀ × 100 W ₀ : Weight of aluminum plate in the sample W ₁ : Weight of the sample W ₂ : Weight of the sample exposed and dried after development. The developing process is made by Fuji Photo Film Co., Ltd.
After being immersed for 5 minutes at 25° C. in a developer prepared so that the weight ratio of DN-3C and water was 1:1, the sample was washed with water. A high gel fraction value indicates high sensitivity and sufficient curing by photopolymerization reaction. ●Solvent resistance test: Two layers of gauze soaked in xylol are used to coat the top of the photocured film for 10 minutes.
The membrane was rubbed several times and observed whether any abnormalities such as swelling or dissolution occurred in the membrane. The results are shown in Table-1. Comparative Examples 1 to 4 Table of benzophenone group-containing polyhydric peroxyesters, 4,4'-bis(dialkylamino)benzophenones, each alone and combinations with photosensitizing dyes, etc.
Samples were prepared in the same manner as in Examples using the photopolymerization initiator shown in 1, and after exposure, gel fraction and solvent resistance tests were conducted. The results are shown in Table-1. Comparative Examples 5 and 6 Samples were prepared in the same manner as in the examples using the photopolymerization initiators shown in Table 2, and tested in the same manner. The results are shown in Table-2. As is clear from the results in Tables 1 and 2,
All of the products of the present invention have a higher gel fraction and better solvent resistance than those of the comparative examples, and in particular have sufficient sensitivity and photocured film strength even when using visible light. Is recognized.

【table】

【table】

【table】

【table】

Claims (1)

[Scope of Claims] 1. A benzophenone group-containing polyhydric peroxyester represented by the following general formula (I), a 4,4'-bis(dialkylamino)benzophenone represented by the general formula (), and a photosensitizing dye shown below. A photopolymerization initiator composition for polymerizing unsaturated monomers. [In the formula, R ₁ and R ₁ ' each have 4 to 8 carbon atoms]
a tertiary alkyl group or a tertiary aralkyl group having 9 to 12 carbon atoms; R ₂ and R ₂ ' are each a hydrogen atom, a tertiary alkoxy group having 4 to 8 carbon atoms, or a tertiary aralkyloxy group having 9 to 12 carbon atoms; represents. [Formula] [In the formula, R represents an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group, or a hydroxyalkyl group. ] Photosensitizing dyes [benzalacetophenones, pyrylium salts,
One or more selected from thiopyrylium salts, cyanine dyes, merocyanine dyes, xanthene dyes, and thiazole dyes]