JPS627703A - Photopolymerization initiator composition - Google Patents

Abstract

PURPOSE:To provide the titled composition consisting of a combination of a benzalacetophenone compound having a specific structure and an organic peroxide, having extremely high photopolymerization-initiation property, capable of increasing the initial rate of polymerization in the photopolymerization of an unsaturated compound and giving a photosensitive resin having high sensitivity. CONSTITUTION:The objective composition can be produced by compounding (A) the benzalacetophenone compound of formula (R1 and R2 are H, 1-4C alkyl, 1-4C alkoxy, phenyl, phenoxy, nitro, amino or halogen) (e.g. benzalacetophenone, nitrobenzalacetophenone, etc.) and (B) an organic peroxide [e.g. methyl ethyl ketone peroxide, 1,1-bis(t-butylperoxy)-3,3,5- trimethylcyclohexane, etc.] preferably at a weight ratio of (3-95):(97-5).

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. Furthermore, this phenomenon is widely used in photopolymers and photoresists used in the production of printing plates, printed circuit boards, C, etc.

[Conventional technology]

Various substances have been reported and actually used as photopolymerization initiators for these. For example, benzoin compounds such as penzoin and hendiine methyl ether; carbonyl compounds such as benzyl, pe/siphenone, acetophenone, and Michael's ketone; azo compounds such as azobisisobutyronitrile and azodibenzoyl; and sulfur compounds such as dibenzothiazole. Halogen compounds such as rusulfide, tecylphenyl sulfide, tetraethylnararum disulfide, etc.
Carbonized carbon 2, tribromphenyl sulfone, etc., and 1
, 2-benzanthraquinone, etc.

However, these photopolymerization initiators are still not fully satisfactory; photopolymerization compositions with various unsaturated compounds do not necessarily have good sensitivity as photopolymers; There is a strong demand for photopolymerization initiators with high sensitivity and good storage stability.

°Also, there are many types and compounds of organic peroxides that have peroxide bonds in their molecules, such as hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxyketals, peroxyesters, and peroxycarbonates. is known to thermally decompose to produce active radical species. For this reason, organic peroxides are widely used as thermal polymerization initiators, thermal polymerization catalysts, thermal polymerization curing agents, thermal polymerization crosslinking agents, etc. for unsaturated compounds. Furthermore, organic peroxides are also decomposed by light energy. Similarly, it has been reported that active radicals 81 are generated. However, these have low photopolymerization initiating ability for use as photopolymerization initiators for unsaturated compounds, and are therefore not suitable for practical use.

Therefore, organic peroxides have rarely been used as photopolymerization initiators for polymerizable photopolymers.

[Means to solve the problem]

Against this background, the present inventors conducted extensive research and found that a combination of benzalacetophenones with a specific structure and an organic peroxide has extremely good photopolymerization initiating ability), The present invention has been achieved by discovering that a highly sensitive photosensitive resin can be obtained by increasing the initial polymerization rate in photopolymerization of a saturated compound and then using the same.

That is, the present invention provides a photopolymerization initiator composition comprising a combination of benzalacetophenones represented by the general formula (Natsu) and an organic peroxide.

Examples of the 7 types of pe/zalacetophenones used in the present invention with general formula (1) include benzalacetophenone,
Benzalmethylacetophenone/, Methylbenzalmethylacetophenone, Methylbenzalethylacetophenone/
, methylbenzalmethoxyacetophenone/, ethylbenzalbutoxyacetophenone, methoxybenzalmethoxyacetophenone, methoxybenzalethyl acetophenone/, ethylbenzalphenoquine acetopheno/, methylpenzalmethoxyacetophenone, benzaldimethylamino Acetophenone, dimethylaminobenzaldimethylaminoacetophenone, methoxybenzaldimethylaminoacetophenone, aminebenzalaminoacetophenone, dimethylaminobenzalmethoxyacetophenone, benzaldiethylaminoacetophenone, dimethylaminobenzalacetopheno:/, butoxybenzaldimethylaminoacetophenone , chlorobenzalmethylacetophenone, methylbenzalnitroacetophenone, benzalnitroacetophenone, nitrobenzalacetophenone, etc., and these can be used alone or in combination of two or more.

Further, the organic peroxide used in the present invention is not particularly limited in its structure, but for example, methyl ethyl ketone peroxide, cyclohexanone peroxide% 3.3.5-
Trimethyl 7-chlorohexanone peroxide, methyl 7-chlorohexanone peroxide.

Acetylacetone peroxide, 1,1-bis(-butylperoxy)-3,3,5-)limethylcyclohexane, 1. I-bis(t-butylperoxy)cyclohexane, n-7'thyl-4,4-bis(t-butylperoxy)nochlorlate, 2,2-bis(4-butylperoxy)butane, t-butylneudro peroxide, cumene hydroperoxide, diimpropylbenzene hydroperoxide, paramenthane hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide.

1, 1.3.3-tetramethylbutyl hydroperoxide, di-t-butyl peroxide, L-butylcumyl peroxide, dicumyl peroxide, α, α'-his(
t-7'tilberoxyisoglobil) pecumene, 2.
5-dimethyl-2,5-di(t-butylperoxy)hexane, 2,5-dimethyl-2,5-di(t-7"tylperoxy)hexyne-3, acetylperoxide, isobutyrylperoxy'= d, octanoyl peroxide, decamyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl 7,
Succinic peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, mettatoluoyl peroxide diimprovil peroxydicarbonate, di-2-
Ethylhexyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, dimethoxyisopropyl peroxydicarbonate, di(3-methyl-3-methoxypnal) peroxydicarbonate, t-butyl peroxyacetate, t-butylperoxyin butyrate, t-;y
"Tylperoxyneodecanoate, t-butylperoxyoctanoate, t-butylperoxy 3.5.5
-trimethylhexanoate, t-butyl peroxylaurate, t-ptervero-dipenzoate, di-t-
Diperoxyisophthalate, 2,5-dimethyl-2,
5-di(benzoylperoxy)benzene, t-butyl peroxide maleic acid, t-butylperoxyisopropyl carbonate, 3.3?4°4'-tetra-(1-butylberoxycarbonyl)benzophenone, 3. 3;
4.4'-tetra-(t-amylperoxycarbonyl)pe/siphenone, 3.3:4-tetra(t-hexylberoxycarbonyl)benzophenone, 3.3?
4.4'-tetra(t-octylperoxycarbonyl)benzophenone, a, 3? 4.4'-tetra (
cumylberoxycarbonyl)benzophenone, 3.3
? 4.4'-tetra(p-isopropylcumylberoxycarbonyl)benzophenone, etc.
It can be used as a species or as a mixture of two or more species.

The photopolymerization initiator composition of the present invention contains the above-mentioned (A) benzalacetophenone with a specific structure and the above-mentioned (B) organic peroxide as active ingredients. (4)=(B) is 1-99:99-1, more preferably 3-95:97-5. If the composition is outside this range, excellent photopolymerization initiation performance cannot be obtained.

The photopolymerization initiator composition of the present invention can photopolymerize almost all unsaturated compounds. For example, unsaturated acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid and its anhydride, phthalic acid and its anhydride, fumaric acid, methyl (meth)acrylate, and (meth)acrylic acid. Ethyl, butyl (meth)acrylate, glycidyl (meth)acrylate, hydroxyethyl (meth)acrylate, dimethyl maleate, diethyl maleate.

Dimethyl fumarate, pentaerythritol tri(meth)
Unsaturated acid ester compounds such as acrylate, trimethylolpropane tri(meth)acrylate, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, styrene, acrylamide, acrylonitrile, N-vinylvinylate, lydone, vinyl acetate, etc. In addition, there are unsaturated polyesters, unsaturated polyethers, unsaturated polyurethanes, and Evoquin (meth)acrylate monomers.

The photopolymerization initiator composition of the present invention is added to one or a mixture of two or more of these unsaturated compounds, and if necessary, a suitable diluting solvent is added to form a photopolymerization compound.

The amount of photopolymerization initiator composition added is 01 to 30 parts by weight, preferably 0.5 to 20 parts by weight, per 100 parts by weight of the unsaturated compound.
This is the important part.

Further, any suitable diluting solvent can be used as long as it dissolves the photopolymerization initiator composition and unsaturated compound of the present invention. For example, water, methanol, ethanol, propanol, butanol, acetone, methyl ether ketone, methyl isobutyl keto/, toluene, xylene, ethyl acetate,
These include mmpur, cellosolve, tetrahydrofuran, dioxane, dichloromethane, chloroform, carbon tetrachloride, trichlorethylene, dimethylformamide, trimethylsulfoxide, and the like.

The photopolymerized composition obtained in this way is exposed to active light such as ultraviolet rays or visible light &! For irradiation, various types of laser lamps such as carbon arc lamps, xenon lamps, metal halide lamps, fluorescent lamps, tungsten lamps, and solar lamps can be used.

〔Effect of the invention〕

The photoinitiator composition of the present invention has significantly higher sensitivity than conventional photoinitiators using a combination of benzalacetophenone and organic peroxide, and is sufficiently sensitive to light even with a weak light source. Therefore, it is excellent in terms of workability and economy.

The photopolymerization initiator composition of the present invention can be used not only for ordinary photopolymerization reactions, but also for a variety of applications such as photocurable paints, printing inks, adhesives, printing plate preparation, and photoresists. 6D is also very effective and can provide the highest sensitivity.

[Examples] The present invention will be explained in more detail below using Examples and Comparative Examples. Note that the part in the example is the "IT" part.

Examples 1-1/ 100 parts of copolymer of methyl methacrylate and methacrylic acid (molecular weight 70000, Shun 1ifli120), pentaerythritol triacrylate (manufactured by Shin Nakamura Chemical @, A-
The photopolymerization initiator composition of the present invention shown in Table IK was added to 120 parts of TMM-3L) in the proportions shown in Table 1, and these were added uniformly to 1000 parts of methyl cellosolve.
This was used as a photosensitive solution. .

These photosensitive solutions were applied onto an anodized aluminum plate using a spinner so that the dry film thickness was 1 μm.
Furthermore, polyvinyl alcohol (@Kuraray, PVA-5)
os) Not oil + t% water bath liquid photosensitivity test is 21;
*Using an ultra-high-pressure mercury lamp, a gray scale (Kodak Stepda Presoto A2) was closely attached to the camera from a distance of 650 mm.
After 4 seconds, the sensitivity was determined by measuring the step number of the remaining cured film after developing it with an IJcum aqueous solution (LJ'f). . The results are shown in Table 1.The number of steps indicates that a two-step difference doubles the sensitivity, and the larger the number, the higher the sensitivity.

Comparative Examples 1 to 8 The same method as in Example i-1 and Table 2 were carried out using the photopolymerization initiators shown in Table 2, including the case of a commercially available photoinitiator, benzalacetophenone, and organic peroxide. As is clear from the results of -2, both the samples of the present invention have a large difference in the number of steps compared to the samples of the comparative example, and it is recognized that they have significantly higher sensitivity.

Claims (2)

[Claims] (1) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼... (I) [In the formula, R_1 and R_2 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a carbon number 1 to 4 represents an alkoxy group, phenyl group, phenoxy group, nitro group, amino group or halogen atom. ] A photopolymerization initiator composition comprising a combination of benzalacetophenones represented by the following and an organic peroxide. (2) The benzalacetophenones are benzalacetophenone, dimethylaminobenzaldimethylacetophenone, methoxybenzaldimethylaminoacetophenone,
The photopolymerization initiator according to claim 1, which is one or more selected from benzaldimethylaminoacetophenone, dimethylaminobenzalacetophenone, butoxybenzalmethylacetophenone, chlorbenzalacetophenone, and benzalnitroacetophenone. Composition.