JP3384119B2 - Photoinitiator composition, photopolymerizable composition and photopolymerization method - Google Patents

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]

DISCLOSURE OF THE INVENTION 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 photopolymerization containing the photoinitiator composition. And a photopolymerization method. More specifically, a photopolymerizable compound is polymerized in a short time, and for example, 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,
The present invention provides a photoinitiator composition, a photopolymerizable composition, and a photopolymerization method, which are suitably used in the fields of photoresists for PCBs, photoresist inks, proof materials, stereolithography resins, hologram materials and the like.

[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 a photoinitiator comprising an iodonium salt (A) represented by the following general formula (1) and a triazine compound (B) having a trihalogenomethyl group and a chromophore group in the molecule. The composition is represented by the general formula (1) (In the formula, R ¹ and R ² are a hydrogen atom, a lower alkyl group or a lower alkyl group.
Rucoxy group, cyano group, nitro group or halogen atom
Where Z is an organic borate represented by the following general formula (2).
Show. ) General formula (2) (In the formula, R ³ , R ⁴ , R ⁵ and R ⁶ are each independently
Alkyl group, substituted alkyl group, aryl group, substituted
Aryl groups, aralkyl groups, and substituted aralkyl groups
Group, alkenyl group, or substituted alkenyl group.
However, all of R ³ , R ⁴ , R ⁵ and R ⁶ are aryl groups.
Others be a substituted aryl group is not Na. ) A second invention is a compound (C) having a free radical-initiated addition-polymerizable ethylenically unsaturated bond in the photoinitiator composition.
Is a photopolymerizable composition obtained by mixing, the third invention,
The photopolymerization composition is a photopolymerization method of initiating radical polymerization by irradiating the triazine compound (B) with an actinic ray in the absorption region, and a fourth invention is the photopolymerizable composition, A photopolymerizable composition further comprising a compound (D) having a cationically polymerizable functional group,
Fifth invention, the photopolymerizable composition by irradiating the active ray absorption wavelength region of the triazine compound (B), the photopolymerization method characterized by to start the radical polymerization and cationic polymerization Is. It is a fee .

The present invention will be described in detail below.
First, as the iodonium salt (A) used in the present invention,
General formula (1)

(Wherein R ¹ and R ² represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, a cyano group, a nitro group or a halogen atom, and Z represents an organic group represented by the general formula (2).
Indicates the rate. )

[0008]

[Chemical 2] [(Wherein R³, R^Four, R^FiveAnd R⁶Are each German
Vertically, alkyl group, substituted alkyl group, aryl
Group, substituted aryl group, aralkyl group, substituted
Aralkyl group, alkenyl group, substituted alkenyl group
Represents (However, R ³, R^Four, R^FiveAnd R⁶All of
Is an aryl group or a substituted aryl group
There is no. )] The iodonium salt represented by

[0009]

Next, the triazine compound (B) having a trihalogenomethyl group and a chromophore group in the molecule, which is 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).

[0011]

[Chemical 3] [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. ]

S-Triazine compounds having at least one chromophore moiety conjugated to the triazine ring by at least one trihalomethyl group and an ethylenically unsaturated group represented by: for example 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.

[0013]

[Chemical 4]

[0014]

[Chemical 5]

[0015]

[Chemical 6]

[0016]

[Chemical 7]

[0017]

[Chemical 8]

[0018]

[Chemical 9]

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

[0020]

[Chemical 10] [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.

[0021]

[Chemical 11]

[0022]

[Chemical 12]

[0023]

[Chemical 13]

[0024]

[Chemical 14]

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

[0026]

[Chemical 15] [In the formula, Ar represents a substituted or unsubstituted mononuclear to trinuclear aromatic group, R ⁷ and R ⁸ represent a hydrogen atom or an alkyl group, and R ⁹ and R ¹¹ are different from each other,
Each represents a hydrogen atom or a 4,6-bis-trichloromethyl-s-triazin-2-yl group, R ¹⁰ , R ¹² and R ¹³ 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).

[0027]

[Chemical 16]

[0028]

[Chemical 17]

[0029]

[Chemical 18]

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 Benzophenone (Nippon Kayaku, Kayacure 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, EAB), 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone (NOF,
BTTB) and other thioxanthone 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 type 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 of so-called onium salts such as tetraarylphosphonium salts, perchlorates in metal arene complexes such as iron arene complexes, tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate, hexafluoroarsenate and p-toluenesulfonates. be able to. Further, aromatic sulfonic acid benzyl esters, aromatic sulfonic acid diaryl iodonium salts and the like can be mentioned.

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. . 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 such as 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 contain 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. It is essential that the light source selected at this time is a light source that generates an actinic ray in the absorption wavelength region of the triazine compound (B) having a trihalogenomethyl group and a chromophore group in the molecule used in the present invention, By irradiating with such actinic rays, radical polymerization and cationic polymerization are initiated in the photopolymerizable composition used in the present invention, and a 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 sealing agent,
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 iodonium salt (A) used in the photoinitiator composition of the present invention and the triazine compound (B) having a trihalogenomethyl group and a chromophore group in the molecule are
The triazine compound (B) is preferably used in an amount such that 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, 0.1% by weight in the composition is used.
It is desirable to use in the range of about 30% by weight. 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 iodonium salt (A) used in the present invention is
Free radicals and acids are generated by the absorption of actinic radiation by the chromophore group in the triazine compound (B) used in the present invention and the subsequent photochemical interaction between both compounds.
Although the mechanism is not clear, iodonium salt (A) and triazine compound (B) are decomposed as a result of photochemical interaction, and a free radical is generated from the cation site of the iodonium salt and the trihalogenomethyl group of the triazine compound. It is presumed that this is eliciting the action of increasing the sensitivity in radical polymerization. Also,
At the same time, it is presumed that an acid is generated by the generation of a halogen radical and the subsequent generation of a halogen ion from the anion site and trihalogenomethyl group of the iodonium salt, and as a result, cationic polymerization becomes possible. On the other hand, when the anion site of the iodonium salt is an organic borate such as n-butyltriphenylboron, it is presumed that the decomposition of the anion site also occurs, and as a result, the free radical generation efficiency is further increased. Further, since the triazine compound in the present invention has a chromophore group, it functions as a sensitizer for sensitizing and decomposing the iodonium salt (A) even after the decomposition of the trihalogenomethyl group, and thus exhibits high activity. It is presumed that it has arrived.

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

The compounds (d) 5 parts of a first embodiment iodonium salt (A), triazine compounds having a trihalogenomethyl group and the chromophore group in the molecule (B) as the compound (1), 5 parts of free radical initiated addition polymerization Is mixed with 100 parts of pentaerythritol triacrylate (PETA) as a compound (C) having an ethylenically unsaturated bond, which is applied to a glass plate with a thickness of about 2 μm, and further with 25 μm of polyethylene terephthalate ( A sample in which a PET) film was adhered was prepared. When this sample was irradiated with a 500 mW lamp, it became tack-free in 1 second.

Examples 2 and 3 Comparative Examples 1 to 3 The same as Example 1 except that the compound ( d ) as the iodonium salt (A) in Example 1 was used in place of that shown in Table 1 . The operation was performed. Table 1 summarizes the tack-free time (seconds).

[0048] Table 1 ----------------- Example Iodonium salt Triazine compound Curing speed (sec) ----------------- Comparative Example 1 Compound (a) Compound (1) 3 Comparative Example 2 Compound (b) Compound (1) 4 Comparative Example 3 Compound (c) Compound (1) 3 Example 1 Compound (d) Compound (1) 1 Example 2 Compound (e) Compound (1) 2 Example 3 Compound (f) Compound (1) 1 -----------------

[0049]

[Chemical 19]

[0050]

[Chemical 20]

[0051]

[Chemical 21]

[0052]

[Chemical formula 22]

[0053]

[Chemical formula 23]

[0054]

[Chemical formula 24]

[0055]

[0056]

[0057]

[0058]

Reference Example 1 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.

Reference Example 2 Instead of 50 parts of ERL4221 in Example 19, as a compound (D) having a cationically polymerizable functional group, triethylene glycol divinyl ether (GAF, Rapi-Cure, a vinyl ether compound) was used.
Except for changing 50 parts of DVE-3), the same operation as in Example 19 was carried out, and it became tack-free in 2 seconds.

Reference Example 3 In Example 1, when irradiation was performed without adhering the PET film, it took 6 seconds to become tack-free.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ identification code FI G03F 7/027 502 G03F 7/027 502 7/029 7/029 (56) Reference JP-A-63-261352 (JP, A) JP-A-4-90547 (JP, A) JP-A-2-292278 (JP, A) JP-A-7-196632 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08F 2/00-2/60 C08G 59/00-59/72

Claims (5)

(57) [Claims] 1. A photoinitiator composition comprising an iodonium salt (A) represented by the following general formula (1) and a triazine compound (B) having a trihalogenomethyl group and a chromophore group in the molecule. object. General formula (1) (In the formula, R ¹ and R ² are a hydrogen atom, a lower alkyl group or a lower alkyl group.
Rucoxy group, cyano group, nitro group or halogen atom
Where Z is an organic borate represented by the following general formula (2).
Show. ) General formula (2) (In the formula, R ³ , R ⁴ , R ⁵ and R ⁶ are each independently
Alkyl group, substituted alkyl group, aryl group, substitution
Aryl groups, aralkyl groups, and substituted aralkyl groups
Group, alkenyl group, or substituted alkenyl group.
However, all of R ³ , R ⁴ , R ⁵ and R ⁶ are aryl groups.
Or a substituted aryl group. ) 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 photopolymerizable wherein the to start the radical polymerization by irradiation with active ray absorption wavelength region of the triazine compound in the photopolymerizable composition of claim 2 (B). 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 an actinic ray in the absorption wavelength region of the triazine compound (B) to initiate radical polymerization and cationic polymerization. .