JPH07103169B2 - Photopolymerization initiator composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a photopolymerization initiator composition for unsaturated compound polymerization.

It is well known that monomers, oligomers and polymers containing an unsaturated bond in the molecule undergo photopolymerization in the presence of a photopolymerization initiator, and so-called photo plates used for producing printed boards, printed circuit boards, ICs, etc. Widely used as polymers and photoresists.

<Prior Art> As a photopolymerization initiator used for these, various substances such as benzoin and benzoin alkyl ether as benzoin compounds, benzyl, benzophenone, acetophenone, benzyl ketal as carbonyl compounds, and azo compounds have been used. Examples thereof include azobisisobutyronitrile and azodibenzoyl, and examples of sulfur compounds include dibenzothiazolyl sulfide and tetraethylthiuram disulfide.

<Problems to be Solved by the Invention> However, it cannot be said that these photopolymerization initiators do not necessarily have good sensitivity, and there is a strong demand for a photopolymerization initiator having high sensitivity and high stability. ing.

Organic peroxides having a peroxide bond in the molecule include many kinds of compounds such as hydroperoxide, dialkyl peroxide, diacyl peroxide, perester ester and percarbonate ester, which are decomposed by heat. It is well known to generate active radical species. Therefore, the organic peroxide is widely used as a thermal polymerization initiator for unsaturated compounds, a thermal polymerization catalyst, a thermal polymerization crosslinking agent, and the like. Furthermore, it has been reported that organic peroxides are decomposed by light energy and similarly generate active radical species. However, when these organic peroxides are used as a photopolymerization initiator for an unsaturated compound, they have low photopolymerization initiation ability and generally low thermal stability, and are not suitable for practical use. Therefore, heretofore, almost no example has been found in which an organic peroxide is used as a photopolymerization initiator for a polymerization type photopolymer.

<Means for Solving Problems> As a result of intensive studies by the present inventors from such a background, a combination of an aminophenyl ketone compound having a specific structure and an organic peroxyester compound has an extremely excellent light emission. The present invention has been accomplished by finding that it has a polymerization initiation ability and increases the initial polymerization rate in the photopolymerization of an unsaturated compound, and by using this, a highly sensitive photosensitive resin can be obtained.

That is, the present invention has the general formula (I) (In the formula, R ₁ and R ₂ represent an alkyl group having 1 to ₂ carbon atoms, R ₃ represents hydrogen or an alkyl group having 1 to 2 carbon atoms, R ₄ represents an alkyl group having 1 to ₄ carbon atoms, and n is 0 or The photopolymerization initiator composition comprises a combination of an aminophenyl ketone compound having a partial structure represented by 1) and an organic perester compound having a benzene skeleton or a benzophenone skeleton in the molecule.

Hereinafter, the present invention will be described in more detail.

In the present invention, the general formula (I) An aminophenyl ketone compound having a partial structure shown in is used. In the formula, R ₁ and R ₂ represent the same or different groups and represent an alkyl group having 1 to 2 carbon atoms. R ₃ represents hydrogen or an alkyl group having 1 to 2 carbon atoms, and R ₁ , R ₂ , R ₃
As a result, an aminophenyl ketone compound having a partial structure showing an alkyl group having 3 or more carbon atoms cannot be used because it is difficult to produce. In the formula, R ₄ represents an alkyl group having 1 to ₄ carbon atoms. N represents 0 or 1. An aminophenylketone compound having a partial structure showing an alkyl group having 5 or more carbon atoms as R ₄ cannot be used because it is difficult to produce, and similarly, when n is 2 or more, the production becomes difficult.

Examples of the aminophenyl ketone compound having a partial structure represented by the general formula (I) used in the present invention include:
1- (2'-dimethylaminophenyl) -2-methoxycarbonyl-2-benzoylethylene, 1- (3'-dimethylaminophenyl) -2-methoxycarbonyl-2
-Benzoylethylene, 1- (4'-dimethylaminophenyl) -2-methoxycarbonyl-2-benzoylethylene, 1- (2'-diethylaminophenyl) -2-
Methoxycarbonyl-2-benzoylethylene, 1-
(3'-diethylaminophenyl) -2-methoxycarbonyl-2-benzoylethylene, 1- (4'-diethylaminophenyl) -2-methoxycarbonyl-2-benzoylethylene, 1- (2'-dimethylaminophenyl) -2 -Ethoxycarbonyl-2-benzoylethylene, 1- (3'-dimethylaminophenyl) -2-ethoxycarbonyl-2-benzoylethylene, 1- (4 '
-Dimethylaminophenyl) -2-ethoxycarbonyl-2-benzoylethylene, 1- (2'-diethylaminophenyl) -2-ethoxycarbonyl-2-benzoylethylene, 1- (3'-diethylaminophenyl)-
2-ethoxycarbonyl-2-benzoylethylene, 1
-(4'-diethylaminophenyl) -2-ethoxycarbonyl-2-benzoylethylene, 1- (2'-dimethylaminophenyl) -2-butoxycarbonyl-2-
Benzoylethylene, 1- (3'-dimethylaminophenyl) -2-butoxycarbonyl-2-benzoylethylene, 1- (4'-dimethylaminophenyl) -2-butoxycarbonyl-2-benzoylethylene, 1-
(2'-diethylaminophenyl) -2-butoxycarbonyl-2-benzoylethylene, 1- (3'-diethylaminophenyl) -2-butoxycarbonyl-2-benzoylethylene, 1- (4'-diethylaminophenyl) -2- Butoxycarbonyl-2-benzoylethylene, 1- (4'-dimethylaminophenyl) -2-methoxycarbonyl-2- (2'-methylbenzoyl) ethylene, 1- (4'-dimethylaminophenyl) -2-methoxycarbonyl -2- (3'-methylbenzoyl) ethylene, 1- (4'-dimethylaminophenyl) -2-
Methoxycarbonyl-2- (4'-methylbenzoyl)
Ethylene, 1- (4'-diethylaminophenyl) -2
-Methoxycarbonyl-2- (2'-methylbenzoyl) ethylene, 1- (4'-diethylaminophenyl)
2-methoxycarbonyl-2- (3′-methylbenzoyl) ethylene, 1- (4′-diethylaminophenyl) -2-methoxycarbonyl-2- (4′-methylbenzoyl) ethylene, 1- (4′-diethylamino) Phenyl) -2-ethoxycarbonyl-2- (2'-methylbenzoyl) ethylene, 1- (4'-diethylaminophenyl) -2-ethoxycarbonyl-2- (3'-methylbenzoyl) ethylene, 1- (4 ' -Diethylaminophenyl) -2-ethoxycarbonyl-2- (4'-methylbenzoyl) ethylene, 1- (4'-diethylaminophenyl) -2-ethoxycarbonyl-2- (2'-
Methoxybenzoyl) ethylene, 1- (4'-diethylaminophenyl) -2-ethoxycarbonyl-2-
(3'-methoxybenzoyl) ethylene, 1- (4'-
Diethylaminophenyl) -2-ethoxycarbonyl-
2- (4'-methoxybenzoyl) ethylene, 1-
(4'-diethylaminophenyl) -2-ethoxycarbonyli-2- (2'-cyanobenzoyl) ethylene,
1- (4'-diethylaminophenyl) -2) -ethoxycarbonyl-2- (3'-cyanobenzoyl) ethylene, 1- (4'-diethylaminophenyl) -2-ethoxycarbonyl-2- (4'-cyanobenzoyl) ) Ethylene, 1- (4'-diethylaminophenyl) -2-ethoxycarbonyl-2- (2'-dimethylaminobenzoyl) ethylene, 1- (4'-diethylaminophenyl) -2-ethoxycarbonyl-2- (3 ' -Dimethylaminobenzoyl) ethylene, 1- (4'-diethylaminophenyl) -2-ethoxycarbonyl-2- (4 '
-Dimethylaminobenzoyl) ethien, 1- (4'-
Diethylaminophenyl) -2-butoxycarbonyl-
2- (2'-butylbenzoyl) ethylene, 1- (4 '
-Diethylaminophenyl) -2-butoxycarbonyl-2- (4'-butylbenzoyl) ethylene, 1-
(2'-Dimethylaminophenyl) -2-methoxycarbonyl-4-benzoyl-1,3-butadiene, 1-
(3'-Dimethylaminophenyl) -2-methoxycarbonyl-4-benzoyl-1,3-butadiene, 1-
(4'-Dimethylaminophenyl) -2-methoxycarbonyl-4-benzoyl-1,3-butadiene, 1-
(2'-Diethylaminophenyl) -2-methoxycarbonyl-4-benzoyl-1,3-butadiene, 1-
(3'-Diethylaminophenyl) -2-methoxycarbonyl-4-benzoyl-1,3-butadiene, 1-
(4'-Diethylaminophenyl) -2-methoxycarbonyl-4-benzoyl-1,3-butadiene, 1-
(2'-Dimethylaminophenyl) -2-ethoxycarbonyl-4-benzoyl-1,3-butadiene, 1-
(3'-Dimethylaminophenyl) -2-ethoxycarbonyl-4-benzoyl-1,3-butadiene, 1-
(4'-Dimethylaminophenyl) -2-ethoxycarbonyl-4-benzoyl-1,3-butadiene, 1-
(2'-Diethylaminophenyl) -2-ethoxycarbonyl-4-benzoyl-1,3-butadiene, 1-
(3'-Diethylaminophenyl) -2-ethoxycarbonyl-4-benzoyl-1,3-butadiene, 1-
(4'-Diethylaminophenyl) -2-ethoxycarbonyl-4-benzoyl-1,3-butadiene, 1-
(4'-Dimethylaminophenyl) -2-methoxycarbonyl-4- (4'-methylbenzoyl) -1,3-butadiene, 1- (4'-dimethylaminophenyl) -2-
Ethoxycarbonyl-4- (4'-methylbenzoyl)
-1,3-butadiene, 1- (4'-diethylaminophenyl) -2-methoxycarbonyl-4- (4'-methylbenzoyl) -1,3-butadiene, 1- (4'-diethylaminophenyl) -2- Ethoxycarbonyl-4-
(4'-methylbenzoyl) -1,3-butadiene, 1-
(4'-Diethylaminophenyl) -2-ethoxycarbonyl-4- (4'-methoxybenzoyl) -1,3-butadiene, 1- (4'-diethylaminophenyl) -2
-Ethoxycarbonyl-4- (4'-cyanobenzoyl) -1,3-butadiene, 1- (4'-diethylaminophenyl) -2-butoxycarbonyl-4- (4'-dimethylaminobenzoyl) -1,3- Butadiene, 1-
(2'-Diethylaminophenyl) -2-ethoxycarbonyl-4- (4'-methylbenzoyl) -1,3-butadiene, 1- (3'-diethylaminophenyl) -2-
Methoxycarbonyl-4- (4'-methoxybenzoyl) -1,3-butadiene, 1- (2'-dimethylaminophenyl) -2-methoxycarbonyl-2-cinnamoylethylene, 1- (3'-dimethylaminophenyl) ) −
2-methoxycarbonyl-2-cinnamoylethylene,
1- (4'-dimethylaminophenyl) -2-methoxycarbonyl-2-cinnamoylethylene, 1- (2'-
Diethylaminophenyl) -2-methoxycarbonyl-
2-cinnamoylethylene, 1- (3'-diethylaminophenyl) -2-methoxycarbonyl-2-cinnamoylethylene, 1- (4'-diethylaminophenyl)
-2-methoxycarbonyl-2-cinnamoylethylene, 1- (2'-dimethylaminophenyl) -2-ethoxycarbonyl-2-cinnamoylethylene, 1-
(3'-Dimethylaminophenyl) -2-ethoxycarbonyl-2-cinnamoylethylene, 1- (4'-dimethylaminophenyl) -2-ethoxycarbonyl-2-
Cinnamoylethylene, 1- (2'-diethylaminophenyl) -2-ethoxycarbonyl-2-cinnamoylethylene, 1- (3'-diethylaminophenyl) -2
-Ethoxycarbonyl-2-cinnamoylethylene, 1
-(4'-diethylaminophenyl) -2-ethoxycarbonyl-2-cinnamoylethylene, 1- (2'-dimethylaminophenyl) -2-butoxycarbonyl-2
-Cinnamoylethylene, 1- (3'-dimethylaminophenyl) -2-butoxycarbonyl-2-cinnamoylethylene, 1- (4'-dimethylaminophenyl)-
2-butoxycarbonyl-2-cinnamoylethylene,
1- (2'-diethylaminophenyl) -2-butoxycarbonyl-2-cinnamoylethylene, 1- (3'-
Diethylaminophenyl) -2-butoxycarbonyl-
2-cinnamoylethylene, 1- (4'-diethylaminophenyl) -2-butoxycarbonyl-2-cinnamoylethylene and the like can be mentioned.

The organic perester compound used in the present invention preferably has a 10-hour half-life temperature of 70 ° C or higher,
For example, tert-butyl peroxybenzoate,
Tert-butyl peroxymethoxybenzoate,
Tertiary butyl peroxy nitrobenzoate, tertiary butyl peroxy ethyl benzoate, phenyl isopropyl peroxy benzoate, ditertiary butyl diperoxy isophthalate, tritertiary butyl triperoxy trimellitate, tritertiary butyl triperoxy trimesinate, tetra tertiary butyl Tetraperoxypyromellitate, 2,
5-dimethyl-2,5-di (benzoylperoxy) hexane, 3,3 ', 4,4'-tetra (tertiarybutylperoxycarbonyl) benzophenone, 3,3', 4,4'-tetra (tertiaryamyl) Examples thereof include peroxycarbonyl) benzophenone and 3,3 ′, 4,4′-tetra (tertiaryhexylperoxycarbonyl) benzophenone.

The photopolymerization initiator composition of the present invention contains the above-mentioned (A) aminophenyl ketone compound and (B) organic perester compound, and the mixing ratio of both (A) and (B) is:
The weight ratio of (A) :( B) is preferably 1:10 to 100: 1, and more preferably 1:30 to 10: 1.

The reason why the photopolymerization initiator composition of the present invention can be a good photopolymerization initiator for an unsaturated compound is considered to be due to effective photosensitized decomposition of an organic perester compound with an aminophenyl ketone compound. And by selecting the amino phenyl ketone compound, it is possible to express the photopolymerization initiating ability in the range from ultraviolet light to visible light, so any light source can be used, and as a photopolymerization initiator for the photosensitive material for visible light laser. Is also available.

The photopolymerization initiator composition of the present invention can photopolymerize almost all unsaturated compounds. That is, the unsaturated compound may be a monomer, oligomer or polymer having a polymerizable ethylenic unsaturated bond,
For example, unsaturated acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid and its anhydride, phthalic acid and its anhydride, fumaric acid, and 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 Unsaturated acid ester compounds such as (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, and acrylamide;
There are monomers such as acrylonitrile, N-vinylpyrrolidone and vinyl acetate, and further unsaturated polyesters, unsaturated polyethers, unsaturated polyurethanes and epoxy (meth) acrylate compounds.

A photopolymerization composition can be prepared by adding the photopolymerization initiator composition of the present invention to one of these unsaturated compounds or a mixture of two or more thereof, and optionally adding an appropriate diluting solvent.

The photopolymerization initiator composition is added in an amount of 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.

Any suitable diluting solvent can be used as long as it dissolves the photopolymerization initiator composition of the present invention and the unsaturated compound.
For example, water, methanol, ethanol, propanol,
Butanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, ethyl acetate, butyl acetate, cellosolve, tetrahydrofuran, dioxane, dichloromethane, chloroform, carbon tetrachloride, trichloroethylene, dimethylformamide, dimethyl sulfoxide and the like.

The photopolymerizable composition thus obtained can be subjected to a polymerization reaction by irradiating with actinic rays such as ultraviolet rays or visible rays. As the light source, various high pressure, high pressure, medium pressure and low pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, fluorescent lamps, tungsten lamps, sunlight, and various laser lamps can be used.

<Effects of the Invention> The photopolymerization initiator composition of the present invention is used in combination with the aminophenylketone compound and the organic peroxyester compound, and therefore has significantly higher sensitivity than conventional photopolymerization initiators. It is excellent in workability and economical efficiency because it is sufficiently exposed to light even with a weak light source.

The photopolymerization initiator composition of the present invention can be used for ordinary photopolymerization reactions, as well as for photocurable coatings, printing inks, adhesives, printing plate preparations, and further for the fixation of photoresists, enzymes, cells, and the like. It can be applied to various fields, and its effect is very good, and the one with the highest sensitivity can be obtained.

<Example> The present invention will be described in more detail with reference to Examples and Comparative Examples. Parts in the examples indicate parts by weight.

Examples 1-18 100 parts of poly (methyl methacrylate / ethyl acrylate / methacrylic acid) (molar ratio 5/4/1; molecular weight 100,000) and pentaerythritol triacrylate (Shin-Nakamura Chemical Co., Ltd.)
(Manufactured by: A-TMM-3L) 100 parts of the photopolymerization initiator composition of the present invention shown in Table-1 was added at a ratio shown in Table-1, and further added.
A photosensitive solution was obtained by uniformly dissolving it in 1000 parts of ethyl cellosolve.

Each of these photosensitive plates was applied onto an anodized aluminum plate using a wahler so that the dry coating film thickness was 2 μm, and dried to obtain a photosensitive test plate. A gray scale (Kodak step tablet No. 2) was vacuum-adhered to this photosensitive test plate, and 2 kw was applied from a distance of 60 cm.
After exposure for 1.5 seconds using the ultra-high pressure mercury lamp of No. 3, the product was developed with a commercially available alkaline developer (DN-3C manufactured by Fuji Photo Film Co., Ltd.), and the sensitivity was measured by reading the number of gray scale steps of the cured part. The results are shown in Table-1. Note that the number of step steps indicates that the sensitivity doubles when there are two steps, and the larger the value, the higher the sensitivity.

Comparative Examples 1 to 8 For comparison with Examples, a commercially available photopolymerization initiator, aminophenyl ketone compound or organic perester compound shown in Table 2 was used instead of the photopolymerization initiator composition of the present invention. A photosensitive test plate was prepared by the same method as in the example, and the sensitivity was measured in the same manner. The results are shown in Table-2.

From the results shown in Tables 1 and 2, it is clear that the examples have a much higher sensitivity than the comparative examples.

Claims (1)

[Claims] 1. A general formula (I) (In the formula, R ₁ and R ₂ represent an alkyl group having 1 to ₂ carbon atoms, R ₃ represents hydrogen or an alkyl group having 1 to 2 carbon atoms, R ₄ represents an alkyl group having 1 to ₄ carbon atoms, and n is 0 or The photopolymerization initiator composition comprises a combination of an aminophenyl ketone compound having a partial structure represented by 1) and an organic perester compound having a benzene skeleton or a benzophenone skeleton in the molecule.