JPH0761964A - New onium salt, photopolymerization initiator, energy ray curing composition containing the same initiator and its cured material - Google Patents

Abstract

PURPOSE:To obtain a new onium salt composed of a specified benzoylaryl compound, excellent in transparency, curing properties and compatibility, low in smells, capable of forming a cured film excellent in gloss and adhesion and useful, e.g. as a photopolymerization initiator for an energy ray curing composition. CONSTITUTION:A new onium salt represented by formula I {Ar is a univalent to tetravalent aromatic group; X is a (substituted) bisphenylsulfonyl; (a) is 1 to 4; (b) is 0 or 1 to 3; (a)+(b) is 1 to 4; (n) is 1 to 4; Z is a halide compound expressed by formula II [M is B, P, As or Sb; Q is a halogen; (m) is 3 to 6; L is 0 or 1; (m)+L is 4 to 6]}. This compound can be synthesized by reacting an aromatic carboxylic acid compound with a diphenyl sulfide compound in a reaction solvent prepared by dissolving phosphoric anhydride in an alkylsulfonic acid. It is useful as a photopolymerization initiator for an energy ray curing composition, excellent in compatibility, transparency and curing properties, low in smells and capable of forming a cured material excellent in gloss and adhesion.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel onium salt having a specific structure, a photopolymerization initiator containing the same as an active ingredient, and an energy ray-curable composition containing the same, which can be cured by irradiation with energy rays. The present invention relates to a composition and a cured product thereof.

[0002]

2. Description of the Related Art Photopolymerizable compositions have been extensively studied in the fields of printing inks, paints, coatings, liquid resist inks, etc., in order to save energy, space, and pollution, and their practical application has been studied. . However, most of these studies were based on the radical polymerization reaction of double bonds. Cationic polymerizable substances, such as epoxy resins, are materials with excellent physical properties, but it is difficult to photopolymerize them, and so far, materials with double bonds introduced by acrylic modification have been mainly used. . As a method of curing an epoxy resin by light, for example, US Pat. No. 379.
No. 4576 proposes a method of using a photosensitive aromatic diazonium salt as a photopolymerization initiator. However, the aromatic diazonium salt releases nitrogen gas by photolysis, and when the film thickness of the epoxy resin becomes 15 μm or more, the coating film foams and is not suitable for thick coating applications. Furthermore,
Also, the mixture with epoxy resin, even in the absence of light,
There is a problem in storage stability such that curing gradually progresses, and a one-part composition cannot be obtained.

[0003]

Various studies have been made to overcome the above-mentioned drawbacks of the diazonium salt-based photopolymerization initiators, and aromatic sulfonium salt-based and aromatic compounds have been developed as techniques for improving thick coating properties and storage stability. Group iodonium salt-based initiators and curable resin compositions containing them are disclosed in JP-B-52-
14278, Japanese Patent Publication No. 52-14277, Japanese Patent Laid-Open No. 54-53181, Japanese Patent Publication No. 59-19581.
It is disclosed in Japanese Patent Publication No. However, compositions containing these aromatic onium salts have the drawback of poorer curability than diazonium salts, and in the case of aromatic sulfonium salts, the odor of the cured product has been a problem.
In order to overcome this drawback, an aromatic sulfonium salt having a specific group has been proposed in JP-A-56-55420. However, although the above-mentioned drawbacks are alleviated, they are not sufficient. Further, as the fields in which the photopolymerizable composition is used are expanded, it is important to provide a novel photopolymerization initiator and a composition containing it in order to meet the market demand.

[0004]

As a result of earnest research to solve the above-mentioned problems, the present inventors have developed a novel photopolymerization initiator, and a composition using the same has a long storage stability and a good phase stability. The present invention has succeeded in providing an energy ray-curable composition having excellent compatibility (particularly, compatibility between various vinyl ethers and the photopolymerization initiator of the present invention) and curability, and having little odor of the cured product. That is, the present invention provides (1) an onium salt represented by the following formula (1),

[0005]

[Chemical 10]

(In the formula, Ar is a monovalent to tetravalent aromatic group, X is a bisphenylsulfonio group which may have a substituent, a
Is 1 to 4, b is 0 or 1 to 3, a + b is 1 to 4, n is 1 to 4, Z is the formula (3) MQ _m -(-OH) _L (3) M is a boron atom, a phosphorus atom, Arsenic atom or antimony atom, Q is a halogen atom, m is 3 to 6, L is 0 or 1,
m + L is 4 to 6). ) (2) Ar

[0007]

[Chemical 11]

(These aromatic groups are (C ₁ -C
₅ ) alkyl group, (C ₁ -C ₅ ) alkyloxycarbonyl group, (C ₁ -C ₅ ) alkylcarbonyloxy group,
It may have one or more substituents selected from a benzoyl group, a cyano group, a (C ₁ -C ₅ ) alkylthio group, and a halogen atom. ), An optionally substituted bisphenylsulfonio group has the formula (2)

[0009]

[Chemical 12]

(Here, R _{1 to} R ₁₀ are hydrogen atoms,
Halogen atom, nitro group, alkoxy group, C ₁ -C ₂₅ alkyl group, phenyl group optionally substituted with a C ₆ -C ₁₈ substituent, phenoxy group, phenylcarbonyl group, alkylthio group, phenylthio group , A benzyloxy group, a C ₁ -C ₂₅ aliphatic group having at least one hydroxyl group, or a formula: —OCH ₂ CH (R ₁₁ ) O— (wherein R ₁₁ is a hydrogen atom or an alkyl group). in an aliphatic group of C ₃ -C ₂₅ containing group represented by. ), A is 1 to 4, b is 0 or 1 to 3, a + b
Is 1-4, n is 1-4, Z is the formula (3) MQ _m -(-OH) _L (3) (where M is a boron atom, phosphorus atom, arsenic atom or antimony atom, Q is a halogen atom, m is 3 to 6, L is 0
Or 1, m + L is 4 to 6). ) Is the onium salt of (1) above, (3) A
r is

[0011]

[Chemical 13]

And R _{1 to} R ₁₀ are each a hydrogen atom,
Halogen atom, alkoxy group of _{C 1 ~C 5, C 1 ~C} 5
And an M is a phosphorus atom or an antimony atom, (4) at least one of R _{1 to} R ₅ is a halogen atom, and the other is a hydrogen atom.
_At least one of _{6 to} R ₁₀ is a halogen atom and the other is a hydrogen atom, and the onium salt of the above (3), (5) Ar is

[0013]

[Chemical 14]

R ₃ and R ₈ are halogen atoms, R ₁ , R ₂ , R _{4 to} R ₇ , R ₉ and R ₁₀ are hydrogen atoms, a is 2, b is 0 and n is n. 2, M is a phosphorus atom or an antimony atom, m is 6, and L is 0; (6) the onium salt of (5), wherein the halogen atom is a fluorine atom; )formula

[0015]

[Chemical 15]

An onium salt represented by the formula (8)

[0017]

[Chemical 16]

An onium salt represented by: (9) a photopolymerization initiator containing the onium salt of (1) to (8) as an active ingredient, (10) a cationically polymerizable substance and (1) to (1) above.
An energy ray-curable composition containing the onium salt of (8), (11) an epoxy compound as a cationically polymerizable substance,
The composition of (10) above, which is a vinyl ether compound or a cyclic ether compound, (12) the composition of (11) above, wherein the epoxy compound is an alicyclic epoxy resin, (1
3) Vinyl ether compounds include triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, cyclohexane-1,4-dimethylol divinyl ether, 1,4-butanediol divinyl ether,

[0019]

[Chemical 17]

Alternatively, the composition of the above (11), which is a urethane polyvinyl ether, or the onium salt (14) is the above (7).
Or the composition of the above (10) which is the onium salt of (8),
(15) The composition according to (10) above, wherein the energy rays are ultraviolet rays, (16) The composition according to (10) above, which contains 0.01 to 20 parts by weight of an onium salt per 100 parts by weight of a cationically polymerizable substance, (17) Alicyclic epoxy resin 100
An ultraviolet curable composition containing 0.1 to 10 parts by weight of the onium salt of (7) or (8) with respect to parts by weight, (1
8) An ultraviolet-curable composition containing 0.1 to 10 parts by weight of the onium salt of (7) or (8) with respect to 100 parts by weight of the vinyl ether compound, and (19) the vinyl ether compound is triethylene glycol divinyl ether. , Tetraethylene glycol divinyl ether, cyclohexane-1,4-dimethylol divinyl ether, 1,4
-Butanediol divinyl ether,

[0021]

[Chemical 18]

Alternatively, the composition of the above (18) which is urethane polyvinyl ether, (20) the above (10) to (19)
(21) A method for curing the composition, which comprises irradiating the composition of (10) to (19) with an energy ray, and (22) the energy ray of which is an ultraviolet ray. 21) The curing method of. In the general formula (1), the aromatic group having a valence of 1 to 4 is, for example,

[0023]

[Chemical 19]

Examples include, but are not limited to, m-phenylene group

[0025]

[Chemical 20]

A divalent group in which the bonding position is in the meta position (1, 3 position) is preferable. The monovalent to tetravalent aromatic group is C ₁ such as methyl group, ethyl group, propyl group and butyl group.
To C ₄ alkyl group, (C _{1 to} C ₄ ) alkylcarbonyloxy group, halogen atom such as fluorine atom, chlorine atom, bromine atom and iodine atom, (C _{1 to} C ₄ ) alkoxy group,
Benzoyl group, a phenyl group, a phenylthio group, (C ₁ ~
It may have one or more kinds of substituents such as C ₄ ) alkylthio group and cyano group.

Examples of the bisphenylsulfonio group of X which may have a substituent include groups represented by the above formula (2). In the substituents R _{1 to} R ₁₀ of the formula (2), examples of the halogen atom include F, Cl, Br and I.
Etc., but F is preferred. Examples of the alkoxy group include C _{1 to} C ₂₅ alkoxy groups such as methoxy group, ethoxy group, propoxy group, butoxy group and pentoxy group, and preferably C _{1 to} C ₅ alkoxy groups. Examples of the alkyl group include C _{1 to} C ₂₅ such as methyl group, ethyl group, propyl group, butyl group and pentyl group.
Alkyl groups of, preferably C _{1 to} C ₅ alkyl groups. As the substituent in the phenyl group which may be substituted with a C _{6 to} C ₁₈ substituent, a C _{6 to} C ₁₈ alkyl group exemplified by a nonyl group is preferable, and the substitution position is the p-position. preferable. As an alkylthio group,
For example, methylthio group, ethylthio group, propylthio group,
Examples thereof include C _{1 to} C ₅ alkylthio groups such as a butylthio group and a pentylthio group. Examples of the C _{1 to} C ₂₅ fatty acid group having at least one hydroxyl group include, for example,

[0028]

[Chemical 21]

, --O--CH ₂ CH ₂ CH ₂ CH ₂ --OH
And the following formula —Y—R — (— OH) _h (where Y is O or S, R is a methyl group, ethyl group, or other C group).
Methylene optionally having _{1 to} C ₅ alkyl group,
C _1-, such as dimethylene, trimethylene, tetramethylene, etc.
C ₂₅ polymethylene or C ₃ -C ₁₀ cycloalkylene, h is 1 to 3. And a group represented by).
C containing a group represented by the formula —OCH ₂ CH (R ₁₁ ) O—
The aliphatic group of ₃ -C ₂₅ for example - (- OCH ₂ CH
_{2 -) 2 -OH, - (} - OCH 2 CH 2 -) 3 -OH,
_{- (- OCH 2 CH 2 -} ) formula, such as ₂ -OCH ₃

[0030]

[Chemical formula 22]

(Wherein R ₁₂ is a hydrogen atom or an alkyl group,
i is 2 to 12, preferably 2 to 5, and R ₁₁ is the same as the above),

[0032]

[Chemical formula 23]

(Wherein j is an integer of 1 to 10, k is 1 or 2, and R ₁₁ is the same as the above). Examples of R ₁₁ include C _{1 to} C ₅ alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. Of these groups, preferred are a halogen atom, an alkyl group, an alkoxy group,
Examples thereof include a C _{1 to} C ₂₅ aliphatic group having at least one hydroxyl group, and a C _{3 to} C ₂₅ aliphatic group containing a group represented by the formula —OCH ₂ HC (R ₁₁ ) O—.

As the combination of the substituents of R _{1 to} R _{10 in} the above formula (2), (a) all of R _{1 to} R ₁₀ are hydrogen atoms,
(B) 9 to 6 of R _{1 to} R ₁₀ are hydrogen atoms, and 1
~ 4 are groups other than hydrogen atoms. Among (b), preferably (c) 3 to 4 of R _{1 to} R ₅ are hydrogen atoms, 1 to 2 are groups other than hydrogen atom, and 3 of R _{6 to} R ₁₀ are preferable.
-5 are hydrogen atoms, and 0-2 are groups other than hydrogen atoms. (C) will be described in more detail. (D) R ₁ , R
Any one of R ₂ and R ₃ , preferably R ₁ or R
₃ is a group other than the above hydrogen atom, the other is a hydrogen atom,
(E) Any one or two of R ₁ , R ₂ , and R ₃ and any one or two of R ₆ , R ₇ , and R ₈ are the above groups, and the others are hydrogen atoms. . In a more preferred embodiment of (e), R ₃ and R ₈ are groups of the above-mentioned, preferably a halogen atom, and the others are hydrogen atoms.

In the above general formula (1), a is preferably 1-2, b is preferably 0, and n is preferably 1-2. Preferred M in Formula (3) of General Formula (1) above
Examples thereof include phosphorus atom and antimony atom, and preferable halogen atom includes fluorine atom. m is 5
6 and L are preferably 0. Preferred specific examples include PF ₆ and SbF ₆ . Examples of the onium salt of the present invention represented by the above formula (1) include the following sulfonium salt compounds.

[0036]

[Chemical formula 24]

[0037]

[Chemical 25]

[0038]

[Chemical formula 26]

[0039]

[Chemical 27]

[0040]

[Chemical 28]

[0041]

[Chemical 29]

The onium salt of the present invention has the formula (5) as a starting material (1).

[0043]

[Chemical 30]

A diphenyl sulfide compound represented by the formula (wherein Ar and c have the same meanings as described above);

[0045]

[Chemical 31]

A method in which a substituted or unsubstituted diphenyl sulfoxide compound represented by the formula (wherein R _{1 to} R ₁₀ have the same meanings as described above) utilizing a known sulfonium salt formation reaction (hereinafter referred to as method (1)) ), (2) pre-synthesizing the corresponding substituted and unsubstituted sulfonium salts, then
It can be synthesized by any of the methods of converting and introducing a substituent (hereinafter referred to as method (2)). First, the method (1) will be described in detail. The diphenyl sulfide compound represented by the formula (5) and the substituted or unsubstituted diphenyl sulfoxide compound represented by the formula (4) are replaced by 1 equivalent of the former terminal sulfide group. On the other hand, it is preferably in the range of 0.25 to 1.2 mol, more preferably 1.0 to 1.1 mol, in a known method, for example, a dehydrating agent (for example, phosphorus pentoxide, concentrated sulfuric acid, acetic anhydride, etc.). In a room temperature to 150 ° C., and then the reaction liquids are represented by the formula (3 ′) B-MQ _m -(— OH) _L (3 ′) (wherein B is an alkali metal, M, Q, m , L has the same meaning as described above.). Examples of the compound represented by the formula (5) include the following compounds.

[0047]

[Chemical 32]

Examples of the compound represented by the formula (4) include diphenyl sulfoxide, 4,4'-difluorodiphenyl sulfoxide, 2,2'-difluorodiphenyl sulfoxide, 3,3'-difluorodiphenyl sulfoxide and 4,2. ′ -Difluorodiphenyl sulfoxide, 4,4′-dibromodiphenyl sulfoxide, 4,
4'-dichlorodiphenyl sulfoxide, 2,2'-dichlorodiphenyl sulfoxide, 2,2 ', 4,4'-
Tetrachlorodiphenyl sulfoxide, 4,4'-dimethyldiphenyl sulfoxide, 4,4'-diethyldiphenyl sulfoxide, 4,4'-dimethoxydiphenyl sulfoxide, 4-methylthiodiphenyl sulfoxide, 4-phenylthiodiphenyl sulfoxide, 4-phenylcarbonyldiphenyl Examples thereof include sulfoxide, 4-benzyloxydiphenyl sulfoxide, 2-nitrodiphenyl sulfoxide, 4-phenyldiphenyl sulfoxide, 4- (p-nonylphenyl) diphenyl sulfoxide and 4-phenyloxydiphenyl sulfoxide.

In the above formula (3 '), examples of A include alkali metals such as Na and K. Examples of the compound represented by the formula (3 ′) include NaSbF ₆ and Na.
PF ₆ , NaAsF ₆ , NaBF ₄ , NaSbF ₅ O
H, KSbF ₆ , KPF ₆ , KAsF ₆ , KSbF ₅ O
H and the like.

The compound represented by the above formula (5) can be obtained by reacting an aromatic carboxylic acid compound with diphenyl sulfide. As the reaction solvent, it is preferable to use one obtained by dissolving phosphoric anhydride in alkylsulfonic acid (for example, methanesulfonic acid etc.), and the reaction temperature is
Room temperature to 130 ° C is preferable. The reaction time is preferably 0.5 to 15 hours. Regarding the use ratio of the aromatic carboxylic acid compound and diphenyl sulfide, it is preferable to react diphenyl sulfide at a molar ratio of about 1 mol with respect to 1 equivalent of the carboxylic acid in the aromatic carboxylic acid compound.

Examples of the aromatic carboxylic acid compound include benzoic acid, o-methyl-benzoic acid, m-methyl-benzoic acid, p-methyl-benzoic acid, 3,5-dimethyl-benzoic acid and p-ethyl-benzoic acid. Acid, p-butyl-benzoic acid, o
-Methylcarbonyloxybenzoic acid, p-methyloxycarbonylbenzoic acid, o-chlorobenzoic acid, m-chlorobenzoic acid, p-chlorobenzoic acid, 2,4-dichlorobenzoic acid, o-fluorobenzoic acid, m-fluoro benzoic acid,
2,4-difluorobenzoic acid, p-methoxybenzoic acid,
o-benzoylbenzoic acid, p-phenylbenzoic acid, naphthalene-2-carboxylic acid, p-phenylthiobenzoic acid,
Aromatic monocarboxylic acids such as o-cyanobenzoic acid, p-cyanobenzoic acid and p-methylthiobenzoic acid, isophthalic acid, terephthalic acid, benzene-1,2,4-tricarboxylic acid, naphthalene-1,4,5 , 8-Tetracarboxylic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-
2,3-dicarboxylic acid,

[0052]

[Chemical 33]

Aromatic mono- or polycarboxylic acids such as Next, the method (2) will be specifically described. The method (2) is the same as in the general formula (1), where R ₁ to
At least one of R ₁₀ is an alkoxy group, at least 1
C ₁ -C ₂₅ aliphatic groups having 4 hydroxyl groups, or
C ₃ containing a group represented by O—CH ₂ (R ₁₁ ) CH—O—
It is suitable for the preparation of compounds which are aliphatic groups -C _25. This method is carried out by using the sulfonium salt synthesized by the method (1), for example, the formula (6)

[0054]

[Chemical 34]

(In the formula, A is a halogen atom, Ar, a, b,
n and Z have the same meanings as described above. ) Compounds etc.
Of halide compounds and alcohols of
Basic compounds (e.g. sodium hydroxide,
Reaction at room temperature to 150 ° C in the presence of
Yes. Examples of alcohols include methanol and ethanol.
, Carbitol, ethylene glycol, polyethylene
Glycol, propylene glycol, glycerin, g
Limethylolpropane, 1,4-butanediol, shik
Rohexanediol, monohydroxyethylthiol, etc.
Can be given. According to the method (2), the halide compound is
The halide part of the product is, for example, -OCH₃, -OC₂H_Five,
-(OCH₂CH₂)₂-OCH₃, -OCH₂CH₂−
OH,-(OCH₂CH₂)₃ -OH, -OCH₂CH
(CH₃) -OH, -SCH₂CH ₂OH, -OCH₂−
CH (OH) -CH₂-OH,

[0056]

[Chemical 35]

, -O-CH ₂ CH ₂ CH ₂ CH ₂ -OH
It is possible to obtain an onium salt converted into a substituent such as. Further, the compound obtained by the method (2) in which the substituent is converted to a substituent having a hydroxyl group further has a lactone group (eg, ε-caprolactone) or an acid group (eg, acetic acid, acetic anhydride, etc.) in the hydroxyl group. The present invention also includes an onium salt obtained by reacting with a known method.

Next, the energy ray-curable composition of the present invention will be described. Examples of the cationically polymerizable substance used in this composition include epoxy compounds, styrene,
Cationically polymerizable vinyl ether compounds such as vinyl ether, and further cyclic ether compounds (preferably spiro cyclic ether compounds such as spiro orthoester, bicyclo orthoester, spiro orthocarbonate)
Is mentioned. Examples of the epoxy compounds include conventionally known aromatic epoxy resins, alicyclic epoxy resins, aliphatic epoxy resins, and further epoxide monomers and episulfide monomers.

Examples of aromatic epoxy resins include polyglycidyl ethers of polyhydric phenols having at least one aromatic nucleus or alkylene oxide adducts thereof, such as bisphenol A, bisphenol F and bisphenol S. Glycidyl ethers produced by the reaction of a bisphenol compound such as bisphenol compound or an alkylene oxide (for example, ethylene oxide, propylene oxide, butylene oxide, etc.) adduct with epichlorohydrin,
Examples thereof include novolac type epoxy resins (for example, phenol / novolac type epoxy resin, cresol / novolac type epoxy resin, brominated phenol / novolac type epoxy resin, etc.) and trisphenolmethane triglycidyl ether.

Specific examples of the alicyclic epoxy resin include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate,
Bis- (3,4-epoxycyclohexylmethyl) adipate, 2- (3,4-epoxycyclohexyl-5,
5-Spiro-3,4-epoxy) cyclohexanone-meta-dioxane, bis (2,3-epoxycyclopentyl) ether, EHPE-3150 (manufactured by Daicel Chemical Industries, Ltd., alicyclic epoxy resin, softening point 71 ° C.) Etc.

Further, examples of the aliphatic epoxy resin include polyglycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof, and representative examples thereof include diglycidyl ethers 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 polyvalents such as glycerin Polyglycidyl ether of polyether polyol obtained by adding one or more kinds of alkylene oxides (for example, ethylene oxide, propylene oxide, etc.) to alcohol And the like. Further, examples of the epoxide monomers include monoglycidyl ether of aliphatic higher alcohol, phenol, cresol, butylphenol, and monoglycidyl ether of polyether alcohol obtained by adding alkylene oxide to these. Examples of cationically polymerizable vinyl ether compounds include triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, cyclohexane-1,4-dimethylol divinyl ether, 1,4-butanediol divinyl ether,

[0062]

[Chemical 36]

And urethane polyvinyl ether (for example, VECtome manufactured by ALLIED-SIGNAL)
r 2010) and the like. These cationically polymerizable substances are used alone or as a mixture of two or more.

The curable composition of the present invention is represented by the above formula (1) in an amount of 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the cationically polymerizable substance. A photopolymerization initiator containing an onium salt as an active ingredient is an essential component, but the specific usage ratio is the nature of the cationically polymerizable substance, the type of energy rays, the irradiation dose, the desired curing time, the temperature and the humidity. It is determined by considering various factors such as coating thickness. In order to facilitate the dissolution of the photopolymerization initiator in the cationically polymerizable substance, the photopolymerization initiator may be used by dissolving it in a solvent (eg, propylene carbonate, carbitol, carbitol acetate, γ-butyrolactone) in advance. it can. The curable composition of the present invention can be prepared by mixing the cationically polymerizable substance and the photopolymerization initiator by a method such as mixing, dissolving or kneading.

The curable composition of the present invention can be cured to a touch-free state or a solvent-insoluble state after 0.1 seconds to a few minutes by irradiating with energy rays such as ultraviolet rays. Any suitable energy ray may be used as long as it has energy that induces decomposition of the photopolymerization initiator, but it is preferably 2000 angstroms to 7,000 obtained from a high or low pressure mercury lamp, a xenon lamp, a germicidal lamp, a laser beam or the like. An electromagnetic wave energy ray having a wavelength of angstrom or an electromagnetic wave energy ray (high energy ray) such as an electron beam, an X-ray or a radiation is used, and an ultraviolet ray is preferable. The exposure to the energy rays depends on the intensity of the energy rays, but usually about 0.1 to 10 seconds is sufficient. However, it is preferable to spend more time on a relatively thick coated object. After 0.1 seconds to several minutes after irradiation with energy rays, most compositions dry by touch due to cationic polymerization, but in order to accelerate the cationic polymerization reaction,
It is also preferable to heat in some cases.

The composition of the present invention further comprises a solvent for dilution, a non-reactive resin for modification and a (meth) acrylic acid ester compound (for example, bisphenol A) within a range not impairing the cationic polymerization. -Type epoxy resin, novolac-type epoxy resin, and other oligomers such as epoxy (meth) acrylate, urethane (meth) acrylate, and polyester poly (meth) acrylate, which are reaction products of (meth) acrylic acid, and 2-hydroxy ( Monomers such as (meth) acrylate, 1,6-hexanediol di (mesi) acrylate, 1,9-nonanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, etc. It can be blended. When the (meth) acrylic acid ester compound is used, it is preferable to also use a photoradical polymerization initiator (for example, 1-hydroxycyclohexyl phenyl ketone, acetophenone dimethyl ketal, benzoyl methyl ether, etc.). Further, for example, an organic carboxylic acid or an acid anhydride may be used for the purpose of improving electric properties, or a polyol or other flexible prepolymer may be mixed for the purpose of imparting rubber elasticity.

The composition of the present invention is mainly used on the surface of an article, for example, 1 μm to 200 μm, preferably 3 μm to 50 μm.
It is usually applied as a transparent liquid, but depending on the application, it may be an inert pigment, dye, filler, antistatic agent, flame retardant, antifoaming agent, flow control agent, thickener, Used as a mixture of a sensitizer, an accelerator, a light stabilizer and the like. The composition of the present invention includes metal, wood, rubber, plastic, glass,
It can be used for ceramic products. Further, specific applications of the present invention include paints, coating agents, inks, resists, liquid resists, inks, adhesives, molding materials, casting materials, putties, glass fiber impregnating agents, and sealing agents.

[0068]

EXAMPLES The present invention will be specifically described below with reference to examples. The parts in the synthesis examples and examples are parts by weight.

(Synthesis Example of the Diphenyl Sulfide Compound Represented by Formula (5)) Synthesis Example 1 (Synthesis of Compound of Formula (i)) 161.7 parts of methanesulfonic acid and 16.2 parts of phosphorus pentoxide are completely added. And diphenyl sulfide 18.6
And 12.2 parts of benzoic acid were charged, the reaction was carried out at 80 ° C. for 1 hour, and the completion of the reaction was confirmed by liquid chromatography. The reaction mixture was mixed with 1000 parts of an aqueous potassium hydroxide solution (800 parts of water). (200 parts of potassium hydroxide dissolved therein) was added dropwise, the precipitate was filtered off and dried, then this was heated to 400 parts of ethanol (60 ° C).
After dissolution and cooling to 5 ° C., the precipitate was filtered off and dried to obtain 20.3 parts of a white solid (i). The melting point of the product is 69-
It was 70 ° C.

Synthesis Example 2 (Synthesis of Compound of Formula (ii)) 180.3 parts of methanesulfonic acid and 18.3 parts of phosphorus pentoxide were completely dissolved, and diphenyl sulfide 18.6 was dissolved therein.
And 13.6 parts of p-methylbenzoic acid were charged, the reaction was carried out at 80 ° C. for 1 hour, and it was confirmed by liquid chromatography that the reaction was completed.
The same treatment as in (2) was performed to obtain 20.2 parts of a white solid (ii). The melting point of the product was 117-118 ° C.

Synthesis Example 3 (Synthesis of Compound of Formula (iii)) 208.2 parts of methanesulfonic acid and 20.8 parts of phosphorus pentoxide were completely dissolved, and diphenyl sulfide 18.6 was dissolved therein.
And 15.7 parts of p-chlorobenzoic acid were charged, the reaction was carried out at 80 ° C. for 1 hour, and it was confirmed by liquid chromatography that the reaction was completed. The reaction mixture was treated in the same manner as in Synthesis Example 1. 21.6 parts of white solid (iii) was obtained. The melting point of the product was 134-135 ° C.

Synthesis Example 4 (Synthesis of Compound of Formula (iv)) 238.6 parts of methanesulfonic acid and 23.9 parts of phosphorus pentoxide were completely dissolved, and diphenyl sulfide 18.6 was dissolved therein.
And 18.0 parts of p-methyloxycarbonylbenzoic acid were charged, the reaction was carried out at 80 ° C. for 1 hour, and it was confirmed by liquid chromatography that the reaction was completed. This reaction mixture was treated in the same manner as in Synthesis Example 1. Treated as a white solid (iv)
21.6 parts were obtained. The melting point of the product was 145-148 ° C.

Synthesis Example 5 (Synthesis of Compound of Formula (v)) 220.1 parts of methanesulfonic acid and 22.0 parts of phosphorus pentoxide were completely dissolved, and diphenyl sulfide 37.2 was dissolved therein.
And 16.6 parts of isophthalic acid were charged, the reaction was carried out at 80 ° C. for 6 hours, and it was confirmed by liquid chromatography that the reaction was completed. The reaction mixture was treated in the same manner as in Synthesis Example 1 and white. 35.2 parts of solid (v) was obtained. The melting point of the product was 147-152 ° C.

Synthesis Example 6 (Synthesis of Compound of Formula (vi)) 286.4 parts of methanesulfonic acid and 28.6 parts of phosphorus pentoxide were completely dissolved, and diphenyl sulfide, 37.
2 parts and 21.6 parts of naphthalene-2,6-dicarboxylic acid were charged, the reaction was carried out at 80 ° C. for 6 hours, and it was confirmed by liquid chromatography that the reaction was completed. The same treatment was performed to obtain 37.0 parts of a white solid (vi). The melting point of the product was 195 to 200 ° C.

(Synthesis Example of Onium Salt Represented by Formula (1)) Example 1 (Synthesis of Compound (a)) 29.0 parts of the compound (4-benzoyl-diphenylsulfide) obtained in Synthesis Example 1 , 4'-Difluorodiphenyl sulfoxide (23.9 parts), phosphorus pentoxide (39.8 parts) and methanesulfonic acid (398 parts) as a solvent were charged at 80 ° C.
The mixture was heated to room temperature and stirred for 3 hours, and then the reaction mixture was stirred while 280.0 parts of an aqueous solution of NaPF ₆ at 5 ° C. (263.2 parts of water to 16.8 parts of NaPF _6).
Part that is melted. ) Little by little, the precipitated white solid was filtered and dried, and then isopropanol 650 was added.
After heating (70 ° C.), the mixture was cooled to 0 ° C., filtered, and dried to obtain 46.0 parts of a white solid (compound (a)). The melting point of the product was 131 to 139 ° C., and the result of elemental analysis almost agreed with the calculated value.

Element Measured value (wt%) Calculated value (wt%) Carbon 56.72 56.71 Hydrogen 3.24 3.22 Sulfur 9.79 9.77 Phosphorus 4.75 4.72 Fluorine 23.17 23. 15

Example 2 (Synthesis of Compound (b)) Compound (4- (p-methylbenzoyl) obtained in Synthesis Example 2
-Diphenyl sulfide) (30.4 parts), diphenyl sulfoxide (20.2 parts) and concentrated sulfuric acid (179.8 parts) were charged and the reaction was carried out at room temperature for 24 hours. Then, while stirring the reaction mixture, an aqueous solution of NaSbF ₆ 431 at 5 ° C was added. 0.1 part (25.8 parts of NaSbF ₆ dissolved in 405.3 parts of water) was added dropwise little by little, the white solid deposited was filtered and dried, and then heated to 650 parts of isopropanol (70 ° C.). After dissolution, cooling to 0 ° C., filtration and drying, 50.8 parts of a white solid (compound (b)) was obtained. The melting point of the product was 110 to 118 ° C., and the result of elemental analysis almost agreed with the calculated value.

Element Measured value (wt%) Calculated value (wt%) Carbon 52.98 52.99 Hydrogen 3.48 3.47 Sulfur 8.85 8.84 Antimony 16.80 16.78 Fluorine 15.73 15. 71

Example 3 (Synthesis of Compound (c)) Compound (4- (p-chlorobenzoyl) obtained in Synthesis Example 3
-Diphenyl sulfide) 32.5 parts, 4,4'-dibromodiphenyl sulfoxide 36 parts, concentrated sulfuric acid 240.
6 parts were charged and the reaction was carried out at room temperature for 24 hours. Then, while stirring the reaction mixture, 431.1 parts of an aqueous solution of NaSbF ₆ at 5 ° C. (25.3 parts of NaSbF ₆ in 405.3 parts of water) was stirred.
What melted 5.8 parts. ), And the precipitated white solid is filtered and dried, then dissolved in 650 parts of isopropanol by heating (70 ° C.), cooled to 0 ° C., filtered and separated, and dried to give a white solid (compound (c)). ) Was obtained. The melting point of the product was 125 to 129 ° C., and the result of elemental analysis almost agreed with the calculated value.

Element Measured value (% by weight) Calculated value (% by weight) Carbon 41.22 41.21 Hydrogen 2.24 2.23 Sulfur 7.10 7.10 Chlorine 3.93 3.92 Bromine 17.72 17. 69 Antimony 13.49 13.47 Fluorine 12.65 12.62

Example 4 (Synthesis of Compound (d)) 34.8 parts of the compound obtained in Synthesis Example 4, 20.2 parts of diphenyl sulfoxide, and 173.1 parts of concentrated sulfuric acid were charged, and the reaction was carried out at room temperature for 24 hours. Then, while stirring the reaction mixture, 431.1 parts of an aqueous solution of NaSbF ₆ at 0 ° C. (water 4
A solution obtained by dissolving 26.8 parts of NaSbF ₆ in 05.3 parts. ) Little by little, and the precipitated white solid is filtered,
Dry and then heat to 650 parts isopropanol (70
(° C), melted, cooled to 0 ° C, filtered and dried to obtain 53.9 parts of a white wax-like product (compound (d)).
The elemental analysis results were in good agreement with the calculated values.

Element Measured value (wt%) Calculated value (wt%) Carbon 51.54 51.52 Hydrogen 3.30 3.28 Sulfur 8.35 8.33 Antimony 15.83 15.82 Fluorine 14.84 14. 82

Example 5 (Synthesis of Compound (e)) 50.3 parts of the compound obtained in Synthesis Example 5, 40.4 parts of diphenyl sulfoxide and 208.1 parts of concentrated sulfuric acid were charged and the reaction was carried out at room temperature for 24 hours. Then, while stirring the reaction mixture, 862.3 parts of an aqueous NaSbF ₆ solution at room temperature (water 81
51.7 parts of NaSbF ₆ dissolved in 0.6 parts. ) Little by little, and the precipitated white solid is filtered,
Dry and then heat to 650 parts isopropanol (70
(° C), dissolved, cooled to 0 ° C, filtered and dried to obtain 94.1 parts of a white solid (compound (e)). The melting point of the product was 152 to 162 ° C., and the result of elemental analysis was in good agreement with the calculated value.

Element Measured value (% by weight) Calculated value (% by weight) Carbon 50.05 50.03 Hydrogen 3.02 3.00 Sulfur 9.57 9.54 Antimony 18.11 18.10 Fluorine 16.99 16. 96

Example 6 (Synthesis of Compound (f)) 55.3 parts of the compound obtained in Synthesis Example 6, 46.1 parts of 4,4'-dimethyldiphenyl sulfoxide, concentrated sulfuric acid 233.4.
The reaction mixture was stirred at room temperature for 24 hours, and then 862.3 parts of an aqueous solution of NaSbF ₆ at room temperature (510.6 parts of NaSbF ₆ was added to 810.6 parts of water) while stirring the reaction mixture.
What melted 7 parts. ) Little by little, the precipitated white solid is filtered and dried, and then isopropanol 65 is added.
Dissolve by heating (70 ° C) with 0 part, cool to 0 ° C, filter,
After drying, 96.5 parts of a white solid (compound (f)) was obtained. The melting point of the product was 201 to 205 ° C., and the result of elemental analysis almost agreed with the calculated value.

Element Measured value (wt%) Calculated value (wt%) Carbon 52.23 52.20 Hydrogen 3.55 3.53 Sulfur 8.98 8.97 Antimony 17.09 17.06 Fluorine 15.99 15. 98

Example 7 (Synthesis of Compound (g)) 50.3 parts of the compound obtained in Synthesis Example 5, 47.6 parts of 4,4′-difluorodiphenyl sulfoxide, concentrated sulfuric acid 225.
4 parts were charged, the reaction was carried out at room temperature for 24 hours, and then the reaction mixture was stirred, while the NaSbF ₆ aqueous solution at room temperature was 862.3 parts. Water 810.6 parts was NaSbF ₆ 51.7.
Part that is melted. ), The white solid that has precipitated is filtered off, dried and then isopropanol 65 is added.
It was heated to 0 part (70 ° C.) and dissolved, cooled to 0 ° C., filtered, and dried to obtain 94.1 parts of a white solid (compound (g)). The melting point of the product was 163 to 172 ° C., and the result of elemental analysis was in good agreement with the calculated value.

Element Measured value (wt%) Calculated value (wt%) Carbon 47.51 47.48 Hydrogen 2.58 2.56 Sulfur 9.07 9.05 Antimony 17.20 17.18 Fluorine 21.49 21. 46

Example 8 (Synthesis of compound (h)) 32.8 parts of the compound obtained in Example 1, 4.0 parts of sodium hydroxide and 100 parts of 1,4-butanediol were charged,
After reacting for 24 hours at room temperature, the mixture was poured into water, the oily substance was separated, and dried to obtain 41.8 parts of a pale yellow liquid product (compound (h)). The results of elemental analysis agreed with the calculated values.

Element Measured value (wt%) Calculated value (wt%) Carbon 52.80 52.78 Hydrogen 4.45 4.43 Sulfur 7.23 7.22 Antimony 13.70 13.71 Fluorine 12.85 12. 84

Example 9 (Synthesis of Compound (j)) 70.8 parts of the compound obtained in Example 7, 4.0 parts of sodium hydroxide and 200 parts of ethylene glycol were charged and reacted at room temperature for 24 hours, and then, The white solid deposited by pouring into water was filtered and dried to obtain a solid product at room temperature.
Then 78.2 parts of the above product, ε-caprolactone 4
Charge 8.5 parts, stannous chloride 0.04 parts, 120 ℃
After reacting for 15 hours, it was confirmed that ε-caprolactone was 1% or less in the reaction mixture, and the reaction was terminated to obtain 126.7 parts of a liquid product (compound (j)). The results of elemental analysis agreed with the calculated values.

Element Measured value (wt%) Calculated value (wt%) Carbon 53.86 53.84 Hydrogen 5.48 5.49 Sulfur 5.15 5.13 Antimony 9.76 9.75 Fluorine 9.13 9. Thirteen

Example 10 (Synthesis of Compound (k)) 50.3 parts of the compound obtained in Synthesis Example 5, 47.6 parts of 4,4'-difluorodiphenyl sulfoxide, concentrated sulfuric acid 225.
4 parts were charged, the reaction was carried out at room temperature for 24 hours, and then the reaction mixture was stirred at room temperature with an aqueous NaPF ₆ solution 5
59.8 parts (33.6 parts of NaPF ₆ dissolved in 526.6 parts of water) were added dropwise little by little, and the precipitated white solid was filtered, dried and then isopropanol 650.
Parts to dissolve (70 ° C.), cool to 0 ° C., filter and dry to a white solid (compound (k)) 104.9.
I got a copy. The melting point of the product was 154-163 ° C, and the results of elemental analysis were in good agreement with the calculated values.

Element Measured value (wt%) Calculated value (wt%) Carbon 54.48 54.46 Hydrogen 2.97 2.94 Sulfur 10.35 10.38 Phosphorus 5.01 5.02 Fluorine 24.59 24. 61

(Examples of Compositions) Examples 11 to 30 and Comparative Examples 1 to 6 Energy ray curable compositions were compounded and mixed in accordance with the compounding compositions (numerical values are parts by weight) shown in Tables 1 and 2. Dissolved. This was applied to an aluminum test panel in a thickness of 5 μm and was irradiated with ultraviolet rays from a distance of 8 cm with a high pressure mercury lamp (80 W / cm) to be cured. The prepared composition was tested for transparency, storage stability, dryness to the touch, gloss of cured coating, and odor. The results are shown in Tables 1 and 2. (Test method)

Transparency: The transparency of the composition was visually evaluated. ○ ・ ・ ・ ・ Completely transparent △ ・ ・ ・ ・ Slightly turbid × ・ ・ ・ ・ White dull XX ・ ・ ・ ・ Immediately separates Storage stability: Composition at 3 ° C at 3 ° C It was stored for 6 months and stability was investigated. ○ ・ ・ ・ ・ No change △ ・ ・ ・ ・ Slightly thickened × ・ ・ ・ ・ Gelled to touch: Dryness to touch (mJ / c)
m ² ) was measured. Gloss: The surface of the cured coating film was visually evaluated after being irradiated with ultraviolet rays until it was dry to the touch. ○ ・ ・ ・ ・ Gloss is good △ ・ ・ ・ ・ Slightly cloudy × ・ ・ ・ ・ No gloss Odor: After irradiating 1000 mJ / cm ² on the coated surface, observe the odor on the surface of the cured coating film did. ○ ・ ・ ・ ・ No odor △ ・ ・ ・ ・ Slight odor × ・ ・ ・ ・ Smelling XX ・ ・ ・ ・ Strong odor

[0097]

[Table 1]

[0098]

[Table 2]

As is clear from the results of Tables 1 and 2, the composition containing the photopolymerization initiator of the present invention has excellent compatibility, is transparent and has excellent curability, and the cured coating film has good gloss. There is little odor in the cured coating film.

[0100]

The energy ray-curable composition containing the photopolymerization initiator of the present invention has excellent compatibility, is transparent and has excellent curability, has a good gloss of the cured coating film, and has an odor of the cured coating film. It also provides a cured product with excellent physical properties that is small and has good adhesion to metal.

Continuation of front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display area C09D 5/00 PNW

Claims (22)

[Claims] 1. An onium salt represented by the following formula (1): (In the formula, Ar is a monovalent to tetravalent aromatic group, X is a bisphenylsulfonio group which may have a substituent, a is 1 to 4, b
Is 0 or 1 to 3, a + b is 1 to 4, n is 1 to 4, Z is the formula (3) MQ _m -(-OH) _L (3) M is a boron atom, a phosphorus atom, an arsenic atom or an antimony atom, Q is a halogen atom, m is 3 to 6, L is 0 or 1,
m + L is 4 to 6). ) 2. Ar is represented by: (These aromatic groups are (C ₁ -C ₅ ) alkyl groups, (C ₁ -C ₅ ) alkyloxycarbonyl groups, (C
₁ -C ₅₎ alkylcarbonyloxy group, benzoyl group, a cyano group may have one or more substituents selected (C ₁ -C ₅₎ alkylthio group, a halogen atom. ), A bisphenylsulfonio group which may have a substituent is represented by the formula (2): (Here, R _{1 to} R ₁₀ are each a hydrogen atom, a halogen atom, a nitro group, an alkoxy group, an alkyl group, a carbon number C ₆
To C ₁₈ substituents which may be substituted with phenyl group, phenoxy group, phenylcarbonyl group, alkylthio group, phenylthio group, benzyloxy group, C _{1 to} C ₂₅ aliphatic group having at least one hydroxyl group, or formula -OCH ₂
CH (R ₁₁ ) O— (wherein R ₁₁ is a hydrogen atom or an alkyl group) is a C ₃ -C ₂₅ aliphatic group. ), A is 1-4, b
Is 0 or 1 to 3, a + b is 1 to 4, n is 1 to 4, Z is a formula (3) MQ _m -(-OH) _L (3) (where M is a boron atom, a phosphorus atom, an arsenic atom or Antimony atom, Q is a halogen atom, m is 3 to 6, L is 0
Or 1, m + L is 4 to 6). ) Is the onium salt of claim 1. 3. Ar is represented by: Wherein R _{1 to} R ₁₀ are each a hydrogen atom, a halogen atom, a C _{1 to} C ₅ alkoxy group, a C _{1 to} C ₅ alkyl group, and M is a phosphorus atom or an antimony atom. salt 4. An onium salt according to claim 3, wherein at least one of R _{1 to} R ₅ is a halogen atom and the other is a hydrogen atom, and at least one of R _{6 to} R ₁₀ is a halogen atom and the other is a hydrogen atom. 5. Ar is represented by: And R ₃ and R ₈ are halogen atoms, and R ₁ and R
₂ , R _{4 to} R ₇ , R ₉ , R ₁₀ are hydrogen atoms, a is 2, b is 0, n is 2, M is a phosphorus atom or an antimony atom, m is 6, and L is 0. The onium salt of claim 2 which is 6. The halogen atom is a fluorine atom.
Onium salt 7. The formula: Onium salt represented by 8. The formula: Onium salt represented by 9. A photopolymerization initiator containing the onium salt according to claim 1 as an active ingredient. 10. An energy ray-curable composition containing a cationically polymerizable substance and the onium salt of claims 1-8. 11. The composition according to claim 10, wherein the cationically polymerizable substance is an epoxy compound, a vinyl ether compound or a cyclic ether compound. 12. The composition according to claim 11, wherein the epoxy compound is an alicyclic epoxy resin. 13. The vinyl ether compound is triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, cyclohexane-1,4-dimethylol divinyl ether, 1,4-butanediol divinyl ether, or Alternatively, it is urethane polyvinyl ether. 14. The composition according to claim 10, wherein the onium salt is the onium salt according to claim 7 or 8. 15. The energy ray is an ultraviolet ray.
Composition of 16. The composition according to claim 10, which contains 0.01 to 20 parts by weight of an onium salt based on 100 parts by weight of a cationically polymerizable substance. 17. An ultraviolet curable composition containing 0.1 to 10 parts by weight of the onium salt of claim 7 or 8 with respect to 100 parts by weight of an alicyclic epoxy resin. 18. An ultraviolet-curable composition containing 0.1 to 10 parts by weight of the onium salt of claim 7 or 8 with respect to 100 parts by weight of a vinyl ether compound. 19. The vinyl ether compound is triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, cyclohexane-1,4-dimethylol divinyl ether, 1,4-butanediol divinyl ether, or Or the composition of claim 19, which is urethane polyvinyl ether. 20. A cured product of the composition of claims 10-19. 21. A method of curing the composition according to claim 10, which comprises irradiating the composition with energy rays. 22. The energy rays are ultraviolet rays.
Curing method