JPH0565305A - Photopolymerization initiator composition and method for photopolymerization and curing - Google Patents

Abstract

PURPOSE:To obtain a photopolymerization initiator composition highly sensitive to visible light, stable against heat, metal, etc., and excellent in storage stability by combining a specified dialkyl peroxide with an organic dye compound. CONSTITUTION:A dialkyl peroxide of formula I (wherein A1 is formula II or formula III; A2 is 1-20C alkyl, C(R5)(R6)(R7) or A3; A3 is formula IV; A4 is C(R10)(R11)OOR9 or H; R1 and R9 are each 4-12C tert. alkyl, 9-12C cycloalkyl or the like; R2, R3, R10 and R11 are each 1-2C alkyl; R4 is 1-3C alkyl or H; R5 and R6 are each 1-4C alkyl or may be combined to form 5-8C cycloalkyl; R7 is hydroxy, chloro, bromo or the like; R8 is 1-12C alkyl, 1-4C alkoxy or the like; (m) is 1 or 2; and (n) is 1-3) is combined with an organic dye compound (e.g. camphorquinone) to produce the objective photoplymerization initiator composition.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a photopolymerization initiator composition for polymerizing and curing an ethylenically unsaturated compound, and a photopolymerization / curing method.

[0002]

2. Description of the Related Art 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 are used in paints, adhesives, printing plates and printed wiring boards, Widely used as a photoresist. In recent years, in the field of information recording, use of visible laser light has been actively studied in place of ultraviolet rays which have been widely used conventionally. For example, a method of directly drawing an image on a PS plate or a dry film using a visible laser beam of argon has been studied. Conventionally, there are many photopolymerization initiator systems sensitive to the ultraviolet region with relatively high sensitivity. For example, conventional photopolymerization initiators such as benzoin alkyl ethers, hydroxyacetophenones and benzyl dimethyl ketal are sensitive to ultraviolet rays and initiate polymerization and curing. However, it has almost no initiation ability with visible light. As one of initiator systems sensitive to visible light, a combined system of an ester type organic peroxide and a dye sensitizer has been developed. For example, the Chemical Society of Japan, 1985, p.
-76503 describes a system using a thiopyrylium salt as a dye, and JP-A-63-23901 describes a system using ketocoumarin as a dye.

[0003]

The ester type organic peroxide and dye sensitizer initiator system is sensitive to visible light.
Ester-type organic peroxides are relatively unstable to heat and to compounds containing heteroatoms and transition metals, and therefore have good stability over time when used as an initiator itself or a photosensitive layer. Absent. Therefore, development of a photopolymerization initiator which is sensitive to not only ultraviolet rays but also visible rays and has excellent storage stability is desired.

[0004]

The present inventors have accomplished the present invention as a result of intensive research to solve the above-mentioned problems. That is, the present invention has the following general formula

[Chemical 5] (In the formula, A ₁ is

[Chemical 6] Or

[Chemical 7] The stands, A ₂ is an alkyl group having 1 to 20 carbon _{atoms, -C (R 5) (R} 6)
Represents (R ₇₎ group or A _3,, A ₃ is

[Chemical 8] And A ₄ represents a —C (R ₁₀ ) (R ₁₁ ) OOR ₉ group or a hydrogen atom, and R ₁ and R ₉ represent a tertiary alkyl group having 4 to 12 carbon atoms,
A cycloalkyl group having 9 to 12 carbon atoms, a substituted tertiary alkyl group or a tertiary aralkyl group having 9 to 12 carbon atoms, R ₂ ,
R ₃ , R ₁₀ and R ₁₁ are alkyl groups having 1 to 2 carbon atoms, R ₄ is an alkyl group having 1 to 3 carbon atoms or a hydrogen atom, and R ₅ and R ₆ are 1 carbon atoms.
~ 4 alkyl group, or R ₅ and R ₆ are bonded to each other, a cycloalkyl group having 5 to 8 carbon atoms in total, R ₇ is a hydroxyl group, a chlorine atom, a bromine atom or an alkoxy group having 1 to 4 carbon atoms, R ₈ is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom or a hydrogen atom, m is 1 or 2, n
Represents an integer of 1 to 3. ) A photopolymerization initiator composition comprising one or more dialkyl peroxides represented by the formula (1) and one or more organic dye compounds, and a photopolymerization initiator for the composition. The present invention provides a method for photopolymerization / curing an ethylenically unsaturated compound, which is used as an agent.

The dialkyl peroxide represented by Chemical formula 5 used as one component of the photopolymerization initiator composition of the present invention is described in JP-A-3-52856, 3-81260, 3-93769 and the like. It can be synthesized by any method. Specifically showing examples of these dialkyl peroxides,
4- (1-t-butylperoxy-1-methylethyl)
Benzophenone, 4- (1-t-amylperoxy-1)
-Methylethyl) benzophenone, 4- (1-t-hexylperoxy-1-methylethyl) benzophenone,
4- (1-t-octylperoxy-1-methylethyl) benzophenone, 4- (1-cumylperoxy-1)
-Methylethyl) benzophenone, 4- {1- (1-cyclohexyl-1-methylethylperoxy) -1-methylethyl} benzophenone, 4- {1- (1,1,5
-Trimethylheptylperoxy) -1-methylethyl} benzophenone, 4- (1-t-butylperoxy-1-methylethyl) -2-methylbenzophenone, 4
-(1-t-Butylperoxy-1-methylethyl)-
2-Propylbenzophenone, 4- (1-t-butylperoxy-1-methylethyl) -2,6-dipropylbenzophenone, 4- (1-t-butylperoxy-1-
Methylethyl) -2,6-dipropyl-4'-t-dodecylbenzophenone, 4- (1-t-butylperoxy-1-methylethyl) -4'-chlorobenzophenone,
4- (1-t-butylperoxy-1-methylethyl)
-4'-Bromobenzophenone, 4- (1-t-butylperoxy-1-methylethyl) -4'-butoxybenzophenone, 4- (1-t-octylperoxy-1-
Methylpropyl) -2,6-dipropyl-2 ', 3',
4'-trimethoxybenzophenone, 4- (1-t-octylperoxy-1-methylpropyl) -2,6-dipropyl-3 ', 4'-diethoxybenzophenone, 3
-(1-t-Butylperoxy-1-methylethyl) benzophenone, 3- (1-t-octylperoxy-1)
-Methylpropyl) -6-propyl-3 ', 4'-diethoxybenzophenone, 4,4'-bis (1-t-butylperoxy-1-methylethyl) benzophenone,
4,4'-bis (1-t-amylperoxy-1-methylethyl) benzophenone, 4,4'-bis (1-t-
Hexylperoxy-1-methylethyl) benzophenone, 4,4'-bis (1-t-octylperoxy-1)
-Methylethyl) benzophenone, 4,4'-bis (1
-Cumylperoxy-1-methylethyl) benzophenone, 4,4'-bis (1-t-butylperoxy-1-
Methylethyl) -2-methylbenzophenone, 4,4 '
-Bis (1-t-butylperoxy-1-methylethyl) -2,6-dimethylbenzophenone, 4,4'-bis (1-t-octylperoxy-1-methylpropyl) -2,6-diisopropylbenzohe Non, 3,
4'-bis (1-t-butylperoxy-1-methylethyl) -6-methylbenzophenone, 3,4'-bis (1-t-octylperoxy-1-methylethyl)-
6-isopropylbenzophenone, 3,3'-bis (1
-T-Butylperoxy-1-methylethyl) -6-methylbenzophenone, 3,3'-bis (1-t-octylperoxy-1-methylethyl) -6-isopropylbenzophenone, 1- {4- (1- t-butylperoxy-1-methylethyl) phenyl} -2-hydroxy-
2-methylpropan-1-one, 1- {4- (1-t-
Amylperoxy-1-methylethyl) phenyl} -2
-Hydroxy-2-methylpropan-1-one, 1-
{4- (1-t-hexylperoxy-1-methylethyl) phenyl} -2-hydroxy-2-methylpropan-1-one, 1- {4- (1-t-octylperoxy-1-methylethyl) Phenyl} -2-hydroxy-2
-Methylpropan-1-one, 1- {4- (1-cumylperoxy-1-methylethyl) phenyl} -2-hydroxy-2-methylpropan-1-one, 1- {4-
(1-t-butylperoxy-1-methylethyl)-
2,6-Dimethylphenyl} -2-hydroxy-2-methylpropan-1-one, 1- {4- (1-t-butylperoxy-1-ethylpropyl) phenyl} -2-hydroxy-2-methylpropane -1-on, 1- {4-
(1-t-Butylperoxy-1-methylethyl) phenyl} -2-hydroxy-2-methylpentan-1-one, 1- {4- (1-t-butylperoxy-1-methylethyl) phenyl}- 2-hydroxy-2-ethylhexan-1-one, 1- {4- (1-t-butylperoxy-1-methylethyl) benzoyl} -1-hydroxycyclopentane, 1- {4- (1-t- Butylperoxy-1-methylethyl) benzoyl} -1-hydroxycyclohexane, 1- {4- (1-t-butylperoxy-1-methylethyl) benzoyl} -1-hydroxycycloheptane, 1- {4- (1 -T-octylperoxy-1-ethylpropyl) -2,6-diisopropylphenyl} -2-hydroxy-2-butylhexane-
1-one, 1- {4- (1-t-butylperoxy-1
-Methylethyl) phenyl} -2-chloro-2-methylpropan-1-one, 1- {4- (1-t-butylperoxy-1-methylethyl) phenyl} -2-bromo-
2-methylpropan-1-one, 1- {4- (1-t-
Butylperoxy-1-methylethyl) phenyl} -2
-Methoxy-2-methylpropan-1-one, 1- {4
-(1-t-Butylperoxy-1-methylethyl) phenyl} -2-butoxy-2-methylpropan-1-one, 1- {3- (1-t-butylperoxy-1-methylethyl) phenyl} -2-hydroxy-2-methyl-
Propan-1-one, 1- {3- (1-t-octylperoxy-1-methylethyl) -6-methylphenyl}
-2-hydroxy-2-methyl-propan-1-one,
1- {3- (1-t-hexylperoxy-1-ethylpropyl) -6-methylphenyl} -2-hydroxy-
2-methyl-propan-1-one, 1- {3- (1-t
-Amylperoxy-1-methylethyl) -6-methylphenyl} -2-chloro-2-methyl-propane-1-
On, 1- {3- (1-t-cumyloctylperoxy-1-methylethyl) -6-methylphenyl} -2-butoxy-2-methyl-propan-1-one, 1- {3-
(1-t-butylperoxy-1-methylethyl) -6
-Methylbenzoyl} -1-hydroxycyclohexane, 1- {3- (1-t-octylperoxy-1-ethylpropyl) -6-isopropylphenyl} -2-hydroxy-2-butylhexan-1-one, 1- {4-
(1-t-Amylperoxy-1-methylethyl) phenyl} ethanone, 1- {4- (1-t-hexylperoxy-1-methylethyl) phenyl} ethanone, 1-
{4- (1-t-octylperoxy-1-methylethyl) phenyl} ethanone, 1- {4- (1-t-butylperoxy-1-methylethyl) -2-methylphenyl} ethanone, 1- {4 -(1-t-Butylperoxy-1-methylethyl) -2,6-dimethylphenyl} ethanone, 1- {4- (1-t-butylperoxy-1-
Methylethyl) -2,6-diisopropylphenyl} ethanone, 1- {4- (1-t-butylperoxy-1-
Methylethyl) -2-phenyl} propan-1-one,
1- {4- (1-t-butylperoxy-1-methylethyl) phenyl} -2,2'-dimethylpropane-1-
On, 1- {4- (1-t-butylperoxy-1-methylethyl) phenyl} dodecane-1-one, 1- {4
-(1-t-Butylperoxy-1-methylethyl) phenyl} eicosan-1-one, 1- {4- (1-t-
Octylperoxy-1-ethylpropyl) -2,6-
Diisopropylphenyl} heneicosan-1-one,
1- {3- (1-t-butylperoxy-1-methylethyl) phenyl} ethanone, 1- {3- (1-t-amylperoxy-1-methylethyl) phenyl} ethanone, 1- {3- ( 1-t-hexylperoxy-1-methylethyl) phenyl} ethanone, 1- {3- (1-t
-Octylperoxy-1-methylethyl) phenyl}
Ethanone, 1- {3- (1-cumylperoxy-1-methylethyl) phenyl} ethanone, 1- {3- (1-t
-Butylperoxy-1-methylethyl) -6-methylphenyl} ethanone, 1- {3- (1-t-butylperoxy-1-methylethyl) -6-isopropenyl}
Ethanone, 1- {3- (1-t-butylperoxy-1
-Methylethyl) -6-methylphenyl} butane-1-
On, 1- {3- (1-t-butylperoxy-1-methylethyl) -6-methylphenyl} 2,2-dimethylpropan-1-one, 1- {3- (1-t-butylperoxy- 1-Methylethyl) -6-methylphenyl} hexan-1-one, 1- {3- (1-t-butylperoxy-1-methylethyl) -6-methylphenyl} decan-1-one, 1- { 3- (1-t-butylperoxy-1-methylethyl) -6-methylphenyl} heneicosan-1-one, 1- {3- (1-t-octylperoxy-1-ethylpropyl) -6-isopropylphenyl } Heneicosan-1-one, 1-phenyl-2-
t-Butylperoxy-2-methylpropan-1-one, 1-phenyl-2-t-amylperoxy-2-methylpropan-1-one, 1-phenyl-2-t-hexylperoxy-2-methylpropane- 1-on, 1-
Phenyl-2-t-octylperoxy-2-methylpropan-1-one, 1-phenyl-2-t-cumylperoxy-2-methylpropan-1-one, 1- (4-methylphenyl) -2- t-Butylperoxy-2-methylpropan-1-one, 1- (4-dodecylphenyl)
-2-t-butylperoxy-2-methylpropane-1
-One, 1- (4-butoxyphenyl) -2-t-butylperoxy-2-methylpropan-1-one, 1-
(2,3,4-Trimethoxyphenyl) -2-t-butylperoxy-2-methylpropan-1-one, 1-
(2,4-Dichlorophenyl) -2-t-butylperoxy-2-methylpropane) -1-one, 1- (2,
4,6-Trimethylphenyl) -2-t-octylperoxy-2-ethylbutan-1-one, 1- (2,4-
Diethylphenyl) -2-t-octylperoxy-2
-Butylhexan-1-one, 1- {4- (1-t-butylperoxy-1-methylethyl) phenyl} -2-
t-Butylperoxy-2-methylpropan-1-one, 1- {4- (1-t-octylperoxy-1-methylpropyl) -2,6-diisopropylphenyl}-
2-t-hexylperoxy-2-butylhexane-1
-One, 1- {3- (1-t-butylperoxy-1-
Methylethyl) phenyl} -2-t-butylperoxy-2-methylpropan-1-one, 1- {3- (1-t
-Octylperoxy-1-methylpropyl) -6-methylphenyl} -2-cumylperoxy-2-butylhexan-1-one.

The organic dye compound used as one component of the photopolymerization initiator composition of the present invention has the following general formula:

[Chemical 9] (In the formula, R ₁₂ , R ₁₃ , and R ₁₄ are each independently a hydrogen atom, a halogen atom, an alkyl group, a haloalkyl group, an ethylenyl group,
Styryl group, alkoxy group, phenyl group, naphthyl group,
Represents an alkylphenyl group, an alkoxyphenyl group, a hydroxyphenyl group, a halophenyl group, a nitrophenyl group, an aminophenyl group, a nitro group, an amino group or a hydroxyl group, X ₁ represents an oxygen atom or a sulfur atom, and Y ₁ represents an anion functional group. .. ) Pyrylium salt or thiopyrylium salt represented by the following general formula

[Chemical 10] (In the formula, R ₁₅ , R ₁₆ and R ₁₇ are each independently a hydrogen atom, a chlorine atom, a lower alkoxy group, a lower dialkylamino group, a lower dialkenylamino group or an alicyclic amino group, Z ₁ is a carbon atom and Heterocyclic group having the total number of hetero atoms of 5 to 9 or the following formula

[Chemical 11] Represents a group represented by. Z ₂ represents a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a lower alkoxy group, a substituted or unsubstituted phenyl group, an unsubstituted styryl group or a substituted or unsubstituted 3′-coumarino group. X ₂ represents a hydrogen atom or a cyano group. ) Coumarin compound represented by the following general formula

[Chemical formula 12] (In the formula, R ₁₈ and R ₁₉ each represent a hydrocarbon group or a substituted hydrocarbon group, and each may be bonded directly or via a divalent hydrocarbon group or a substituted hydrocarbon group, and R ₁₈ ,
R ₁₉ may be taken together to form a condensed aromatic ring structure. Examples of the α-diketones, cyanine dyes, merocyanine dyes, xanthene dyes, thiazole dyes and the like.

The pyrylium salt or thiopyrylium salt represented by Chemical formula 9 can be synthesized by the method described in Helv. Chim. Acta, 39, 5 (1956). Examples of the anionic functional group represented by Y ₁ in Chemical formula 9 include perchlorate, trifluoroborate, chloroaluminate, chloroferrate, sulfaacetate, methosulfate, and thiocyanate. Specific examples of these dyes are 2,4,6-triphenylpyrylium perchlorate, 4- (4-methoxyphenyl) -2,6.
-Diphenylpyrylium tetrafluoroborate, 2,
There are 4,6-tri (4-methoxyphenyl) thiopyrylium perchlorate, 2,6-bis (4-methoxyphenyl) -4- (4-butoxyphenyl) thiapyrylium tetrafluoroborate and the like.

The coumarin compound represented by the chemical formula 10 is Organi
c Reactions, 15, 204, ChemicalReviews, 36, 1 (1945)
And Tetrahedron, 38, 1203 (1982) and the like. Specific examples of these dyes include 3-acetyl-7-diethylaminocoumarin, methyl 7-diethylamino-3-coumarinnoyl acetate and 7-diethylamino-7'-methoxy-3,3'-carbonylbiscoumarin. 3- (2'benzimidazolyl) -7-diethylaminocoumarin, 3-
Methoxycarbonyl-7-diethylaminocoumarin,
3,3'-carbonylbis (4-cyano-7-diethylamino) coumarin and the like.

Specific examples of the α-diketones represented by Chemical formula 12 are biacetyl, 2,3-pentadione, and 2,3-
Octadione, benzyl, 4,4'-dimethylbenzyl, 4,4'-chlorobenzyl, acenaphthenequinone,
9,10-phenanthrenequinone, camphorquinone, β
-There are naphthoquinones.

In addition to the above, the specific organic dye compound used in the present invention has a specific structure as shown below, which exhibits a yellow to red color gamut.

A: Cyanine dye a)

[Chemical 13] (In the formula, R ₂₀ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms,
An aryl group, an alkoxy group or a dialkylamino group,
R ₂₁ is a hydrogen atom, an alkyl group or an aryl group having 1 to 10 carbon atoms, X ₃ is a halogen atom, n is an integer of 1 to 3, and Z ₃ is

[Chemical 14] ), B)

[Chemical 15] (In the formula, R _{22 and} R ₂₃ are each independently a hydrogen atom and a carbon number of 1-10.
An alkyl group or an aryl group, X ₃ represents a halogen atom,

[Chemical 16] Is

[Chemical 17] Stands for) and c)

[Chemical 18] (In the formula, R ₂₄ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms,
An aryl group or an alkoxy group, R ₂₁ is a hydrogen atom, an alkyl group or an aryl group having 1 to 10 carbon atoms, X ₃ is a halogen atom, n is an integer of 1 to 3, and Z ₄ is

[Chemical 19] Represents. )

B: Merocyanine dye a)

[Chemical 20] (In the formula, R ₂₅ and R ₂₆ are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, n is an integer of 1 to 3, and Z ₅ is the following formula.

[Chemical 21] Represents. ), B)

[Chemical formula 22] (In the formula, R ₂₇ , R ₂₈ , and R ₂₉ represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group), and c).

[Chemical formula 23] (In the formula, R ₂₇ , R ₂₈ , and R ₂₉ represent a hydrogen atom, an alkyl group or an aryl group having 1 to 6 carbon atoms, and M represents a hydrogen atom or an alkali metal.)

C: xanthene dye a)

[Chemical formula 24] (In the formula, M represents a hydrogen atom or an alkali metal, and X ₄ represents a hydrogen atom or a halogen atom.) B)

[Chemical 25] (In the formula, R ₂₇ , R ₂₈ , R ₂₉ , and R ₃₀ are hydrogen atoms and have 1 to 6 carbon atoms.
Alkyl group or aryl group, X ₃ is a halogen atom, M
Represents a hydrogen atom or an alkali metal. )

D: Thiazole dye a)

[Chemical formula 26] (In the formula, R ₃₁ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms,
Aryl group, alkoxy group, nitro group or amino group,
Z ₆ represents an amino group or a phenylamino group. ), B)

[Chemical 27] (In the formula, R ₂₇ , R ₂₈ , R ₂₉ , and R ₃₀ are hydrogen atoms and have 1 to 6 carbon atoms.
Is an alkyl group or an aryl group, R ₃₂ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group, or a sulfonic acid group, and X ₅ is a halogen atom or a hydroxyl group. ).

The photopolymerization initiator composition of the present invention contains one or more dialkyl peroxides represented by Chemical formula 5 and one or more of the organic dye compounds as active ingredients. The mixing ratio of the two is a weight ratio, and the dialkyl peroxide: organic dye compound is 1:
It is in the range of 100 to 100: 1, preferably 10: 1 to 5: 1.

The photopolymerization initiator composition of the present invention is used as a photopolymerization initiator for photopolymerization or photocuring of an ethylenically unsaturated compound. At this time, a binder polymer, a thermal polymerization inhibitor, if necessary, in a mixture of one or more ethylenically unsaturated compounds and the photopolymerization initiator of the present invention,
A photosensitive composition can be prepared by adding a plasticizer, a diluting solvent and the like. Such a photosensitive composition is used for paints, adhesives, printing inks, printing reliefs, printed wiring boards, photoresists and the like.

Examples of the ethylenically unsaturated compound which can be photopolymerized and photocured by blending the photopolymerization initiator composition of the present invention include a polymerizable monomer, a polymerizable oligomer, and a polymerizable unsaturated polymer. Be done. The polymerizable monomer is a compound having one or more polymerizable double bonds, for example, unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, and , Derivatives of these unsaturated carboxylic acids, eg methyl (meth) acrylate, butyl (meth) acrylate, 2-
Monoesters such as ethylhexyl (meth) acrylate, phenyl (meth) acrylate and benzyl (meth) acrylate, hydroxyesters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate, ethylene glycol di (Meth) acrylate, polyethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate and other polyvalent esters, (meth) acrylonitrile, (Meth) acrylamide, N-substituted (meth) acrylamide, etc., vinyl acetate, vinyl propionate, vinyl acetate, vinyl succinate, etc. Ethers, vinyl ethers, styrene, alkyl styrene, halogenated styrene, divinylbenzene, vinyl naphthalene, N- vinylpyrrolidone, diallyl phthalate, diallyl maleate,
Examples thereof include vinyl compounds such as triallyl isocyanate and triallyl phosphate. Examples of the polymerizable oligomer and the polymerizable unsaturated polymer include a curable resin having a malate group, a fumarate group, an allyl group, a (meth) acrylate group, an unsaturated polyester, an unsaturated acrylic resin, and an isocyanate-modified acrylic resin. Examples thereof include oligomers, polyester acrylic oligomers, and polyether acrylic oligomers.

When the photopolymerization initiator composition of the present invention is used by adding it to an ethylenically unsaturated compound, if the addition amount is too small, the efficiency of photopolymerization / curing is poor, and if it is too large, it is uneconomical. Not only that, the light does not reach the inside,
It becomes less efficient. Therefore, it is preferable to add the photopolymerization initiator composition of the present invention in the range of 0.1 to 30 parts by weight to 100 parts by weight of the ethylenically unsaturated compound.

As the binder polymer, any polymer capable of forming a coating film can be used. For example, Poly-N
-Vinylpyrrolidone, polymethylmethacrylate, polystyrene, polyvinylacetate, and copolymers thereof.

Any solvent can be used as the diluting solvent as long as it can be dissolved or dispersed. For example, methyl ethyl ketone, methyl isobutyl ketone, acetone, ethyl acetate, butyl acetate, benzene, toluene, xylene, methyl cellosolve, ethyl cellosolve, methanol, ethanol, propanol. , Butanol, tetrahydrofuran, dioxane, dichloromethane, chloroform, carbon tetrachloride, trichloroethylene, trichloroethane, dimethylformamide, dimethylsulfoxide, and the like.

The photosensitive composition thus obtained is
The polymerization reaction can be carried out by irradiating with actinic rays such as ultraviolet rays and visible rays. The irradiation light may be ultraviolet light, but visible light of 400 to 700 nm is preferable. As the light source, a xenon lamp, various low-pressure, medium-pressure, high-pressure, and ultra-high-pressure mercury lamps, chemical lamps, tungsten lamps, fluorescent lamps, sunlight, various lasers, and the like can be used.

[0022]

Since the photopolymerization initiator composition of the present invention is used in combination with a dialkyl peroxide and an organic dye compound, it has high sensitivity to visible light and completes polymerization and curing in a short time even under weak light. However, it is excellent in terms of economy and workability. Further, the initiator composition of the present invention is stable to heat and metals, and thus has good storage stability. The photopolymerization initiator composition of the present invention can be used for ordinary photopolymerization reaction,
It can be applied to various fields such as photo-curable paints, printing inks, adhesives, printing plates, photoresists and holography.

[0023]

EXAMPLES Next, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. In addition, "part" in an example shows a "weight part."

Examples 1 to 16 Acrylic polymer prepared by a conventional method (methyl methacrylate / methacrylic acid / ethyl acrylate = 60/20/20) 1
After dissolving 00 parts and 100 parts of pentaerythritol acrylate in 1000 parts of methyl cellosolve, the photopolymerization initiator shown in Table 1 was added in an amount shown in Table 1 to prepare a photosensitive solution.
This photosensitive solution was applied onto a polyethylene terephthalate sheet using a bar coater so that the dry film thickness was 2 μm, and then dried with a hot air dryer at 80 ° C. for 10 minutes. A sample was prepared by heating and press-bonding this film on an anodized aluminum plate so that the coating film was in contact with the aluminum surface. Then, a gray scale (Kodak Step Tablet No. 2) was brought into close contact with the prepared sample polyethylene terephthalate film, and a photosensitivity test by irradiation with visible light was performed. Visible light was exposed for 20 seconds from a distance of 50 cm through a Toshiba colored glass filter Y-43 using a 500 W xenon lamp as a light source. Then, the polyethylene terephthalate film was removed, and the film was developed with a 0.1% sodium silicate aqueous solution, and the number of steps of the remaining cured film was measured. The results are shown in Table 1.
The larger the step number, the higher the sensitivity.

Comparative Examples 1 to 5 As photopolymerization initiators in the compositions of Example 1, Table 2
The sensitivity was evaluated in exactly the same manner except that it was replaced with the one shown in. The results are shown in Table 2.

[0026]

[Table 1]

[0027]

[Table 2] Abbreviations in the table are as follows. PBP: 4- (1-t-butylperoxy-1-methylethyl) benzophenone PPBP: 4,4'-bis (1-t-butylperoxy-1)
-Methylethyl) benzophenone PAP: 1- {4- (1-t-butylperoxy-1-methylethyl) phenyl} ethanone MAP: 1- {3- (1-t-butylperoxy-1-methylethyl) phenyl} Ethanone AIP: 1-phenyl-2-t-butylperoxy-2-
Methylpropan-1-one PHIP: 1- {4- (1-t-butylperoxy-1-methylethyl) phenyl} -2-hydroxy-2-methylpropan-1-one BTF: 4- (4-butoxyphenyl ) -2,6-Di (4
-Methoxyphenyl) thiopyrylium tetrafluoroborate AMCC: 7-diethylamino-7'-methoxy-3,3 '
-Carbonylbiscoumarin CQ: Camphorquinone A-1:

[Chemical 28] B-1:

[Chemical 29] C-1:

[Chemical 30] D-1:

[Chemical 31] BIF: di-t-butyl peroxyisophthalate BIBP: benzoin isobutyl ether

From Tables 1 and 2, it is clear that the photopolymerization initiator composition of the present invention has higher sensitivity than the comparative examples.

Test Examples 1 to 10 The photosensitive solutions of Examples 1 to 7, 10 , and 13 to 16 were applied to a copper plate, respectively, dried, and allowed to stand at 80 ° C. for 3 hours, and then washed with a 0.1% sodium silicate aqueous solution without exposure. However, neither was cured.

Test Examples 11 to 13 The photosensitive solutions of Comparative Examples 1 to 3 were applied to a copper plate, dried, and allowed to stand at 80 ° C. for 3 hours, and then washed with a 0.1% sodium silicate aqueous solution without being exposed. Was.

As shown in Test Examples 11 to 13, the photosensitive solution containing a photopolymerization initiator other than the present invention is cured by heating and contact with copper. As described above, the photosensitive solution containing the photopolymerization initiator composition of the present invention does not cure even under the same conditions. From this, it can be seen that the photosensitizer containing the photopolymerization initiator composition of the present invention is stable to heat and metals, and has excellent storage stability under conditions other than light irradiation, that is, in the dark. ..

Claims (2)

[Claims] 1. The following general formula: (In the formula, A ₁ is Or [Chemical 3] The stands, A ₂ is an alkyl group having 1 to 20 carbon _{atoms, -C (R 5) (R} 6) (R
₇ ) group, or A ₃ , wherein A ₃ is And A ₄ represents a —C (R ₁₀ ) (R ₁₁ ) OOR ₉ group or a hydrogen atom, and R ₁ and R ₉ represent a tertiary alkyl group having 4 to 12 carbon atoms,
A cycloalkyl group having 9 to 12 carbon atoms, a substituted tertiary alkyl group or a tertiary aralkyl group having 9 to 12 carbon atoms, R ₂ ,
R ₃ , R ₁₀ and R ₁₁ are alkyl groups having 1 to 2 carbon atoms, R ₄ is an alkyl group having 1 to 3 carbon atoms or a hydrogen atom, and R ₅ and R ₆ are 1 carbon atoms.
~ 4 alkyl group, or R ₅ and R ₆ are bonded to each other, a cycloalkyl group having 5 to 8 carbon atoms in total, R ₇ is a hydroxyl group, a chlorine atom, a bromine atom or an alkoxy group having 1 to 4 carbon atoms, R ₈ is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom or a hydrogen atom, m is 1 or 2, n
Represents an integer of 1 to 3. ) One or more dialkyl peroxides represented by
A photopolymerization initiator composition comprising one or a combination of two or more species. 2. A photopolymerization of an ethylenically unsaturated compound, characterized in that the photopolymerization initiator composition according to claim 1 is used as an initiator for the visible light polymerization / curing of an ethylenically unsaturated compound. Curing method.