JPH0410482B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a photoinitiator composition for the polymerization of ethylenically unsaturated compounds, and more particularly to a highly sensitive photoinitiator composition that is sensitive to ultraviolet light and visible light at low doses and can be used for laser applications. It is. It is well known that monomers, dimers, trimers, oligomers, and polymers containing unsaturated bonds in their molecules are photopolymerized in the presence of a photoinitiator. This phenomenon is also widely used in photopolymerizable photopolymers and photoresists used in the production of printing plates, printed circuit boards, ICs, and the like. Various substances have been reported and actually used as photopolymerization initiators for these. For example, benzoin compounds include benzoin, benzoin methyl ether, and benzoin ethyl ether; carbonyl compounds include benzyl, benzophenone, acetophenone, and Michael's ketone; azo compounds include azobisisobutyronitrile and azodibenzoyl; and sulfur compounds include dibenzothia Examples of halogen compounds include zolyl sulfide and tetraethylthiuram disulfide, carbon tetrabromide, tribromphenyl sulfone, and 1,2-benzanthraquinone. However, these photopolymerization initiators are not yet fully satisfactory, and when combined with various unsaturated compounds, they cannot necessarily be said to have good sensitivity as photopolymers. In addition, in recent years, methods of forming images using lasers have been studied, and methods such as direct laser engraving, laser facsimile, and holography for printing plate production are already at the stage of practical application, and further applications are being considered in many fields in the future. expected. The laser photosensitive materials used in this case include silver salt photosensitive materials, electrophotographic materials, photochromic materials, and photopolymers, but photopolymers are extremely sensitive compared to silver salt photosensitive materials and electrophotographic materials. Furthermore, its sensitivity wavelength range is from ultraviolet to visible light. For example, the sensitivity of silver halide film (Kodalis Orthofilm 2556 Type 3) is 0.0205 mJ/cm 2, although the required energy amount for monochromatic light with a wavelength of 488 nm from Ar ⁺ laser is 0.0205 mJ/cm ² .
Photopolymer (Kodatsu Polymer Chrysoplate LN-L) requires an energy of 7000 mJ/cm ² , and even if ultraviolet rays with a wavelength of 351/364 nm are used, an energy of 100 mJ/cm ² is required. As described above, conventional photopolymers are unsatisfactory in both sensitivity and sensitive wavelength range, and are particularly unsuitable as photosensitive materials for visible light lasers. Against this background, the inventors of the present invention have conducted intensive research while keeping in mind the above points, and have found that a composition that combines a specific organic peroxide and a specific organic dye compound is very good even in the visible light region. The present invention was achieved based on the discovery that the photopolymerization initiation ability is high, and the sensitivity is close to that of silver salt photosensitive materials. That is, the present invention is based on the general formula () [In the formula, R ₁ and R' ₁ are each a tertiary alkyl group having 4 to 8 carbon atoms or a tertiary aralyl group having 9 to 12 carbon atoms, and R ₂ and R' ₂ are each a hydrogen atom or a tertiary alkyl group having 4 to 12 carbon atoms. 8 tertiary alkoxy group or a tertiary aralkyloxy group having 9 to 12 carbon atoms. ] The present invention provides a photoinitiator composition comprising a combination of the benzophenone group-containing polyhydric peroxyester compound represented by the following and any of the organic dye compounds specified below. Examples of peroxyester compounds represented by the general formula () used in the present invention include 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',4,4'-tetra(p-isopropylcumylperoxycarbonyl)benzophenone, 3,
3'-di(t-butylperoxycarbonyl)-4,
4′-di(carboxy)benzophenone, 3,3′-
di(t-hexylperoxycarbonyl)-4,
Examples include 4'-di(carboxy)benzophenone. In addition, the organic dye compound used in the present invention has the general formula () [In the formula, R ₁ , R ₂ , and R ₃ each independently represent a hydrogen atom, a halogen, an alkyl group, a haloalkyl group, an ethylenyl group, a styryl group, an alkoxy group, a phenyl group,
Represents a naphthyl group, an alkyl phenyl group, an alkoxyphenyl group, a hydroxyphenyl group, a halophenyl group, a nitrophenyl group, an amino phenyl group, a nitro group, an amino group or a hydroxyl group, X represents oxygen, sulfur or selenium, and Y represents an anion. Represents a functional group. ] There are pyrylium salts, thiapyrylium salts, and selenopyrillium salts represented by the formula (), and the anionic functional groups represented by Y in the general formula () include perchlorate, fluoroborate, chloroaluminate, chloropherate, sulfur acetate,
Methosulfate, thiocyanate, etc. Specific examples of the compound represented by the general formula () 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, 4-(4-methoxyphenyl) )-2,6-diphenylthiapyrylium perchlorate, 6-(4-ethoxyphenyl)-2,4-diphenylthiapyrylium perchlorate, 2,4,6-tri(4-methoxyphenyl) Thiapyrylium perchlorate, 4-(4-amyloxyphenyl)-2,6-bis(4-ethylphenyl)thiapyrylium perchlorate, 2,4,6-triphenylthiapyrylium fluoroborate, 2,4 , 6-triphenylthiapyrylium sulfate, 4-(4-methoxyphenyl)-2,6-diphenylthiapyrylium fluoroborate, 2-(4-amyloxyphenyl)-4,6-diphenyl Thiapyrylium fluoroborate, 4-(4-amyloxyphenyl)-2,6-bis(4-methoxyphenyl)thiapyrylium perchlorate, 4-(4-methoxyphenyl)-2,6-bis (4
-ethylphenyl)thiapyrylium perchlorate, 4-(2,4-dichlorophenyl)-2,6-diphenylpyrylium perchlorate, 2-(3,4-dichlorophenyl)-4-(4-methoxy phenyl)-6-phenylpyrylium perchlorate, 4-(4-amyloxyphenyl)-2,6-bis(4-ethylphenyl)pyrylium perchlorate, 2,6-bis(4-ethylphenyl)- 4-(4-
methoxyphenyl)pyrylium fluoroborate, 6-(3,4-diethoxystyryl)-2,4-diphenylpyrylium perchlorate, 6-(4-dimethylamino-β-ethylstyryl)
-2,4-diphenylpyrylium fluoroborate, 6-(4-dimethylaminostyryl)-2,4-diphenylpyrylium perchlorate, 6-(β-methyl-4-dimethylaminostyryl)
-2,4-diphenylpyrylium fluoroborate, 6-[β,β-bis(4-dimethylaminophenyl)vinylene]-2,4-diphenylpyrylium fluoroborate, 4-(4-dimethylaminophenyl) enyl)-2,6-diphenylpyrylium perchlorate, 2,6-bis(4-ethylphenyl)-4-methoxyphenylthiapyrylium fluoroborate, 4-(4-butoxyphenyl)-2,6-bis( 4
-methoxyphenyl)thiapyrylium fluoroborate, 2,6-bis(4-methoxyphenyl)-4-phenylthiapyrylium perchlorate, 4-(2,4-dichlorophenyl)-2,6- Diphenylthiapyrylium perchlorate, 6-(4-dimethylaminostyryl)-2,4-diphenylthiapyrylium perchlorate, 2-(3,4-diethoxystyryl)-4,6-diphenylthiapyryl Lium perchlorate, 2,6-bis(4-aminoxyphenyl)-4-
(4-methoxyphenyl)thiapyrylium perchlorate, 6-(3,4-diethoxy-β-ethylstyryl)
-2,4-diphenylpyrylium fluoroborate, 6-(4-methoxy-β-ethylstyryl)-2,
4-diphenylpyrylium fluoroborate, 2,4,6-triphenylselenopyrylium perchlorate, 4-(4-methoxyphenyl)-2,6-diphenylselenopyrylium fluoroborate, 6-(4- methoxyphenyl)-2,4-diphenylselenopyrylium perchlorate, 4-(4-ethoxyphenyl)-2,6-diphenylselenopyrylium perchlorate, 6-(3,4-diethoxy-β- aminostyryl)
-2,4-diphenylselenopyrylium fluoroborate, 2,6-bis(4-ethylphenyl)-4-phenylselenopyrylium perchlorate, 2,4,6-triphenylthiapyrylium fluoroborate, 2, 4,6-triphenylthiapyrylium fluoroantimonate, 4-(4-methoxyphenyl)-2,6-diphenylpyrylium fluoroborate, 2,6-bis(4-methoxyphenyl)-4-phenyl enylpyrylium fluoroborate, 2,6-bis(4-methoxyphenyl)-4-phenylthiapyrylium fluoroborate, 2,6-bis(4-methoxyphenyl)-4-phenylthiapyrylium fluoro antimonate, 4-(4-butoxyphenyl)-2,6-diphenylpyrylium fluoroborate, 4-(4-butoxyphenyl)-2,5-diphenylthiapyrylium perchlorate, 4-(4-butoxyphenyl)- 2,6-Diphenylthiapyrylium fluoroborate, 4-(4-butoxyphenyl)-2,6-diphenylthiapyrylium fluoroantimonate, 2,6-bis(4-ethylphenyl)-4-(4-
amyloxyphenyl)pyrylium fluoroborate, 2,6-bis(4-ethylphenyl)-4-(4-
amyloxyphenyl) thiapyrylium perchlorate, 2,6-bis(4-ethylphenyl)-4-(4-
amyloxyphenyl) thiapyrylium fluoroborate, 2,6-bis(4-ethylphenyl)-4-(4-
amyloxyphenyl) thiapyrylium fluorophosphonate, 6-(4-ethoxyphenyl)-2,4-diphenylpyrylium perchlorate, 6-(4-ethoxyphenyl)-2,4-diphenylpyrylium Fluoroborate, 6-(4-ethoxyphenyl)-2,4-diphenylthiapyrylium fluoroborate, 2,4,6-tri(4-methoxyphenyl)pyrylium perchlorate, 2,4,6- Tri(4-methoxyphenyl)pyrylium fluoroborate, 2,4,6-tri(4-methoxyphenyl)thiapyrylium fluoroborate, 2,4,6-tri(4-methoxyphenyl)thiapyrylium Fluoroantimonate, 2,6-bis(4-ethylphenyl)-4-(4-
amyloxyphenyl)pyrylium fluoroborate, 2,6-bis(4-ethylphenyl)-4-(4-
amyloxyphenyl) thiapyrylium fluoroborate, 2,6-bis(4-ethylphenyl)-4-(4-
amyloxyphenyl) thiapyrylium fluorophosphonate, 2-(4-amyloxyphenyl)-4,6-diphenylpyrylium perchlorate, 2-(4-amyloxyphenyl)-4,6-diphenyl Pyrylium fluoroborate, 2-(4-amyloxyphenyl)-4,6-diphenylthiapyrylium perchlorate, 2,6-bis(4-methoxyphenyl)-4-(4
-amyloxyphenyl)pyrylium perchlorate, 2,6-bis(4-methoxyphenyl)-4-(4
-amyloxyphenyl)pyrylium fluoroborate, 2,6-bis(4-methoxyphenyl)-4-(4
-amyloxyphenyl)thiapyrylium fluoroborate, 2,6-bis(4-ethylphenyl)-4-(4-
methoxyphenyl)pyrylium perchlorate, 2,6-bis(4-ethylphenyl)-4-(4-
methoxyphenyl)thiapyrylium fluoroantimonate, 4-(2,4-dichlorophenyl)-2,6-diphenylpyrylium fluoroborate, 4-(2,4-dichlorophenyl)-2,6- Diphenylthiapyrylium fluoroborate, 4-(2,4-dichlorophenyl)-2,6-diphenylthiapyrylium fluorophosphonate, 2-(3,4-dichlorophenyl)-4-(4-methoxy phenyl)-6-phenylpyrylium fluoroborate, 2-(3,4-dichlorophenyl)-4-(4-methoxyphenyl)-6-phenylthiapyrylium perchlorate, 2-(3, 4-dichlorophenyl)-4-(4-methoxyphenyl)-6-phenylthiapyrylium fluoroborate, 6-(3,4-diethoxystyryl)-2,4-diphenylpyrylium fluoroborate, 6-(3,4-diethoxystyryl)-2,4-diphenylthiapyrylium perchlorate, 6-(3,4-diethoxystyryl)-2,4-diphenylthiapyrylium fluoroborate, 6- (4-dimethylamino-β-ethylstyryl)
-2,4-diphenylpyrylium perchlorate, 6-(4-dimethylamino-β-ethylstyryl)
-2,4-diphenylthiapyrylium fluoroborate, 6-(4-dimethylamino-β-ethylstyryl)
-2,4-diphenylthiapyrylium fluoroantimonate, 6-(4-dimethylaminostyryl)-2,4-diphenylpyrylium fluoroborate, 6-(4-dimethylaminostyryl)-2,4-diph enylthiapyrylium fluoroborate, 6-(4-dimethylamino-β-methylstyryl)
-2,4-diphenylpyrylium perchlorate, 6-(4-dimethylamino-β-methylstyryl)
-2,4-diphenylthiapyrylium perchlorate, 6-(4-dimethylamino-β-methylstyryl)
-2,4-diphenylthiapyrylium fluoroborate, 6-[β,β-bis(4-dimethylaminophenyl)vinylene]-2,4-diphenylpyrylium perchlorate, 6-[β,β- Bis(4-dimethylaminophenyl)vinylene]-2,4-diphenylthiapyrylium perchlorate, 6-[β,β-bis(4-dimethylaminophenyl)vinylene]-2,4-diphenylthia Pyrylium fluoroborate, 6-[β,β-bis(4-dimethylaminophenyl)vinylene]-2,4-diphenylthiapyrylium fluorophosphonate, 4-(4-dimethylaminophenyl)-2,6 -diphenylpyrylium fluoroborate, 4-(4-dimethylaminophenyl)-2,6-diphenylthiapyrylium perchlorate, 4-(4-dimethylaminophenyl)-2,6-diphenylthiapyri fluoroborate, 4-(4-dimethylaminophenyl)-2,6-diphenylthiapyrylium fluoroantimonate, 2,6-bis(4-methoxyphenyl)-4-(4
-butoxyphenyl)pyrylium perchlorate, 2,6-bis(4-methoxyphenyl)-4-(4
-butoxyphenyl)pyrylium fluoroborate, 2,6-bis(4-methoxyphenyl)-4-(4
-butoxyphenyl)thiapyrylium perchlorate, 2,6-bis(4-aminoxyphenyl)-4-
(4-methoxyphenyl)pyrylium perchlorate, 2,6-bis(4-aminoxyphenyl)-4-
(4-methoxyphenyl)pyrylium fluoroborate, 2,6-bis(4-aminoxyphenyl)-4-
(4-methoxyphenyl)thiapyrylium fluoroborate, 2,6-bis(4-aminoxyphenyl)-4-
(4-methoxyphenyl)thiapyrylium fluoroantimonate, 6-(3,4-diethoxy-β-ethylstyryl)
-2,4-diphenylthiapyrylium fluoroborate, 6-(4-methoxy-β-ethylstyryl)-2,
4-diphenylthiapyrylium perchlorate, 6-(4-methoxy-β-ethylstyryl)-2,
4-Diphenylthiapyrylium fluoroborate, 6-(4-methoxyphenyl)-2,4-diphenylpyrylium perchlorate, 6-(4-methoxyphenyl)-2,4-diphenylpyrylium fluoro Borate, 6-(4-methoxyphenyl)-2,4-diphenylthiapyrylium perchlorate, 6-(4-methoxyphenyl)-2,4-diphenylthiapyrylium fluoroborate, 4-(4 -ethoxyphenyl)-2,6-diphenylpyrylium fluoroborate, 4-(4-ethoxyphenyl)-2,6-diphenylthiapyrylium fluoroborate, 6-(3,4-diethoxy-β- aminostyryl)
-2,4-diphenylpyrylium perchlorate, 6-(3,4-diethoxy-β-aminostyryl)
-2,4-diphenylpyrylium fluoroborate, 6-(3,4-diethoxy-β-aminostyryl)
-2,4-diphenylthiapyrylium perchlorate, 6-(3,4-diethoxy-β-aminostyryl)
-2,4-diphenylthiapyrylium fluoroborate, 6-(3,4-diethoxy-β-aminostyryl)
-2,4-diphenylthiapyrylium fluoroantimonate, 2,6-bis(4-ethylphenyl)-4-phenylpyrylium perchlorate, 2,6-bis(4-ethylphenyl)-4-phenylthia Pyrylium perchlorate, 2,6-bis(4-ethylphenyl)-4-phenylthiapyrylium fluoroborate, 2-(4-nitrophenyl)-4,6-bis(4-
butylphenyl)pyrylium perchlorate, 2-(4-nitrophenyl)-4,6-bis(4-
butylphenyl)pyrylium fluoroborate, 2-(4-nitrophenyl)-4,6-bis(4-
butylphenyl) thiapyrylium perchlorate, 2-(4-nitrophenyl)-4,6-bis(4-
butylphenyl) thiapyrylium fluoroborate, 2-(4-nitrophenyl)-4,6-bis(4-
butylphenyl) thiapyrylium fluoroantimonate, 2,6-bis(4-methoxyphenyl)-4-methylpyrylium perchlorate, 2,6-bis(4-methoxyphenyl)-4-methylpyrylium fluoroborate , 2,6-bis(4-methoxyphenyl)-4-methylthiapyrylium perchlorate, 2,6-bis(4-methoxyphenyl)-4-methylthiapyrylium fluoroborate, 2-hydroxy-4 , 6-bis(4-dimethylaminostyryl)pyrylium perchlorate, 2-hydroxy-4,6-bis(4-dimethylaminostyryl)pyrylium fluoroborate, 2-hydroxy-4,6-bis(4-dimethyl aminostyryl) thiapyrylium perchlorate, 2-hydroxy-4,6-bis(4-dimethylaminostyryl) thiapyrylium fluoroborate, 2-hydroxy-4,6-bis(4-dimethylamino-β-methoxystyryl) ) Thiapyrylium perchlorate, 2-nitro-4-(4-methoxystyryl)-6-
Phenylpyrylium perchlorate, 2-nitro-4-(4-methoxystyryl)-6-
Phenylpyrylium fluoroborate, 2-nitro-4-(4-methoxystyryl)-6-
Phenylthiapyrylium perchlorate, 2-nitro-4-(4-methoxystyryl)-6-
Phenylthiapyrylium fluoroborate, 2-nitro-4-(4-methoxystyryl)-6-
Phenylthiapyrylium fluoroantimonate, 2-nitro-4,6-bis(4-dimethylaminostyryl)pyrylium fluoroborate, 2-nitro-4,6-bis(4-dimethylaminostyryl)thiapyrylium fluoro borate, 2-amino-4,6-bis(4-butoxyphenyl)pyrylium perchlorate, 2-amino-4,6-bis(4-butoxyphenyl)pyrylium fluoroborate, 2-amino-4,6-bis( 4-butoxyphenyl) thiapyrylium perchlorate, 2-amino-4,6-bis(4-butoxyphenyl) thiapyrylium fluoroborate, 2-amino-4,6-bis(4-methoxy-β-
ethylstyryl) thiapyrylium fluoroborate, 4(4-dimethylaminostyryl)-6-[β,β
-bis(4-dimethylaminophenyl)vinylene]thiapyrylium perchlorate, 2-methoxy-4-naphthyl-6-styrylthiapyrylium fluoroborate, and the like. Furthermore, the specific organic dye compound used in the present invention is one that exhibits a yellow to red color range and has a specific structure as exemplified below. 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, and n represents an integer from 1 to 3.
Y is

【formula】

【formula】

[expression] or

Represents [formula]. ] [R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group,
X represents halogen;

【ceremony

【formula】

【formula】

【formula】

[expression] 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, _R2 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group, X represents a halogen, and n represents 1
Represents an integer from ~3. Y is

【formula】

【formula】

【formula】 or

Represents [formula]. ] B: Merocyanine dye [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,
X is

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

[Formula] Ma Taha

Represents [formula]. ] [R ₁ , R ₂ , and R ₃ represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group. ] [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. ] [R ₁ , R ₂ , R ₃ , and R ₄ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group, X represents a halogen, and Y represents a hydrogen atom or an alkali metal. ] D: Thiazole dye [R is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms,
It represents 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 , and R ₄ each independently 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, or an aryl group. or represents a sulfonic acid group, and X represents a halogen or a hydroxyl group. ] The photoinitiator composition of the present invention comprises one of the benzophenone group-containing polyhydric peroxyester compounds (A).
species or two or more species, and one of the organic dye compounds (B) above.
or two or more types as active ingredients, and the weight ratio of (A):(B) is 1 to 99:99 to 1, preferably 5 to 95:95. ~
5, more preferably 10-90:90-10. Excellent effects cannot be obtained with compositions outside the above range. The photoinitiator composition of the present invention is capable of photopolymerizing almost all unsaturated compounds with ultraviolet and visible light in a very short time. These unsaturated compounds include monomers, oligomers, and polymers having polymerizable ethylenically unsaturated bonds, such as acrylic acid, methacrylic acid, itaconic acid, maleic acid and its anhydride, phthalic acid and its anhydride, and fumaric acid. Unsaturated acids such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, glycidyl (meth)acrylate, hydroxyethyl (meth)acrylate,
Unsaturated acid esters such as dimethyl maleate, diethyl maleate, dimethyl fumarate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, etc. , styrene, acrylamide, acrylonitrile, N-vinylpyrrolidone, vinyl acetate, and various unsaturated polyesters, unsaturated polyethers, unsaturated polyurethanes, and epoxy (meth)acrylate compounds. The photoinitiator composition of the present invention is added to one or a mixture of two or more of these unsaturated compounds, and if necessary, a binder, various conventional additives, inhibitors, etc., and a suitable diluting solvent are added. A photopolymerizable composition is prepared. The amount of the photoinitiator composition added is 0.01 to 30 parts by weight, preferably 0.1 to 30 parts by weight, per 100 parts by weight of the unsaturated compound.
It is 20 parts by weight. As a binder, any polymer with film-forming ability can be used; examples include poly-N-vinylpyrrolidone, polymethyl methacrylate, polystyrene, polyvinyl acetate, and their copolymers; In terms of sensitivity, N-vinylpyrrolidone polymers are particularly preferred. Any suitable diluting solvent can be used as long as it dissolves or disperses the photoinitiator composition of the present invention and the unsaturated compound used, such as water, methanol, ethanol, propanol, butanol, acetone, and methyl ethyl ketone. , methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, benzene, toluene, xylene, ethyl acetate, butyl acetate, tetrahydrofuran, dioxane, dichloromethane, chloroform, carbon tetrachloride, trichloroethylene, dimethylformamide, dimethyl sulfoxide, and the like. The photopolymerizable composition thus obtained undergoes a polymerization reaction within a very short time by irradiating it with active light in a wide range from ultraviolet to visible light.
As light sources, ultra-high pressure, high pressure, medium pressure, and low pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, various visible and ultraviolet laser lamps, fluorescent lamps, tungsten lamps, sunlight, etc. can be used. . The photoinitiator composition of the present invention can be used not only for ordinary photopolymerization reactions, but also for the production of photocurable paints, printing inks, adhesives and printing plates, and as a photoresist for the production of printed circuit boards, ICs, etc. It can be applied to many countries, and its effects are also very good. In particular, the photoinitiator composition of the present invention has surprisingly good effects when applied to photosensitive materials for visible light lasers such as Ar ⁺ laser due to its high sensitivity and wide spectral sensitivity characteristics that extend to the visible light region. can get. The present invention will be explained in more detail below using Examples and Comparative Examples. Note that parts in the examples are parts by weight.
These examples are provided for illustrative purposes and are not intended to limit the invention in any way. Examples 1 to 39 100 parts of pentaerythritol triacrylate as unsaturated compound, poly-N as binder
- Using 100 parts of vinylpyrrolidone, 39 types of photoinitiator compositions of the present invention were selected in Table 1.
These were added in the proportions shown below, and these were further uniformly dissolved in 1000 parts of methyl cellosolve to prepare 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. The photosensitivity test uses visible light (wavelength = 488nm), ultraviolet light (wavelength = 365nm) and laser light (wavelength =
Monochromatic light of 488 nm) was used. 488nm of visible light
The monochromatic light was obtained by using a 500W xenon lamp as a light source and passing it through two Toshiba color glass filters Y-47 and KL-49. Monochromatic light of 365 nm was obtained by using a 450 W high-pressure mercury lamp as a light source and passing it through a Toshiba color glass filter UVD35.
The laser beam used was a single line of 2.5 W Ar ⁺ laser with a wavelength of 488 nm and a beam diameter of 1.25 mm. The photoresist film was exposed to each monochromatic light, and the sensitivity was measured by the cumulative light energy until the coating film was completely photocured. The results are shown in Table 1, in which all amounts of photoinitiator composition are based on 100 parts of pentaerythritol triacrylate. Comparative Examples 1 to 17 The same photosensitivity tests as in the examples were conducted using conventionally known photoinitiators, organic peroxides, and organic dye compounds in place of the photoinitiator composition of the present invention. The sensitivity was measured. The results are shown in Table 2, and the amounts of photoinitiators in the table are all pentaerythritol triacrylate 100
This is for the department.

【table】

【table】

[Table] The abbreviations in Tables 1 and 2 that indicate what was not done are as follows.・Benzophenone group-containing peroxy ester compound BTTB: 3,3',4,4'-tetra-(t-butylperoxycarbonyl)benzophenone BTTH: 3,3',4,4'-tetra-(t-amylperoxycarbonyl) Benzophenone BTTC: 3,3',4,4'-tetra(cumylperoxycarbonyl)benzophenone BTDB: 3,3'-di(t-butylperoxycarbonyl)-4,4'-di(carboxy)benzophenone organic dye Compound pyrylium salts MTF: 2,4,6-tri(4-methoxyphenyl)thiapyrylium fluoroborate BTF: 4-(4-butoxyphenyl)-2,6-
Di(4-methoxyphenyl)thiapyrylium fluoroborate AST: 6-(4-dimethylaminostyryl)-2,
4-Diphenylthiapyrylium perchlorate TSP: 2,4,6-triphenylselenopyrylium perchlorate EPP: 2,6-bis(4-ethylphenyl)-4
-(4-Methoxyphenyl)pyrylium fluoroborate NDS: 2-nitro-4,6-bis(4-dimethylaminostyryl)thiapyrylium fluoroborate SMP: 2-hydroxy-4,6-bis(4-dimethyl Amino-β-methoxystyryl) thiapyrylium perchlorate MNS: 2,4,6-triphenyl thiapyrylium perchlorate BBT: 2,4,6-tri(4-butoxyphenyl)pyrylium perchlorate - Known photoinitiator BIPE: benzoin isopropyl ether BP: benzophenone MK: Michaeler's ketone 1,2-BA: 1,2-benzanthraquinone As is clear from Tables 1 and 2, all examples are comparative examples. It has very high sensitivity to both ultraviolet light and visible light, especially to visible light with a wavelength of 488 nm. From the above, the photoinitiator composition of the present invention is
It can be widely applied to a variety of photosensitive materials, and is particularly suitable for those that require high sensitivity characteristics, such as photosensitive materials for visible light lasers.

Claims (1)

[Claims] 1 General formula () [In the formula, R ₁ and R' ₁ are each a tertiary alkyl group having 4 to 8 carbon atoms or a tertiary aralkyl group having 9 to 12 carbon atoms, and R ₂ and R' ₂ are each a hydrogen atom or a tertiary aralkyl group having 4 carbon atoms. represents a tertiary alkoxy group having from 9 to 8 carbon atoms or a tertiary aralkyloxy group having 9 to 12 carbon atoms. ] A photoinitiator composition comprising a benzophenone group-containing polyvalent peroxyester compound shown in the following combination, and any one of the organic dye compounds shown in the following (1) to (5). (1) General formula () [In the formula, R ₁ , R ₂ , R ₃ are each independently a hydrogen atom,
Halogen, alkyl group, haloalkyl group, ethylenyl group, styryl group, alkoxy group, phenyl group, naphthyl group, alkyl phenyl group, alkoxyphenyl group, hydroxyphenyl group, halofenyl group, nitrophenyl group, aminophenyl group, nitro group, amino group or hydroxyl group, X represents oxygen, sulfur or selenium, Y
represents an anionic functional group. ] Pyrylium salt represented by. Thiapyrylium salt or selenopyrillium salt compounds (2) Cyanine dyes (3) Merocyanine dyes (4) Xanthene dyes (5) Thiazole dyes