JPH11279212A - Photocurable composition containing new iodonium salt compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new compound scarcely coloring, capable of readily synthesizing in high yield, sensitive at a high sensitivity to irradiation of active energy beam, having high solubility to monomers, having low toxicity, curable in a short time and useful as a photopolymerization initiator capable of providing a photocurable composition having excellent physical properties of cured product. SOLUTION: This compound is represented by formula I or formula II [R1 and R2 are each hydrogen, an alkyl, or the like; R3 and R4 are each hydrogen, a cycloalkyl, or the like; R5 is hydroxyl group, an alkyl or the like; (l) and (m) are each 0-3; (n) is 1-3; X is a non-nucleophilic anion residue], e.g. 4- methoxycarbonylmethoxy-phenylphenyliodonium hexafluorophosphate. The compound of formula I is obtained by reacting, e.g. a compound of formula III with a compound of formula IV in the presence of a sulfuric acid catalyst at -20 deg.C to room temperature for one to several ten hr and reacting the product with a compound of the formula MX (M is an alkali metal).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel iodonium salt compound and a photocurable composition containing the compound, and more particularly, to a method for irradiating an active energy ray such as light, electron beam or X-ray in a short time. The present invention relates to a curable photocationically curable composition. Since the cured product of the composition has excellent physical properties, it is suitably used as a paint, an adhesive, a photoresist, an ink, a silicone release and the like.

[0002]

2. Description of the Related Art Japanese Patent Application Laid-Open Nos. 50-151996 and 60-47029 describe an iodonium salt compound similar to the iodonium salt compound of the present invention.
It is also described that these iodonium salt compounds can be used as a catalyst for curing a cationically polymerizable compound such as an epoxy compound by radiation such as light, electron beam and X-ray.

[0003] In general, iodonium salt compounds have problems such as low solubility in monomers and high toxicity, and as a method for solving these problems, a functional group is introduced,
It is desirable that various modifications can be made. For example, Japanese Patent Application Laid-Open Nos. 50-151996 and 60
In the synthesis of compounds described in JP-A-47029 and the like, many substituents such as an alkyl group, an alkoxy group, and a carbonyl group are difficult to chemically modify, and coloring often occurs during the synthesis. On the other hand, it is known that the yield of an iodonium salt compound in which a chemically modifiable functional group such as a carboxyl group is directly introduced into an aromatic ring is as low as about 20%.

It is known that the photocuring of iodonium salt compounds is significantly reduced when the counter anion thereof is other than antimony hexafluoride or tetraperfluorophenyl borate, for example, phosphonate hexafluoride or tetrafluoroborate. . Therefore, these iodonium salt compounds having a counter anion are not suitable for photocuring a clear composition or a composition containing a pigment, and no effective sensitizer has been found for them. .

[0005]

An object of the present invention is to provide a high-yield and easy-to-synthesize low-color iodonium salt compound and a high sensitivity to irradiation with active energy rays such as light, electron beams and X-rays. In addition to providing an iodonium salt compound which is highly soluble in monomers and has low toxicity, it has a short anion even when the counter anion is hexafluorophosphonate or tetrafluoride borate, regardless of whether the composition is clear or pigment. An object of the present invention is to provide a photocurable composition which can be cured in a short time and has excellent cured physical properties.

[0006]

Means for Solving the Problems The present inventors have studied diligently to solve the above-mentioned problems, and when synthesized from a specific substrate, produce an iodonium salt compound having a colorless carboxyl group or ester group in a high yield. It has been found that the compound can be easily synthesized, and furthermore, by using such an iodonium salt compound and a sensitizer in combination, it can be cured in a short time by irradiation with active energy rays such as light, an electron beam, and an X-ray. The present inventors have found that a photocurable composition having excellent physical properties can be obtained, and have completed the present invention.

That is, the present invention relates to an iodonium salt compound represented by the following general formula [I] or general formula [II].

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Embedded image [Wherein, R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group, or a cycloalkyl group, and R ₃ and R ₄ each independently represent a hydrogen atom, an optionally substituted alkyl group, Represents an alkyl group, R ₅ represents a hydroxyl group, an optionally substituted alkyl group, a cycloalkyl group, an alkenyl group, a phenyl group, a phenoxy group, an optionally substituted alkoxy group, and a cycloalkyloxy group; And m
Each independently represents 0, 1, 2 or 3, and n represents 1, 2 or 3. When n = 1, R ₃ and R ₅ may combine to form a ring. X represents a non-nucleophilic anion residue]

[0008] The present invention also relates to a photopolymerization initiator comprising at least one of the above iodonium salt compounds.

Further, the present invention provides a photocurable composition containing at least one of the above-mentioned iodonium salt compounds and a cationically polymerizable compound, and a sensitizer comprising at least one of the above-mentioned iodonium salt compounds and a cationically polymerizable compound. And a photocurable composition containing at least one of the iodonium salt compounds, the cationic polymerizable compound and the sensitizer, and further containing a pigment or a radical polymerizable compound. .

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The novel iodonium salt compound of the present invention is represented by the following general formula [I] or general formula [II].

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Embedded image [Wherein, R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group, or a cycloalkyl group, and R ₃ and R ₄ each independently represent a hydrogen atom, an optionally substituted alkyl group, Represents an alkyl group, R ₅ represents a hydroxyl group, an optionally substituted alkyl group, a cycloalkyl group, an alkenyl group, a phenyl group, a phenoxy group, an optionally substituted alkoxy group, and a cycloalkyloxy group; And m
Each independently represents 0, 1, 2 or 3, and n represents 1, 2 or 3. When n = 1, R ₃ and R ₅ may combine to form a ring. X represents a non-nucleophilic anion residue. ]

The R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , l, m, n and X in the general formulas [I] and [II] will be described more specifically. R ₁ and R ₂ each independently represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group,
Represents an alkyl group such as a decyl group and a dodecyl group; and a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group.

R ₃ and R ₄ each independently represent a hydrogen atom, an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a decyl group or a dodecyl group. And a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, and the alkyl group is an aryl group such as a phenoxy group, a phenyl group, a phenylthio group, a hydroxy group, a methoxy group, an ethoxy group, a propyl group, a butoxy group, and a hexyloxy group. Group, decyloxy group, alkoxy group such as dodecyloxy group, carboxyl group, acetoxy group, propionyloxy group, decylcarbonyloxy group, alkylcarbonyl group such as dodecylcarbonyloxy group, aromatic carbonyl group such as benzoyloxy group, fluorine, Halogen atoms such as chlorine, bromine and iodine It may be.

R ₅ represents a hydroxyl group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group,
t-butyl group, decyl group, alkyl group such as dodecyl group, cyclopentyl group, cycloalkyl group such as cyclohexyl group, alkenyl group such as styryl group, phenyl group,
Phenoxy group, methoxy group, ethoxy group, propoxy group, butoxy group, hexyloxy group, decyloxy group,
Represents an alkoxy group such as a dodecyloxy group, and a cycloalkyloxy group such as a cyclopentyloxy group and a cyclohexyloxy group, wherein the alkyl group is a hydroxy group,
Methoxy, ethoxy, propoxy, butoxy,
Hexyloxy group, decyloxy group, alkoxy groups such as dodecyloxy group, carboxyl group, acetoxy group, propionyloxy group, decylcarbonyloxy group, alkylcarbonyl group such as dodecylcarbonyloxy group, aromatic carbonyl group such as benzoyloxy group, Fluorine, chlorine, bromine, may be substituted with a halogen atom such as iodine, and the alkoxy group is a hydroxy group, a methoxy group, an ethoxy group, a propyl group, a butoxy group, a hexyloxy group, a decyloxy group, a dodecyloxy Groups, such as alkoxy groups, acetoxy groups, propionyloxy groups, decylcarbonyloxy groups, alkylcarbonyl groups such as dodecylcarbonyloxy groups, aromatic carbonyl groups such as benzoyloxy groups, phenyl groups, naphthyl groups, phenoxy groups, fluorine, salts , Bromine, halogen atom of iodine,
Allyl group, 2-butenyl group, alkenyl group such as cinnamyl group, cyclohexyl group, cyclopentyl group, 2-indanyl group, 1-acenaphthenyl group, bicyclononyl group,
It may be substituted with an aliphatic cyclic compound such as a norbornyl group, a coumarinyl group, and a dihydrobenzofuranyl group.

1 and m each independently represent 0, 1, 2 or 3, and n represents 1, 2 or 3. When n = 1, R ₃ and R ₅ may combine to form a ring.
X is a non-nucleophilic anionic residue, SbF ₆ , As
Examples include F ₆ , PF ₆ , BF ₄ or (F ₅ C ₅ ) ₄ B.

Representative examples of the iodonium salt compound of the present invention are shown in the following (Chemical formulas 7 to 14). Where X in the formula is
A non-nucleophilic anion residue such as SbF ₆ , AsF ₆ , PF ₆ , BF ₄ or (F ₅ C ₅ ) ₄ B is shown.

[0016]

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[0017]

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[0018]

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[0019]

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[0020]

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[0021]

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[0022]

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[0023]

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The iodonium salt compound represented by the general formula [I] of the present invention has the following reaction formula wherein M represents an alkali metal. ]. The reaction of the compounds [1] and [2] with a sulfuric acid catalyst is carried out in an organic solvent such as acetic acid or acetic anhydride at -20 ° C to room temperature for 1 hour to several tens of hours, if necessary. After the completion of the reaction, water is added to the reaction solution, followed by stirring. The precipitated compound is collected by filtration or extracted with an organic solvent to obtain the compound [3], and the desired product [4] is obtained by an addition reaction or a condensation reaction.

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The iodonium salt compound represented by the general formula [II] of the present invention has the following reaction formula [where M represents an alkali metal. ]. The reaction of the compounds [1] and [5] with a sulfuric acid catalyst is performed in an organic solvent such as acetic acid or acetic anhydride at -20 ° C to room temperature for 1 hour to several tens of hours, if necessary. After the completion of the reaction, water is added to the reaction solution, followed by stirring. The precipitated compound is collected by filtration or extracted with an organic solvent to obtain the compound [6], and the desired product [7] is obtained by an addition reaction or a condensation reaction.

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The iodonium salt compound of the present invention can cure a cationically polymerizable compound by irradiation with an active energy ray such as light, an electron beam, or an X-ray as a photopolymerization initiator. As a light source, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a xenon lamp, a carbon arc lamp, or the like is used. Further, it can be easily cured by a laser beam such as a semiconductor laser, an argon laser, a He-Cd laser, or an ionizing radiation such as an α-ray, a β-ray, a γ-ray, a neutron beam, an X-ray, and an accelerating electron beam. . Furthermore, by using together with a sensitizer, curing can be performed in a shorter time than when not using a sensitizer.

As the cationically polymerizable compound used in the present invention, any cationically polymerizable monomer, oligomer and polymer can be used irrespective of the kind thereof. Oxirane compounds such as cyclic epoxy compounds and oxetane compounds and vinyl ether compounds can be exemplified.

The cationically polymerizable compound used in the present invention will be more specifically described below. (A) As the vinyl compound, styrene compounds such as styrene, α-methylstyrene, p-methoxystyrene, pt-butoxystyrene, methyl vinyl ether, n-
Butyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether,
Alkyl vinyl ether compounds such as 2-chloroethyl vinyl ether, 2-phenoxyethyl vinyl ether, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, stearyl vinyl ether, and 2-acetoxyethyl vinyl ether; allyl vinyl ether; 2-methacryloyloxyethyl vinyl ether; Alkenyl vinyl ether compounds such as acryloyloxyethyl vinyl ether; aryl vinyl ether compounds such as phenyl vinyl ether and p-methoxyphenyl vinyl ether; N-vinyl carbazole;
-Polyfunctional such as cationically polymerizable nitrogen-containing compounds such as vinylpyrrolidone, butanediol divinyl ether, triethylene glycol divinyl ether, cyclohexanediol divinyl ether, 1,4-benzenedimethanol divinyl ether, hydroquinone divinyl ether, and sasolcinol divinyl ether. And vinyl compounds.

(B) Epoxy compounds include phenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, 1,2-butylene oxide, 1,3-butadiene Monooxide, 1,2-dodecylene oxide,
Monofunctional such as epichlorohydrin, 1,2-epoxydecane, ethylene oxide, propylene oxide, styrene oxide, cyclohexene oxide, 3-methacryloyloxymethylcyclohexene oxide, 3-acryloyloxymethylcyclohexene oxide, 3-vinylcyclohexene oxide monomer,
1,13-tetradecadienedoxide, limonenedoxide, 3,4-epoxycyclohexylmethyl-
(3,4-epoxycyclohexyl) carboxylate, di (3,4-epoxycyclohexyl) adipate, bisphenol A type epoxy resin, bisphenol F type epoxy resin, o-, m-, p-cresol novolak type epoxy resin, phenol novolak And polyfunctional epoxy compounds such as polyepoxy resin and polyglycidyl ether of polyhydric alcohol.

(C) The bicycloorthoester compounds include 1-phenyl-4-ethyl-2,6,7-trioxabicyclo [2,2,2] octane and 1-ethyl-4
And compounds such as -hydroxymethyl-2,6,7-trioxabicyclo [2,2,2] octane.

(D) Spiro orthocarbonate compounds include 1,5,7,11-tetraoxaspiro [5,
5] undecane, 3,9-dibenzyl-1,5,7,1
1-tetraoxaspiro [5,5] undecane, 1,
4,6-trioxaspiro [4,4] nonane, 2-methyl-1,4,6-trioxaspiro [4,4] nonane,
Compounds such as 1,4,6-trioxaspiro [4,5] decane are exemplified.

(E) Oxetane compounds include 3,3
-Dimethyloxetane, 3,3-bis (chloromethyl)
Oxetane, 2-hydroxymethyloxetane, 3-methyl-3-oxetanemethanol, 3-methyl-3-methoxymethyloxetane, 3-ethyl-3-phenoxymethyloxetane, resorcinol bis (3-methyl-
Compounds such as 3-oxetanylethyl) ether and m-xylylenebis (3-ethyl-3-oxetanylethylether) are exemplified. These may be used alone or in combination of two or more.

The sensitizer used in the present invention may be any compound that promotes the photoreaction of the above-mentioned iodonium salt compound. For example, as a known sensitizer, Journal of Polymer Science
nce: Polymer Chemistry Edi
tion, Vol. 16,2441 (1978), a redox system in combination with a dye such as acridine orange, acridine yellow, or benzoflavin, a coumarin derivative, or a photoradical generator. Furthermore, 4-methoxyphenol, 4-benzyloxyphenol, 4-methoxy-2- (t-butyl) phenol, hydroquinone, 4-methoxy-1-
Phenol derivatives such as naphthol and 2-hydroxydibenzofuran, 1-naphthol, 2-naphthol, 1-methoxynaphthalene, 2-methoxynaphthalene, 1-hydroxyphenanthrene, glycidyl-1-naphthyl ether, 2- (2-naphthoxy) ethyl vinyl ether ,
1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,
7-dihydroxynaphthalene, 2,7-dimethoxynaphthalene, 1,1′-thiobis (2-naphthol), 1,
1'-bi-2-naphthol, 1,5-naphthyldiglycidyl ether, 2,7-di (2-vinyloxyethyl)
Naphthyl ether, 4-methoxy-1-naphthol, E
SN-175 (epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.) or a series thereof; an epoxy compound obtained by reacting a naphthol derivative with epichlorohydrin; a condensate of a mixture of a naphthol derivative and a phenol derivative with formalin; Epoxy compound reacted with phosphorus, condensate of naphthol derivative with formalin, 9.1
0-dimethoxyanthracene, 2-ethyl-9,10-
Dimethoxyanthracene, 2-tbutyl-9,10-dimethoxyanthracene, 2,3-dimethyl-9,10-
Dimethoxyanthracene, 9-methoxy-10-methylanthracene, 9,10-diethoxyanthracene, 2
-Ethyl-9,10-diethoxyanthracene, 2-t
Butyl-9,10-diethoxyanthracene, 2,3-
Dimethyl-9,10-diethoxyanthracene, 9-ethoxy-10-methylanthracene, 9,10-dipropoxyanthracene, 2-ethyl-9,10-dipropoxyanthracene, 2-tbutyl-9,10-dipropoxy Anthracene, 2,3-dimethyl-9,10-dipropoxyanthracene, 9-isopropoxy-10-methylanthracene, 9,10-dibenzyloxyanthracene, 2-ethyl-9,10-dibenzyloxyanthracene, 2- t-butyl-9,10-dibenzyloxyanthracene, 2,3-dimethyl-9,10-dibenzyloxyanthracene, 9-benzyloxy-10-methylanthracene, 9,10-di-α-methylbenzyloxyanthracene; 2-ethyl-9,10-di-α-
Methylbenzyloxyanthracene, 2-tbutyl-
Anthracene derivatives such as 9,10-di-α-methylbenzyloxyanthracene, 2,3-dimethyl-9,10-di-α-methylbenzyloxyanthracene, 9- (α-methylbenzyloxy) -10-methylanthracene 1,4-dimethoxychrysene, 1,4-diethoxychrysene, 1,4-dipropoxychrysene, 1,4-
Chrysene derivatives such as dimebenzyloxychrysene and 1,4-di-α-methylbenzyloxychrysene, 9-hydroxyphenanthrene, 9-methoxyphenanthrene,
9-ethoxyphenanthrene, 9-benzyloxyphenanthrene, 9,10-dimethoxyphenanthrene,
9,10-diethoxyphenanthrene, 9,10-dipropoxyphenanthrene, 9,10-dibenzyloxyphenanthrene, 9,10-di-α-methylbenzyloxyphenanthrene, 9-hydroxy-10-methoxyphenanthrene, 9-hydroxy Phenanthrene derivatives such as -10-ethoxyphenanthrene, (thio) xanthone derivatives such as xanthone, thioxanthone and 2,4-diethylthioxanthone, carbazole derivatives such as carbazole, N-vinylcarbazole and N-ethylcarbazole can be used, but are preferred. Is 2-ethyl-
9,10-dialkoxyanthracene derivatives such as 9,10-dimethoxyanthracene; phenanthrene derivatives such as 9,10-dimethoxyphenanthrene; thioxanthone derivatives such as 2,4-diethylthioxanthone; carbazole derivatives such as N-ethylcarbazole; Examples include naphthalene derivatives such as naphthol and 2-methoxynaphthalene. In addition, thioxanthones and various dye derivatives generally known as sensitizers for iodonium salt compounds can also be used.

In the present invention, the mixing ratio of the iodonium salt compound represented by the general formula [I] or [II] and the cationic polymerizable compound is 100
Parts (parts by weight, hereinafter the same). The iodonium salt compound may be used in an amount of 0.01 to 20 parts, preferably 0.1 to 10 parts. When this iodonium salt compound is small,
The curability of the cationically polymerizable compound is reduced, and if it is excessive, the properties of the cured product are reduced.

On the other hand, the compounding ratio of the sensitizer to the cationic polymerizable compound is 0.001 to 10 parts, preferably 0.01 to 10 parts, to 100 parts of the cationic polymerizable compound.
It can be 5 parts. When the amount of the sensitizer is small, the photoreactivity of the iodonium salt compound used as the photopolymerization initiator decreases, and when the amount is excessive, the properties of the cured product deteriorate. However, for example, a sensitizer having a cationically polymerizable group such as an epoxy group or a vinyl ether group is not limited thereto.
The mixing ratio can be arbitrarily changed.

When the photocurable composition of the present invention contains a pigment, it is used for inks and photoresists. As the pigment used in the present invention, carbon black, acetylene black, orchid black, black pigments such as aniline black, graphite, zinc yellow, cadmium yellow, yellow iron oxide, mineral fast yellow, nickel titanium yellow, navels yellow, Yellow pigments such as naphthol yellow S, Hanza yellow G, Hanza yellow 10G, benzidine yellow G, benzidine yellow GR, quinoline yellow lake, permanent yellow NCG, tartrazine lake, red mouth lead, molybdenum orange,
Permanent Orange GTR, Pyrazolone Orange, Vulcan Orange, Indus Ren Brilliant Orange R
Orange pigments such as K, benzidine orange G, and indus len brilliant orange GK, red bengal, cadmium red, lead red, cadmium mercury sulfide, permanent red 4
Red pigments such as R, Risor Red, Pyrazolone Red, Watching Red Calcium Salt, Lake Red D, Brilliant Carmine 6B, Eosin Lake, Rhodamine Lake B, Alizarin Lake, Brilliant Carmine 3B, Manganese Purple, Fast Violet B, Methyl Violet Lake Purple pigment, navy blue, cobalt blue, etc.
Alkaline blue lake, Victoria blue lake, phthalocyanine blue, metal-free phthalocyanine blue, partially chlorinated phthalocyanine blue, blue pigments such as fast sky blue, induslen blue BC, chrome green, chromium oxide, pigment green B, malachite green lake, Examples include green pigments such as Null Yellow Green G, white pigments such as zinc white, titanium dioxide, antimony white, and zinc sulfide, and extender pigments such as barite powder, barium carbonate, clay, silica, white carbon, talc, and alumina white. be able to.

In order to control the physical properties, curability and the like of the cured product of the photocurable composition according to the present invention, a radical polymerizable compound can be used. As the radical polymerizable compound used in the present invention, any monomers, oligomers and polymers having radical polymerizability can be used regardless of the kind thereof. As the radical polymerizable monomer, monofunctional or polyfunctional acrylate or methacrylate monomer, etc., as the radical polymerizable oligomer, epoxy acrylate, epoxy methacrylate, polyester acrylate, polyester methacrylate, polyether acrylate, polyether methacrylate, polyurethane acrylate, Polyurethane methacrylate, polybutadiene acrylate, polybutadiene methacrylate, and the like, and radical polymerizable polymers include polyester, polybutadiene, and polyether. , Urethane, each acrylates such as epoxy, the methacrylate compounds, can be exemplified unsaturated polyesters.

Examples of the radically polymerizable reactive diluent include acrylate monomers such as acrylic acid and ethyl acrylate, methacrylate monomers such as methacrylic acid and methyl methacrylate, and styrene.

[0039]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. Example 1 [Synthesis of 4-methoxycarbonylmethoxyphenylphenyliodonium hexafluorophosphonate] 6.3 g of methyl phenoxyacetate, 12.2 g of iodosobenzene acetate, 190 g of acetic acid, 17.6 g of acetic anhydride
Was stirred at room temperature. After dissolution of iodosobenzene acetate, 3.7 g of sulfuric acid was added dropwise at 15 ° C., and the mixture was stirred at room temperature for 3 hours. After standing overnight, an aqueous solution in which 7.0 g of potassium hexafluorophosphate was dissolved in 50 g of pure water was added dropwise with stirring under ice cooling. The reaction crude solution was poured into 1 liter of water, and the precipitate was separated by filtration, washed with water, and dried at 40 ° C. under reduced pressure to obtain white powder 13.0.
g was obtained. Table 1 shows the NMR spectrum data of this product.

[0040]

[Table 1]

Example 2 [Synthesis of 4-methoxycarbonylmethoxyphenyl-4'-methylphenyliodonium hexafluorophosphonate] The same as Example 1 except that 12.8 g of iodosotoluene acetate was used instead of iodosobenzene acetate. The reaction treatment was performed to obtain 13.4 g of a white powder. Table 1 shows the NMR spectrum data of this product.

Example 3 [Synthesis of 4-carboxymethoxyphenyl-4'-methylphenyliodonium hexafluorophosphonate] 5.8 g of phenoxyacetic acid, 12.8 g of iodosotoluene acetate, 190 g of acetic acid and 17.6 g of acetic anhydride were added at room temperature. And stirred. After dissolution of iodosobenzene acetate, 1
3.7 g of sulfuric acid was added dropwise at 5 ° C., and the mixture was stirred at room temperature for 3 hours. After standing overnight, an aqueous solution in which 7.0 g of potassium hexafluorophosphate was dissolved in 50 g of pure water was added dropwise with stirring under ice cooling. The crude reaction solution was poured into 1 liter of water, extracted with ethyl acetate, washed with water, dried at 40 ° C. under reduced pressure, and 6.7 as a white powder.
g was obtained. Table 1 shows the NMR spectrum data of this product.

Example 4 [Preparation of photocurable composition] The iodonium salt compound synthesized in Examples 1 to 3 was dissolved in γ-butyrolactone, and UVR-61 was used together with a sensitizer.
10 (UCC alicyclic epoxy) to prepare a photocurable composition. Table 2 shows the mixing ratio of the photocurable composition. All the mixing ratios at this time are expressed in parts by weight in terms of pure components.

[0044]

[Table 2]

Example 5 [Photocurable Test (1)] The photocurable composition was applied to a tin plate to a thickness of 5 μm and photocured under the following conditions. Table 3 shows the results. In Table 3, the mark “○” indicates that there was no tack. UV irradiation device: belt conveyor type UV irradiation device manufactured by I-Graphics Lamp: 80 w / cm condensing metal halide lamp, distance 10 cm

Example 6 Photocurable Test (2) The photocurable composition was applied to a tin plate to a thickness of 5 μm and photocured under the following conditions. Table 3 shows the results. In Table 3, the mark “○” indicates that the inside was cured. UV irradiation equipment: belt conveyor type UV irradiation equipment manufactured by Eye Graphics Lamp: 160 w / cm condensing gallium-containing metal halide lamp, distance 10 cm

[0047]

[Table 3]

As can be seen from Table 3, the photocurable composition of the present invention, particularly the photocurable composition using an iodonium salt compound and a sensitizer in combination, cures in a short time by irradiation with ultraviolet light, It was found that a photocurable composition having the above physical properties was obtained. In addition, it has been confirmed that the photocurable composition of the present invention has low toxicity.

[0049]

Industrial Applicability The iodonium salt compound of the present invention is a colorless solid without coloring, can be easily synthesized in a high yield, and can be used in combination with a sensitizer to obtain a clear or pigment-based compound. It exhibits excellent photoactivity and can cure a cationically polymerizable compound in a short time by irradiation with active energy rays such as light, an electron beam and X-rays. In addition, since the cured product of the composition has excellent physical properties, it can be suitably used as a paint, an adhesive, a photoresist, an ink, a silicone release and the like.

Claims (7)

[Claims] 1. An iodonium salt compound represented by the following general formula [I] or general formula [II]. Embedded image Embedded image [Wherein, R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group, or a cycloalkyl group, and R ₃ and R ₄ each independently represent a hydrogen atom, an optionally substituted alkyl group, Represents an alkyl group, R ₅ represents a hydroxyl group, an optionally substituted alkyl group, a cycloalkyl group, an alkenyl group, a phenyl group, a phenoxy group, an optionally substituted alkoxy group, and a cycloalkyloxy group; And m
Each independently represents 0, 1, 2 or 3, and n represents 1, 2 or 3. When n = 1, R ₃ and R ₅ may combine to form a ring. X represents a non-nucleophilic anionic residue. ] 2. A photopolymerization initiator comprising at least one iodonium salt compound represented by the general formula [I] or [II]. 3. A photocurable composition comprising at least one iodonium salt compound represented by the general formula [I] or [II] and a cationically polymerizable compound. 4. The photocurable composition according to claim 3, wherein the photocurable composition further contains a sensitizer. 5. The method according to claim 1, wherein the sensitizer is one or more compounds selected from the group consisting of 9,10-dialkoxyanthracene derivatives, phenanthrene derivatives, thioxanthone derivatives, carbazole derivatives, and naphthalene derivatives. The photocurable composition according to claim 4, wherein 6. The photocurable composition according to claim 3, wherein the photocurable composition further contains a pigment. 7. The photocurable composition according to claim 3, wherein the photocurable composition further contains a radical polymerizable compound.