JPH08217812A - Photoinitiator composition, photopolymerizable composition and photopolymerization method - Google Patents

Abstract

(57) [Summary] (Modified) [Purpose] Fields that require photopolymerizable compounds to be polymerized in a short time, such as photocurable inks, photocurable paints and coating agents, photocurable adhesives. Agent and sealant,
Photocurable encapsulant and composite agent, photocurable ink jet, photocurable microcapsule, photosensitive printing plate,
It is preferably used in applications such as photoresist inks, proof materials, stereolithography resins, hologram materials and the like. [Structure] A compound composed of a transition metal coordination complex cation and an organic boron anion that generates a free radical and an acid when exposed to actinic radiation, and a triazine compound having a trihalogenomethyl group and a chromophore group in the molecule. A photoinitiator composition comprising, and a compound having an ethylenically unsaturated bond capable of free radical initiated addition polymerization thereto,
A photopolymerizable composition further comprising a compound having a functional group capable of cationic polymerization, and a photopolymerization method.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a photoinitiator composition which generates free radicals and acids when exposed to actinic radiation, a photopolymerizable composition containing the photoinitiator composition, and the photopolymerizable composition. The present invention relates to a polymerization method of. More specifically, by polymerizing a photopolymerizable compound in a short time, for example, a photocurable ink, a photocurable paint and a coating agent, a photocurable adhesive and a sealant, a photocurable sealant and a composite agent. , A photocurable ink jet, a photocurable microcapsule, a photosensitive printing plate, a photoresist ink, a proof material, a stereolithography resin, a hologram material, and the like, which is preferably used as a photoinitiator composition, a photopolymerizable composition, and It relates to a photopolymerization method.

[0002]

2. Description of the Related Art In recent years, application as a photopolymerization initiator has been reported, focusing on the ability of polyhalogenated compounds to generate free radicals and acids. For example, JP-A-53-13342
No. 8 (Japanese Patent Publication No. 62-44258) discloses an s-triazine compound having one substituted or unsubstituted dinuclear or trinuclear aromatic group or heterocyclic aromatic ring group and two halomethyl groups. In JP-A-60-89473, trihalogenomethyl group-substituted triazine compounds having a carbonylmethylene heterocycle are disclosed in JP-A-60-1056.
In No. 67, the arylvinylphenyl-bis-trichloromethyl-s-triazine compound is also disclosed in JP-A-2-3686, JP-A-2-4782, and JP-A-2-47.
87 and JP-A-2-292278 disclose various triazine compounds having a trihalogenomethyl group.

By combining the photopolymerization initiator system of these known documents with a compound having a free radical-polymerizable ethylenically unsaturated bond or a compound capable of undergoing cationic polymerization, polymerization is possible by irradiation with light in the ultraviolet to visible region. Although a photopolymerizable composition can be obtained, further improvement in sensitivity characteristics has been desired. In particular, in order to improve the polymerization characteristics of the triazine compound having a trihalogenomethyl group, development of a combination initiator has been desired.

[0004]

The present invention is directed to a photoinitiator composition which generates a free radical and an acid capable of being polymerized in a short time by exposure to actinic radiation, and a photoinitiator containing the photoinitiator composition. A polymerizable composition and a photopolymerization method are provided. More specifically, by polymerizing a photopolymerizable compound in a short time, for example, a photocurable ink, a photocurable paint and a coating agent, a photocurable adhesive and a sealant, a photocurable sealant and a composite agent. , Photo-curable ink jets, photo-curable microcapsules, photosensitive printing plates, photoresist inks, proof materials, stereolithography resins, hologram materials, and other suitable photoinitiator compositions, photopolymerizable compositions And a photopolymerization method.

[0005]

Means for Solving the Problems In consideration of the above points, the present inventors have made earnest studies to achieve the above object, and as a result,
The present invention has been achieved. That is, the first invention of the present invention is represented by the general formula (1)

[0006]

Embedded image (In the formula, C ^{n +} is a transition metal complex coordination complex cation,
R ¹ , R ² , R ³ and R ⁴ are each an alkyl group, an aryl group, an alkaryl group, an allyl group, an aralkyl group, an alkenyl group, an alkynyl group, an alicyclic group, and a saturated or unsaturated heterocyclic group. Each is independently selected from the group and n is an integer from 1 to 3. ), A photoinitiator comprising a compound (A) composed of a transition metal coordination complex cation and an organic boron anion, and a triazine compound (B) having a trihalogenomethyl group and a chromophore group in the molecule. A second invention is a photopolymerizable composition, wherein the photoinitiator composition is compounded with a compound (C) having a free radical-initiated addition-polymerizable ethylenically unsaturated bond, A third invention is a photopolymerization method of initiating radical polymerization by irradiating the photopolymerization composition with an actinic ray, and a fourth invention is the photopolymerizable composition, further comprising a cationically polymerizable functional group. A fifth aspect of the present invention is a photopolymerizable composition comprising a compound (D) having a group, wherein the photopolymerizable composition is irradiated with actinic rays to initiate radical polymerization and cationic polymerization. Special A photopolymerization method according to.

The present invention will be described in detail below.
First, the compound (A) composed of a transition metal coordination complex cation and an organic boron anion used in the present invention is represented by the general formula (1)

[0008]

Embedded image (In the formula, C ^{n +} is a transition metal complex coordination complex cation,
R ¹ , R ² , R ³ and R ⁴ are each an alkyl group, an aryl group, an alkaryl group, an allyl group, an aralkyl group, an alkenyl group, an alkynyl group, an alicyclic group, and a saturated or unsaturated heterocyclic group. Each is independently selected from the group and n is an integer from 1 to 3. ) Is shown. The complex C ^{n +} preferably has the general formula (2)

[0009]

[Chemical 4] (Wherein M is a central transition metal atom, L is one or more identical or different ligands shared by the central transition metal atom, X is an integer of 2 to 6, and n is 1 to 3) Is an integer of.). The complex can have a coordination number of 4, 5, 6, 7 or 8, but more preferred complex cations have a coordination number of 6. Examples of useful transition metal atoms include Re (I), Fe (II), Ru (I
I), Os (II), Co (III) and Ir (II
I) and the like. In the present invention, in particular Ru
(II) has been found to be useful.

Examples of the ligand capable of coordinating with a transition metal atom to form a transition metal coordination complex include pyridine (try) and substituted pyridine, 2,2'-bipyridine (bipy), 4 , 4'-dimethyl-2,2'-bipyridine (Me ₂ bipy), 1,10- phenanthroline (phen), 3,4,7,8-tetramethyl-1,1
0-phenanthroline (Me ₄ phen), 2,2 ′,
2 ″ -terpyridine, 5,6-dimethyl-1,10-phenanthroline (5,6-Me ₂ ph
en), 5-methyl-1,10-phenanthroline (5
-Mephen), 5-chloro-1,10-phenanthroline (5-Clphen), 5-nitro-1,10-.
Phenanthroline (5-NO ₂ phen), 4,7-dimethyl-1,10-phenanthroline (4,7-Me ₂
phen), 6,6′-dimethyl-4,4′-bipyrimidine (6,6′-Me ₂ bpym) and 2,4,6-
Examples thereof include tri (2-pyridyl-s-triazine) (TPTZ) and its substituted derivatives. Juris et al. "Coordination Che
The ligands described in "Mistry Reviews", Vol. 84, p. 85 (1988) can also be used.

Therefore, it is suitable for use in the present invention.
Specific examples of the transition metal coordination complex include Co (bip)
y)₃ ²⁺, Co (Me₂bipy)₃ ²⁺, Co (Me₂bi
py) (bipy)₂ ²⁺, Co (terpy)₂ ²⁺, Co
(Phen)₃ ²⁺, Co (5-Mephen)₃ ²⁺, Co
(5-Clphen)₃ ²⁺, Co (5-NO₂phen)
₃ ²⁺, Co (Me_Fourphen)₃ ²⁺, Co (5,6-Me₂
phen)₃ ²⁺, Co (4,7-Me₂phen)₃ ²⁺,
Co (phen) (bipy)₂ ²⁺, Co (6,6'-
Me₂bpym)₃ ²⁺, Co (TPTZ)₂ ²⁺, Ru (b
ipy)₃ ²⁺, Ru (Me₂bipy)₃ ²⁺, Ru (Me₂
bipy) (bipy)₂ ²⁺, Ru (terpy)₂ ²⁺,
Ru (phen)₃ ²⁺, Ru (5-Mephen)₃ ²⁺,
Ru (5-Clphen)₃ ²⁺, Ru (5-NO₂phe
n)₃ ²⁺, Ru (Me_Fourphen)₃ ²⁺, Ru (5,6-
Me₂phen)₃ ²⁺, Ru (4,7-Me₂phen)₃
²⁺, Ru (phen) (bipy)₂ ²⁺, Ru (6
6'-Me₂bpym)₃ ²⁺, Ru (TPTZ)₂ ²⁺, F
e (bipy)₃ ²⁺, Fe (Me₂bipy)₃ ²⁺, Fe
(Me ₂bipy) (bipy)₂ ²⁺, Fe (terp
y)₂ ²⁺, Fe (phen)₃ ²⁺, Fe (5-Mephe
n)₃ ²⁺, Fe (5-Clphen)₃ ²⁺, Fe (5-N
O ₂phen)₃ ²⁺, Fe (Me_Fourphen)₃ ²⁺, Fe
(5,6-Me₂phen)₃ ²⁺, Fe (4,7-Me₂
phen)₃ ²⁺, Fe (phen) (bipy)₂ ²⁺, F
e (6,6'-Me₂bpym)₃ ²⁺, Fe (TPTZ)
₂ ²⁺, Os (bipy)₃ ²⁺, Os (Me₂bip
y)₃ ²⁺, Os (Me₂bipy) (bipy)₂ ²⁺, O
s (terpy)₂ ²⁺, Os (phen)₃ ²⁺, Os (5
-Mephen)₃ ²⁺, Os (5-Clphen)₃ ²⁺,
Os (5-NO₂phen)₃ ²⁺, Os (Me_Fourphe
n)₃ ²⁺, Os (5,6-Me₂phen)₃ ²⁺, Os
(4,7-Me₂phen)₃ ²⁺, Os (phen) (b
ipy)₂ ²⁺, Os (6,6'-Me₂bpym)₃ ²⁺,
Os (TPTZ)₂ ²⁺, Ir (bipy)₃ ²⁺, Ir (M
e₂bipy) ₃ ²⁺, Ir (Me₂bipy) (bip
y)₂ ²⁺, Ir (terpy)₂ ²⁺, Ir (phen)₃
²⁺, Ir (5-Mephen)₃ ²⁺, Ir (5-Clp
hen)₃ ²⁺, Ir (5-NO₂phen)₃ ²⁺, Ir
(Me_Fourphen)₃ ²⁺, Ir (5,6-Me₂phe
n)₃ ²⁺, Ir (4,7-Me₂phen)₃ ²⁺, Ir
(Phen) (bipy)₂ ²⁺, Ir (6,6'-Me₂
bpym)₃ ²⁺, Ir (TPTZ)₂ ²⁺For example
However, in addition, A. Juris et al. "Coord
Ination Chemistry Review
s ”, Vol. 84, p. 85 (1988).
The body can also be used.

Next, the substituents R ¹ , R ² , R ³ and R ⁴ on the organic boron anion in the general formula (1) will be described. R ¹ , R ² , R ³ and R ⁴ are an alkyl group, an aryl group, an alkaryl group, an allyl group, an aralkyl group, an alkenyl group, an alkynyl group, an alicyclic group, and a saturated or unsaturated heterocyclic group. Is selected from the group consisting of As typical examples of the alkyl group, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, decyl group, stearyl group. There are groups. The alkyl group may be substituted with, for example, one or more halogen groups, cyano groups, acyloxy groups, acyl groups, alkoxy groups, or hydroxyl groups. Typical examples of the aryl group include a phenyl group and p
-Tolyl group, xylyl group, mesityl group, cumenyl group, p
-Methoxyphenyl group, naphthyl group, 2,4-bis (trifluoromethyl) phenyl group, p-fluorophenyl group, p-chlorophenyl group, p-bromophenyl group and the like. Representative examples of the aralkyl group include benzyl group, p-methylbenzyl, p-methoxybenzyl and the like. A typical example of the alkenyl group is a vinyl group,
1-propenyl group, 1-butenyl group and the like. Typical examples of the alkynyl group include ethenyl group and 2-te.
Examples include rt-butylethenyl group and 2-phenylethenyl group. Typical examples of the alicyclic group include a cyclobutyl group, a cyclopentyl group and a cyclohexyl group.

In such an organic boron anion, a borate radical generated when an electron moves to a transition metal coordination complex cation or a triazine compound having a trihalogenomethyl group and a chromophore in the molecule by light irradiation, It is important to design so as to decompose with the generation of radicals as follows.

[0014] BR ₄ ^over → BR ₃ + R ₁ ·

Accordingly, a particularly preferred organoboron anion is the triarylmonoalkylboron anion. The reason is that the anion can be easily dissociated into triarylborane and an alkyl radical with electron transfer. A compound composed of these transition metal coordination complex cations and an organic boron anion can be obtained according to the method described in JP-A-2-182701 or European Patent 0368629. Compounds (a) to (l) are shown below as typical compounds.

[0016]

Embedded image

[0017]

[Chemical 6]

[0018]

[Chemical 7]

[0019]

Embedded image

Next, the triazine compound (B) having a trihalogenomethyl group and a chromophore group in the molecule used in the present invention will be described. Examples of such triazine compounds include 2-phenyl-4,6-bis (trichloromethyl) -s-triazine and 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s.
-Triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl) -s-
Examples thereof include triazine, 2-piperonyl-4,6-bis (trichloromethyl) -s-triazine and their tribromomethyl derivatives. Further, a triazine compound having improved absorption characteristics in the ultraviolet to visible region by extending the conjugated system of the chromophore group is more preferably used in the present invention. As an example, first, Japanese Patent Laid-Open No. 48-3628.
General formula (3) described in No. 1 (Japanese Patent Publication No. 59-1281).

[0021]

[Chemical 9] [In the formula, X is bromine or chlorine, and Y is -CX ₃ ,-.
NH ₂ , -NHR, -NR ₂ or -OR (where R
Is phenyl or lower alkyl having 1 to 6 carbon atoms,
n is an integer of 1 to 3, W represents a substituted or unsubstituted aromatic ring or heterocycle. ]

An s-triazine compound having at least one chromophore moiety conjugated to the triazine ring by at least one trihalomethyl group represented by and an ethylenically unsaturated group, eg vinyl-halomethyl-s-triazine And methyl-halomethyl-s-triazine,
For example, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2,4-bis (trichloromethyl) -6-p-methoxystyryl-s-triazine,
2,4-bis (trichloromethyl) -6- (1-p-dimethylaminophenyl-1,3-butadienyl) -s-
Triazine, 2,4-bis (trichloromethyl) -6
(N-ethyl-2 (3H) -benzoxazolidine)
-Ethylidene s-triazine, 2-trichloromethyl-
4-amino-6-p-methoxystyryl-s-triazine, 2,4-bis (tribromomethyl) -6-styryl-s-triazine, 2,4-bis (tribromomethyl)
-6-p-methoxystyryl-s-triazine, 2,4
-Bis (tribromomethyl) -6- (1-p-dimethylaminophenyl-1,3-butadienyl) -s-triazine, 2,4-bis (tribromomethyl) -6 (N-ethyl-2 (3H ) -Benzoxazolidine) -ethylidene-s-triazine, 2-tribromomethyl-4-amino-6-p-methoxystyryl-s-triazine,
2,4-bis (trichloromethyl) -6-methyl-s-
Triazine, 2,4-bis (tribromomethyl) -6-
Methyl-s-triazine etc. can be mentioned. Compounds (1) to (6) are shown below as typical compounds.

[0023]

[Chemical 10]

[0024]

[Chemical 11]

Next, the general formula (4) described in JP-A-53-133428 (Japanese Patent Publication No. 62-44258).

[0026]

[Chemical 12] [In the formula, X represents bromine or chlorine, and Q represents a substituted or unsubstituted binuclear or trinuclear aromatic ring or heterocycle. ]
An s-triazine compound having one substituted or unsubstituted dinuclear or trinuclear aromatic group or heterocyclic aromatic ring group and two trihalogenomethyl groups, for example, 2
-(Naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s
-Triazine, 2- (4-ethoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-butoxy-naphth-1-yl) -4,
6-bis (trichloromethyl) -s-triazine, 2-
[4- (2-Methoxyethyl) -naphth-1-yl]-
4,6-bis (trichloromethyl) -s-triazine,
2- [4- (2-Ethoxyethyl) -naphth-1-yl] -4,6-bis (trichloromethyl) -s-triazine, 2- [4- (2-butoxyethyl) -naphth-1
-Yl] -4,6-bis (trichloromethyl) -s-triazine, 2- (2-methoxy-naphth-1-yl)-
4,6-bis (trichloromethyl) -s-triazine,
2- (6-methoxy-5-methyl-naphth-2-yl)
-4,6-bis (trichloromethyl) -s-triazine, 2- (6-methoxynaphth-2-yl) -4,6-
Bis (trichloromethyl) -s-triazine, 2- (5
-Methoxynaphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4,7-dimethoxynaphth-1-yl) -4,6-bis (trichloromethyl) -s- Triazine, 2- (6-methoxynaphtho-
2-yl) -4,6-bis (trichloromethyl) -s-
Triazine, 2- (4,5-dimethoxynaphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (acenaphth-5-yl) -4,6-bis (trichloromethyl) -S-triazine, 2- (naphth-2-yl) -4,6-bis (trichloromethyl) -s
-Triazine, 2- (phenanthryl-9-yl)-
4,6-bis (trichloromethyl) -s-triazine,
2- (dibenzothien-2-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (benzopyran-3-yl) -4,6-bis (trichloromethyl)-
s-triazine, 2- (4-methoxyanthracene-1)
-Yl) -4,6-bis (trichloromethyl) -s-triazine and tribromomethyl-substituted derivatives thereof and the like. Compounds (7) to (10) are shown below as typical compounds.

[0027]

[Chemical 13]

Next, the following general formula (5) described in JP-A-60-105667 is used.

[0029]

Embedded image [Wherein Ar represents a substituted or unsubstituted mononuclear to trinuclear aromatic group, R ⁵ and R ⁶ represent a hydrogen atom or an alkyl group, and R ⁷ and R ⁹ are different from each other,
Each represents a hydrogen atom or a 4,6-bis-trichloromethyl-s-triazin-2-yl group, R ⁸ , R ¹⁰ and R ¹¹ are the same or different and each represents a hydrogen atom, a halogen atom, a substituted or unsubstituted Represents an alkyl, alkenyl or alkoxy group. ] The aryl vinyl phenyl-bis-trihalogenomethyl-s-triazine compound represented by these. Specific examples include compounds (11) to (13).

[0030]

[Chemical 15]

Further, as the triazine compound having a trihalogenomethyl group, which is preferably used in the present invention, a trihalogenomethyl group-containing carbonylmethylene heterocyclic compound described in JP-A-60-89473, specifically, 2- (p-trichloromethylbenzoylmethylene) -3-ethyl-benzothiazole, 2- (p-trichloromethylbenzoylmethylene) -3-ethyl-5
Methylbenzothiazoline, 2- (p-trichloromethylbenzoylmethylene) -3-benzylbenzothiazoline, 2- (p-trichloromethylbenzoylmethylene)
-3-methylbenzothiazoline, 2- (trichloroacetylmethylene) -3-methylbenzothiazoline, 2-
(P-Trichloromethylbenzoylmethylene) -3-
(2-Methoxyethyl) -benzothiazoline, 2- (p
-Trichloromethylbenzoylmethylene) -3-n-hexylbenzothiazoline, 2- (p-trichloromethylbenzoylmethylene) -3-methyl-naphtho [1,2-
d] thiazoline, 2- [3,5-bis (trichloromethyl) benzoylmethylene] -3-methyl-naphtho [1,
2-d] thiazoline, 2-trichloroacetylmethylene-3-methyl-naphtho [1,2-d] thiazoline, 2-
(P-Trichloromethylbenzoylmethylene) -3-ethyl-5-methylbenzoselenazoline, 2- (p-trichloromethylbenzoylmethylene) -3-ethyl-5
Methoxybenzoselenazoline, 2-trichloroacetylmethylene-3-ethylbenzoselenazoline, 2- (p-
Trichloromethylbenzoylmethylene) -1,3,3-
Triethyl-5-chloroindoline, 2- (m-trichloromethylbenzoylmethylene) -1,3,3-trimethylindoline, 2-trichloroacetylmethylene-
1,3,3-trimethylindoline, 2-trichloroacetylmethylene-1,3,3-trimethyl-5-chloroindoline, 2- [3,5-bis (trichloromethyl)
-Benzomethylene] -1,3,3, -trimethylindoline, 2- [bis (p-trichloromethylbenzoyl)
-Methylene] -3-ethylbenzothiazoline, 2-trichloroacetylmethylene-3-ethylbenzothiazoline, 2-trichloroacetylmethylene-3-ethyl-5
-Methylbenzothiazoline, 2-trichloroacetylmethylene-3-benzylbenzothiazoline, 2- (p-trichloromethylbenzoylmethylene) -3-ethyl-4
-Methyl-5-ethoxycarbonylthiazoline, 2-trichloroacetylmethylene-3-ethyl-4-methyl-
5-ethoxycarbonylthiazoline, 2- (p-trichloromethylbenzoylmethylene) -3-ethyl-4,5
-Diphenylthiazoline, 2-trichloroacetylmethylene-3-ethyl-4,5-diphenylthiazoline, 2
-Trichloroacetylmethylene-3-ethyl-5-phenylthiazoline, 2-trichloroacetylmethylene-1
-Methyl-1,2-dihydroquinoline, 2-bis (trichloroacetylmethylene) -1-methyl-1,2-dihydroquinoline and the like, and further JP-A-2-3686, JP-A-2-4782, JP-A-2-4787 and , JP-A-2-
The triazine compound described in 292278 can be mentioned.

The photoinitiator composition used in the present invention may be used in combination with other initiators and sensitizers for the purpose of further improving sensitivity or adjusting spectral characteristics. It is possible. Other initiators and sensitizers that can be used by mixing with the photoinitiator composition of the present invention include:
Kiyomi Kato, "Ultraviolet Curing System", p. 102, (1
Initiator described in General Technology Center (1988). Specifically, acetophenone-based initiator 4-phenoxydichloroacetophenone (Sand
oz, Sandory 1000), 4-t-butyl-
Dichloroacetophenone (AKZO, Trigonal
-P2), 4-t-butyl-trichloroacetophenone (AKZO, Trigonal-P1), diethoxyacetophenone (Upjohn, DEAP), 2-hydroxy-2-methyl-1-phenylpropan-1-one (Merck, Darocur 1173). ), 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one (Merck, Darocur 1116), 1-
(4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one (Merck, Darocur 95
3), 4- (2-hydroxyethoxy) -phenyl-
(2-hydroxy-2-propyl) ketone (Merck, Darocur 2959), 1-hydroxycyclohexylphenyl ketone (Ciba Geigy, Irgacure 18)
4), 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1 (Ciba Geigy, Irgacure 907), and other benzoin initiators such as benzoin (Nippon Soda, Nissocur BO), benzoin methyl Ether (Nippon Sure, Nisso Cure MB
O), benzoin ethyl ether (Nippon Soda, Nisso Cure EBO), benzoin isopropyl ether (Nippon Soda, Nisso Cure IBPO), benzoin isobutyl ether (Kokukin Kasei, Solvathlon BIBE), benzyl dimethyl ketal (Ciba Geigy, Irgacure 651), benzophenone -Based initiators benzophenone (Nippon Kayaku, Kayakyu BP), benzoylbenzoic acid (Sanyo Kokusaku Pulp, Sanyo OBA), methyl benzoylbenzoate (Sanyo Kokusaku Pulp, Sanyo OB)
M), 4-phenylbenzophenone (AKZO, Tri
Gonal 12), hydroxybenzophenone (UC
B, Uvecryl P-36), acrylated benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide (Nippon Kayaku, Kayacure BMS), 3, 3 ′
-Dimethyl-4-methoxybenzophenone (Nippon Kayaku,
Kayakyu MBP), 4,4'-dimethylaminobenzophenone (Nippon Soda, Nissocur MABP),
4,4'-diethylaminobenzophenone (Hodogaya Chemical Co., EAB), 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone (NOF Corporation,
BTTB) and other thioxanthone type initiators such as thioxanthone (Nippon Soda, Nisso Cure TX), 2-chlorothioxanthone (Nippon Kayaku, Kaya Cure CTX),
2-Methylthioxanthone (Nippon Soda, Nisso Cure MTX), 2,4-Dimethylthioxanthone (Nippon Kayaku, Kayacure RTX), 2,4-Diethylthioxanthone (Nippon Kayaku, Kayacure DETX), 2,4-
Diisopropylthioxanthone (Nippon Kayaku, Kayacure DITX), Isopropylthioxanthone (Nippon Kayaku, Kayacure ITX), 1-chloro-4-propoxythioxanthone (Nippon Kayaku, Kayacure CPT)
X), 2,4-dichlorothioxanthone (Nippon Kayaku, Kayacure CTX) and the like, which are ketone initiators such as α-acyloxime ester, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone and camphorquinone. , Dibenzosuberone, 2-ethylanthraquinone, 4 ′, 4 ″ -diethylisophthalophenone and the like. As other initiators, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1, which is an imidazole-based initiator,
2'-imidazole (Esprit, BCIM), carbazole initiator A-Cure (Asahi Denka Kogyo),
Acylphosphine oxide-based initiator 2,4,6
Examples thereof include trimethylbenzoyldiphenylphosphine oxide.

Further, in order to further enhance the acid generating effect, the present initiator composition can be used in combination with the following acid generators. Specific examples of such an acid generator include:
Aryl diazonium salt, triaryl sulfonium salt, triaryl (oxo) sulfonium salt, triaryl selenium salt, dialkylphenacyl (oxo) sulfonium salt, alkylarylphenacyl (oxo)
Sulfonium salt, diarylphenacyl (oxo) sulfonium salt, dialkylbenzyl (oxo) sulfonium salt, diarylbenzyl (oxo) sulfonium salt,
Benzylpyridinium salt, phenacylpyridinium salt,
Examples include so-called onium salts such as tetraarylphosphonium salts, perchlorates in metal arene complexes, tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate, hexafluoroarsenate, p-toluenesulfonates. In addition, aromatic sulfonic acid benzyl esters, an ion-bonding compound of an aromatic sulfonic acid anion and a diaryliodonium cation (or a triarylsulfonium cation and a dialkylphenacylsulfonium cation), and the like can be given.

Next, as the compound (C) having an ethylenically unsaturated bond capable of free radical initiation addition polymerization used in the present invention, unsaturated acid compounds such as (meth) acrylic acid, itaconic acid and maleic acid are used. , (Meth) acrylic acid alkyl ester compounds such as methyl (meth) acrylate, ethyl (meth) acrylate, cyclohexyl (meth) acrylate, and isobornyl (meth) acrylate, tetrahydrofuryl (meth) acrylate, glycidyl (meth) acrylate, allyl ( (Meth) acrylate, dimethylaminoethyl (meth) acrylate, morpholinoethyl (meth) acrylate, (meth) acrylamide, diacetone (meth) acrylamide, 2-hydroxyethyl (meth) acrylate, vinyl-molybdenum such as N-vinylcarbazole. And further aliphatic polyhydroxy compounds such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, neopentyl glycol, 1,3-propane. Diol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,10-
Decanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, neopentyl glycol, sorbitol, mannitol and other di- or poly (meth) acrylic esters, trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, hexa Fluorine atom-containing (meth) acrylate compounds such as fluoropropyl (meth) acrylate, octafluoropentyl (meth) acrylate and heptadecafluorodecyl (meth) acrylate,
Bromine atom such as 2,3-dibromopropyl (meth) acrylate, tribromophenoltriethylene oxide (meth) acrylate, p-bromophenoxyethyl (meth) acrylate, tetrabromobisphenol A ethi (propyrene) oxide-modified di (meth) acrylate Containing (meth) acrylate compound, phenyl (meth) acrylate, 4-methoxycarbonylphenyl (meth) acrylate, 4-ethoxycarbonylphenyl (meth)
Acrylate, 4-butoxycarbonylphenyl (meth) acrylate, 4-tert-butylphenyl (meth) acrylate, benzyl (meth) acrylate, 4
-Phenoxyethyl (meth) acrylate, 4-phenylethyl (meth) acrylate, 4-phenoxydiethylene glycol (meth) acrylate, 4-phenoxytetraethylene glycol (meth) acrylate, 4-
Aromatic ring-containing (meth) acrylate compounds such as phenoxyhexaethylene glycol (meth) acrylate, 4-biphenylyl (meth) acrylate, and epichlorohydrin phthalate-modified di (meth) acrylate; aromatic polyhydroxy compounds such as hydroquinone and resorcin , Catechol, pyrogallol, and other di- or poly (meth) acrylate compounds, isocyanuric acid eth (propylene) oxide-modified (meth) acrylate, bisphenol A eth (propylene) oxide-modified di (meth) acrylate, (meth) acrylated epoxy resin ,
Examples thereof include heavy metal atom-containing (meth) acrylate compounds such as ferrocenylmethyl (meth) acrylate, ferrocenylethyl (meth) acrylate, and zinc di (meth) acrylate.

Next, examples of the compound (D) having a cationically polymerizable functional group used in the present invention include styrenes, epoxy compounds, vinyl ether compounds, spiro orthoesters, spill orthocarbonates and the like. . In particular, examples of the compound having a functional group capable of cationic polymerization that is preferably used in the present invention include an epoxy compound and a vinyl ether compound.

Specific examples of the epoxy compound include phenyl glycidyl ether, o-cresyl glycidyl ether, p-cresyl glycidyl ether, tert-butylphenyl glycidyl ether, bisphenol-A-diglycidyl ether, and tetrabromobisphenol-A.
-Diglycidyl ether, bisphenol-F-diglycidyl ether, tetrabromobisphenol-F-diglycidyl ether, diglycidyl resorcinol ether, 2-phenylethylene oxide, isophthalic acid diglycidyl ester, cardo epoxy resin (manufactured by Nippon Steel Chemical Co., Ltd.) , ESF-300) and other aromatic epoxy monomers, (brominated) bisphenol A type epoxy resin, (brominated) bisphenol F type epoxy resin, (brominated) phenol novolac type epoxy resin, (brominated) cresol novolac Examples include aromatic epoxy resins such as mold resins. Further, alkylene oxides of bisphenol compounds (for example, ethylene oxide,
Examples thereof include glycidyl ethers obtained by the reaction of a propylene oxide) adduct with epichlorohydrin.

Further, as the aliphatic epoxy compound, an alicyclic epoxy compound, for example, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, bis- (3,4-epoxycyclohexylmethyl) is used. ) Adipate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexanone-meta-dioxane, bis (2,2)
3-epoxycyclopentyl) ether, EHPE-3
150 (manufactured by Daicel Chemical Industries, Ltd., alicyclic epoxy resin), or polyglycidyl ether monomers of aliphatic polyhydric alcohol or its alkylene oxide adduct, for example, diglycidyl ether of 1,4-butanediol, 1 , 6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, ethylene glycol, propylene glycol, aliphatic such as glycerin Polyglycidyl ether of a polyether polyol obtained by adding one or more alkylene oxides (ethylene oxide, propylene oxide) to a polyhydric alcohol Le and the like.

Next, as vinyl ether compounds, monofunctional vinyl ethers such as hydroxybutyl vinyl ether (GAF, Rapi-Cure HBVE) and dodecyl vinyl ether (GAF, Rapi-Cur) are used.
e DDVE), propenyl ether propylene carbonate (GAF, Rapi-Cure PEP)
C), polyvinyl ethers of polyhydric alcohols, for example, 1,4-butanediol divinyl ether, triethylene glycol divinyl ether (manufactured by GAF, Ra.
pi-Cure DVE-3), tripropylene glycol divinyl ether, 3-methyl-1,5-pentanediol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether and trimethylolpropane trivinyl ether. Further, vinyl ether compounds having an aromatic ring or a heterocycle in the molecule can also be exemplified. Examples of such compounds include 4-vinyl ether styrene, hydroquinone divinyl ether, phenyl vinyl ether, bisphenol A divinyl ether, tetrabromobisphenol A divinyl ether, bisphenol F divinyl ether, tetrabromobisphenor F divinyl ether, phenoxyethylene vinyl ether. , P-bromophenoxyethylene vinyl ether, 2-carbazoyl vinyl ether and the like.

The photopolymerizable composition of the present invention may be used in combination with various additives in order to solve various problems in practical use. For example, for the purpose of preventing thermal polymerization during storage, addition of a thermal polymerization inhibitor such as p-methoxyphenol, hydroquinone, catechol, phenothiazine, cuperone, and the like for the purpose of promoting polymerization, an amine,
It is possible to add a chain transfer agent such as thiol or disulfide, or to add an antifoaming agent, a leveling agent, a plasticizer, an antioxidant, a flame retardant, an antistatic agent, an antihalation agent or the like.

In the photopolymerizable composition of the present invention, when the compound having an ethylenically unsaturated bond or the compound having a functional group capable of cationic polymerization used is a liquid, the photoinitiator composition is treated with ethylene. It can be used by being dissolved or dispersed in a compound having a cationic unsaturated bond or a compound having a functional group capable of cationic polymerization. On the other hand, when the compound having an ethylenically unsaturated bond or the compound having a functional group capable of cationic polymerization used is solid, it can be dissolved or dispersed in an aqueous or organic solvent before use.

The photopolymerizable composition thus prepared is
Coating, printing or transfer on a suitable substrate, injection into molded products,
The photosensitive layer is formed by encapsulating between the base materials. A spinner or coater is preferably used for coating. For printing, letterpress printing, planographic printing, intaglio printing, screen printing, etc. are preferably used. Further, a dipping method or the like may be used for coating on a curved surface, and electrodeposition coating may be used. Then, the photosensitive layer is treated with a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a xenon lamp, a carbon arc lamp, a metal halide lamp, a fluorescent lamp, a white lamp, a tungsten lamp, various gases (ion, semiconductor or solid). By applying light energy with various light sources such as a laser light source, an LED, a CRT light source, and a plasma light source, a desired polymer or cured product can be obtained.

The method of applying light energy can be selected according to the purpose of use, such as direct irradiation of the photosensitive layer, pattern exposure through a mask film, scanning exposure, or interference exposure using a laser. Further, post-baking can be performed at an appropriate temperature after exposure with various light sources. Especially when a compound having a functional group capable of cationic polymerization is blended, post-baking is preferably used for the purpose of promoting polymerization. The temperature is in the range of 40 ° C to 250 ° C, more preferably 80 ° C to 2
It is carried out in the range of 00 ° C.

Therefore, the photoinitiator composition and the photopolymerizable composition according to the present invention include a photocurable ink, a photocurable paint and a coating agent, a photocurable adhesive and a sealant,
Photocurable encapsulant and composite agent, photocurable ink jet, photocurable microcapsule, photosensitive printing plate,
It can be suitably used in the fields of photoresist ink, proofing material for printing, stereolithography resin, hologram material and the like by selecting a composition that matches each purpose.

The compound (A) composed of a transition metal coordination complex cation and an organic boron anion used in the photoinitiator composition of the present invention, and a triazine having a trihalogenomethyl group and a chromophore group in the molecule. Compound (B)
Can be combined at any mixing ratio, but it is preferable to mix both compounds within a range in which the absorbance with respect to the wavelength of the light source used for exposure does not exceed 2. When the photoinitiator composition is used as a photopolymerizable composition, it is desirable to use the photoinitiator composition in the range of about 0.1% by weight to 30% by weight in the composition. When a compound having a cationically polymerizable functional group is further blended with the compound having an ethylenically unsaturated bond capable of free radical initiated addition polymerization in the photopolymerizable composition, an arbitrary blending ratio, that is, each is 0. It is possible to combine them in an amount of up to 100% by weight, but considering the curing rate, it is desirable that the free radical polymerizable compound is contained in at least 10% by weight or more based on the cationically polymerizable compound. .

Further, the photopolymerizable composition of the present invention can be used by adding an oligomer and a high molecular polymer depending on the purpose, and the oligomer or the high molecular polymer is radically or cationically polymerized. It may or may not be a reactive compound having a functional group.

The compound (A) composed of the transition metal coordination complex cation and the organic boron anion used in the present invention
Is a free radical due to the absorption of actinic radiation by the chromophore group in the triazine compound (B) used in the present invention or the absorption of actinic radiation possessed by the transition metal coordination complex itself and the photochemical interaction between the two compounds which occurs subsequently. And generate acid. Although the mechanism is not clear, the compound (A) and the triazine compound (B), which are composed of a transition metal coordination complex and an organic boron anion, decompose as a result of photochemical interaction between the two compounds, and the transition metal coordination compound is decomposed. It is presumed that free radicals are generated from both the site of the organic boron anion of the coordination complex and the site of the trihalogenomethyl group of the triazine compound, and this is considered to bring out the effect of increasing the sensitivity in radical polymerization. Further, it is presumed that an acid is generated by the generation of a halogen radical from the trihalogenomethyl group and the subsequent generation of a halogen ion, and as a result, cationic polymerization becomes possible. Further, since the triazine compound in the present invention has a chromophore group,
Even after the decomposition of the trihalogenomethyl group, it functions as a sensitizer that sensitizes and decomposes the transition metal coordination complex (A).
It is presumed that high activity was reached.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

Example 1 5 parts of compound (a) as a compound (A) composed of a transition metal coordination complex cation and an organic boron anion, a triazine compound (B) having a trihalogenomethyl group and a chromophore group in the molecule. 5 parts of the compound (1) and 100 parts of pentaerythritol triacrylate (PETA) as the compound (C) having an ethylenically unsaturated bond capable of free radical initiated addition polymerization are mixed and coated on a glass plate at a thickness of about 2 μm. Then, a polyethylene terephthalate (PET) film having a thickness of 25 μm was further adhered onto the sample to prepare a sample. When this sample was irradiated with a 500 mW Xe lamp, it became tack-free in 3 seconds.

Examples 2 to 12 The same operation as in Example 1 was carried out except that the compound (b) to the compound (l) were used in place of the compound (a) in Example 1. Table 1 summarizes the tack-free time (seconds).

[0049]

[Table 1]

Examples 13 to 24 Instead of the triazine compound (1) in Example 1,
The same operation as in Example 1 was performed except that the compounds (2) to (13) were used. Table 2 summarizes the tack-free time (seconds).

[0051]

[Table 2]

Comparative Example 1 When the same operation as in Example 1 was carried out except that the compound (a) in Example 1 was not used, the tack-free irradiation time was 10 seconds.

Comparative Example 2 When the same operation as in Example 1 was carried out except that the compound (1) in Example 1 was not used, the tack-free irradiation time was 8 seconds.

Example 25 Instead of 100 parts of PETA in Example 1, PET was used.
3,4-epoxycyclohexylmethyl-as compound (D) having a functional group capable of undergoing cationic polymerization with A50 part
3,4-epoxycyclohexanecarboxylate (U
CC, ERL4221) 50 parts were mixed and coated on a glass plate with a thickness of about 2 μm to prepare a sample. At this time, PE
When the film was directly irradiated with a 500 mW Xe lamp without adhering the T film, it became tack-free in 3 seconds.

Example 26 In place of 50 parts of ERL4221 in Example 25, triethylene glycol divinyl ether (GAF, Rapi-Cure, a vinyl ether compound as a compound (D) having a cationically polymerizable functional group) was used.
Except for changing 50 parts of DVE-3), the same operation as in Example 25 was carried out, and it became tack-free in 2 seconds.

Claims (5)

[Claims] 1. A compound (A) composed of a transition metal coordination complex cation represented by the following general formula (1) and an organic boron anion, and a triazine having a trihalogenomethyl group and a chromophore group in the molecule. A photoinitiator composition comprising the compound (B). Embedded image (In the formula, C ^{n +} is a transition metal complex coordination complex cation,
R ¹ , R ² , R ³ and R ⁴ are each an alkyl group, an aryl group, an alkaryl group, an allyl group, an aralkyl group, an alkenyl group, an alkynyl group, an alicyclic group, and a saturated or unsaturated heterocyclic group. Each independently selected from the group and n is an integer from 1 to 3. ) 2. A photopolymerizable composition obtained by blending the photoinitiator composition according to claim 1 with a compound (C) having an ethylenically unsaturated bond capable of free radical initiated addition polymerization. 3. A photopolymerization method comprising irradiating the photopolymerizable composition according to claim 2 with actinic radiation to initiate radical polymerization. 4. The photopolymerizable composition according to claim 2, further comprising a compound (D) having a functional group capable of cationic polymerization. 5. A photopolymerization method comprising irradiating the photopolymerizable composition according to claim 4 with actinic radiation to initiate radical polymerization and cationic polymerization.