JPH0827209A - Photopolymerization initiator, actinic energy-curing polymer composition containing the initiator and cured article - Google Patents

Abstract

PURPOSE:To obtain a photopolymerization initiator consisting of a specific sulfonium salt or sulfoxonium salt and capable of producing a cured coating film excellent in compatibility and storage stability, having excellent transparency, curability and glossiness and free from smell when used in cation- polymerizable material. CONSTITUTION:This initiator is a sulfonium salt or sulfoxonium salt expressed by formula I [X is formula II; R1 to R10 are each H, a halogen, nitro, an alkoxy, a 1-18C aliphatic group, phenyl, a phenoxy, a thiophenoxy, (CH2)mOH, (OCH2 CH2)1OH ((m) and (1) are each 1-5), OCH2CH=CH2, etc.; G is sulfur or formula III; Ar is a monovalent to 4-valent aromatic group; Y is formula IV or V; a=1-4; b=0-3; a+b=1-4; Z is MQp or MQp-1 (OH) (M is phosphorus, boron, arsenic or antimony; Q is a halogen; p=4-6)]. The objective composition is obtained by compounding a cation-polymerizable material with the sulfonium salt or sulfoxonium salt as a polymerization initiator. An epoxy resin, styrene, etc., is used as the polymerizable material.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a sulfonium salt or sulfoxonium salt having a novel specific structure, a photopolymerization initiator composed of the same, and an energy ray-curable resin containing the same which can be cured by irradiation with energy rays. 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. .

[0003]

Although the epoxy resin is cured by light, for example, in US Pat. No. 3,794,576, a photosensitive aromatic diazonium salt is used as a photopolymerization initiator. A method of polymerizing an epoxy resin by decomposing and releasing a Lewis acid has been proposed. However, the aromatic diazonium salt releases nitrogen gas at the same time as Lewis acid 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. Further, the mixture with the epoxy resin has a problem in storage stability such as gradual curing even in the absence of light, and cannot be a one-part composition. In order to overcome the above-mentioned drawbacks of the diazonium salt-based initiator, various investigations have been made, and as a technique with improved thick coatability and storage stability, an aromatic sulfonium salt-based or aromatic iodonium salt-based initiator and containing them are contained. Curable resin compositions are disclosed in JP-B-52-1278, JP-B-52-14277, JP-A-54-53181, JP-B-59-19581 and the like. 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. But,
Although the above 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. We have succeeded in providing an energy ray-curable composition which has excellent acceptability and curability and has a cured product with little odor. That is, the present invention is

Expression (1)

[0006]

[Chemical 10]

(Where X is a group represented by the following formula (2)

[0008]

[Chemical 11]

(R _{1 to} R ₁₀ are each a hydrogen atom, a halogen atom, a nitro group, an alkoxy group, a C _{1 to} C ₁₈ aliphatic group, a phenyl group, a phenoxy group, a thiophenoxy group,

[0010]

[Chemical 12]

Or

[0012]

[Chemical 13]

A group selected from any of the following: m and l are numbers from 1 to 5, G is a sulfur atom or

[0014]

Embedded image

[0015] ), Ar is a monovalent to tetravalent aromatic group,
Y is

[0016]

[Chemical 15]

Or

[0018]

Embedded image

Where a is 1 to 4 and b is 0 or 1
3, a + b is 1 to 4, n is 1 to 4, Z is represented by the formula (3) or the formula (4),

[0020]

[Chemical 17]

[0021]

Embedded image

M is a phosphorus atom, boron atom, arsenic atom or antimony atom, Q is a halogen atom,
p is an integer of 4-6. ) A sulfonium salt or a sulfoxonium salt, (2) a photopolymerization initiator comprising these salts, (3) a cationically polymerizable substance (A) and (1) the photopolymerization initiator (B). TECHNICAL FIELD The present invention relates to an energy ray-curable composition and a cured product thereof.

Cationic polymerizable substance (A) used in the present invention
Examples thereof include cationically polymerizable vinyl compounds such as epoxy resin, styrene and vinyl ether, and cyclic ethers such as spiro orthoester, bicyclo orthoester and spiro orthocarbonate.
Examples of the epoxy resin include conventionally known aromatic epoxy resins, alicyclic epoxy resins, aliphatic epoxy resins, and further epoxide monomers and episulfide monomers. Here, as an example of the aromatic epoxy resin, a polyglycidyl ether of a polyhydric phenol having at least one aromatic nucleus or an alkylene oxide adduct thereof, such as bisphenol A, bisphenol F, and bisphenol S Glycidyl ethers produced by reacting a compound or an alkylene oxide (for example, ethylene oxide, propylene oxide, butylene oxide, etc.) adduct of a bisphenol compound 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, and 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 7
1 ° C.) and the like. 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 ether of 1,4-butanediol and 1,6-hexane. Diglycidyl ether of diol, triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, diglycidyl ether of polyethylene glycol, diglycidyl ether of propylene glycol, aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin 1 Examples include polyglycidyl ethers of polyether polyols obtained by adding one kind or two or more kinds of alkylene oxides (ethylene oxide, propylene oxide). 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. As the cationically polymerizable vinyl compound, for example, triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, cyclohexane-1,4-dimethylol divinyl ether, 1,4-butanediol divinyl ether,

[0024]

[Chemical 19]

And

[0026]

Embedded image

And the like. Further, these cationically polymerizable organic materials may be used alone or as a mixture of two or more kinds.

The sulfonium salt or sulfoxonium salt represented by the general formula (1) used in the present invention is, for example, the sulfonium salt represented by the general formula (5).

[0029]

[Chemical 21]

(In the formula, R _{1 to} R ₁₀ are each a hydrogen atom, a halogen atom, a nitro group, an alkoxy group, and C ₁ to C.
₁₈ aliphatic groups, phenyl group, phenoxy group, thiophenoxy group,

[0031]

[Chemical formula 22] Or

[0032]

[Chemical formula 23]

A group selected from any of the following: m and l are numbers from 1 to 5, Ar is a monovalent to tetravalent aromatic group, a is 1 to 4, b is 0 or 1 to 3, and a + b is 1 to 1.
4, n is 1 to 4, and Z is represented by the above formula (3) or formula (4). ) Can be obtained.
The sulfonium salt represented by the general formula (5) includes: 1) a diphenyl sulfide compound represented by the formula (6) as a starting material.

[0034]

[Chemical formula 24]

(Wherein C is 1 to 4 and Ar is a 1 to 4 valent aromatic group) and a substituted or unsubstituted diphenyl sulfoxide compound is utilized by a known sulfonium salt formation reaction (hereinafter 1) method), 2) preliminarily synthesizing corresponding substituted and unsubstituted sulfonium salts, and then converting and introducing a substituent (hereinafter referred to as 2) method)
Can be synthesized by any of the following.

First, the method 1) will be described in detail by using the equation (6).
A diphenyl sulfide compound represented by the formula (as specific examples, benzoic acid, o-methyl-benzoic acid, m-methyl-benzoic acid, p-methyl-benzoic acid, 3,5-dimethyl-benzoic acid, p -Ethyl-benzoic acid, p-butylbenzoic acid, o-methylcarbonyloxybenzoic acid, p-methyloxycarbonylbenzoic acid, o-chloro-benzoic acid,
m-chloro-benzoic 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, Aromatic monocarboxylic acids such as p-phenylthiobenzoic acid, o-cyanobenzoic acid, p-cyanobenzoic acid, 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

[0037]

[Chemical 25]

[0038]

[Chemical formula 26]

[0039]

[Chemical 27]

[0040]

[Chemical 28]

[0041]

[Chemical 29]

[0042]

Embedded image

[0043]

[Chemical 31]

It can be obtained by reacting an aromatic carboxylic acid compound such as an aromatic polycarboxylic acid with a diphenyl sulfide. As the reaction solvent, it is preferable to use one obtained by dissolving phosphoric anhydride in alkylsulfonic acid (for example, methanesulfonic acid), and the reaction temperature is preferably room temperature to 130 ° C. The reaction time is preferably 0.5 to 15 hours. It is preferable to react about 1 mol of diphenyl sulfide with respect to 1 equivalent of the carboxylic acid in the aromatic carboxylic acid compound. ) And a substituted or unsubstituted diphenyl sulfoxide compound (eg, diphenyl sulfoxide, 4,4′-difluorodiphenyl sulfoxide,
2,2'-difluorodiphenyl sulfoxide, 3,
3'-difluorodiphenyl sulfoxide, 4,2'-
Difluorodiphenyl sulfoxide, 4,4'-dibromodiphenyl sulfoxide, 4,4'-dichlorodiphenyl sulfoxide, 2,2'-dichlorodiphenyl sulfoxide, 2,2 ', 4,4'-tetrachlorodiphenyl sulfoxide, 4,4 ′ -Dimethylphenyl sulfoxide, 4,4′-diethyldiphenyl sulfoxide,
4,4'-dimethoxydiphenyl sulfoxide, 4-methylthiodiphenyl sulfoxide, 4-phenylthiodiphenyl sulfoxide, 4-phenylcarbonyldiphenyl sulfoxide, 4-benzoyloxydiphenyl sulfoxide and the like are known methods, for example, a dehydrating agent (for example,
Phosphorus pentoxide, concentrated sulfuric acid, acetic anhydride, etc.) at room temperature to 150
Condensation reaction is carried out at ℃, and then these reaction solutions are subjected to formula (3) or formula (4) (eg NaSbF ₆ , NaPF ₆ , NaAs).
_{F 6, NaBF 4, NaSbF 5} OH, KSbF 6, KPF 6, KAsF 6, KSbF 5 O
Sulfonium salt can be obtained by dropwise addition to an aqueous solution of H 2).

The method 2) will be described in detail. A sulfonium salt synthesized by the method 1), for example, the formula (7)

[0046]

Embedded image

(In the formula, Ar is a monovalent to tetravalent aromatic group, A is a halogen atom, a is 1 to 4, b is 0 or 1
3, a + b is 1 to 4, n is 1 to 4, and Z is represented by the above formula (3) or formula (4). In a known method, for example, in the presence of a basic compound (for example, sodium hydroxide, potassium hydroxide, potassium carbonate, etc.), a halide compound such as a compound represented by Ethanol, carbitol, ethylene glycol, polyethylene glycol, propylene glycol, glycerin, trimethylolpropane, 1,4
-Butanediol, glycidol, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, allyl alcohol, etc.) at room temperature to 15
By reacting at 0 ° C. in the presence of an organic solvent such as dimethyl sulfoxide, if necessary, the halide part of the halide compound can be converted into

[0048]

[Chemical 33]

[0049]

Embedded image

[0050]

Embedded image

[0051]

Embedded image

A sulfonium salt converted to a substituent such as can be obtained. It can be obtained by reacting the sulfonium salt thus obtained with an oxidizing agent (for example, hydrogen peroxide, sodium peroxide, etc.) at 0 to 30 ° C. If necessary, organic solvents (eg, dichloromethane, acetone, butyrolactone, acetic acid, etc.) can be used.

Typical examples of the compound represented by the general formula (1) include the compounds shown in Tables 1 to 3, but the compounds are not limited to these.

[0054]

[Table 1]

[0055]

[Table 2]

[0056]

[Table 3] 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). The sulfonium salt or sulfoxonium salt (B) is used as an essential component, but an appropriate ratio is the nature of the cationically polymerizable substance, the type of energy ray, the irradiation dose, the desired curing time,
It is determined by considering various factors such as temperature, humidity and coating thickness. In order to facilitate the dissolution of the sulfonium salt or sulfoxonium salt in the cationically polymerizable substance, the sulfonium salt or sulfoxonium salt is previously dissolved in a solvent (eg, propylene carbonate, carbitol, carbitol acetate, butyrolactone).
It can be dissolved in and used. The curable composition of the present invention can be prepared by a method such as mixing, dissolving or kneading a cationically polymerizable substance and a sulfonium salt or a sulfoxonium salt.

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 several minutes by irradiating with energy rays such as ultraviolet rays. The appropriate energy ray may be any one as long as it has an energy that induces the dissociation of the sulfonium salt or the sulfoxonium salt, but is preferably high.
2000 angstrom to 7000 obtained from low-pressure mercury lamp, xenon lamp, germicidal lamp, laser light, etc.
Electromagnetic wave energy having a wavelength of angstrom and high energy rays such as electron beam, X-ray, and radiation are used. Exposure to energy rays depends on the intensity of the energy rays,
Generally, 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.
It is also preferable in some cases to use heating in combination to accelerate the cationic polymerization reaction.

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 ( (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, etc. It can be blended. When a (meth) acrylic acid ester compound is used, it is preferable to use a photoradical polymerization initiator (eg, 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 polymer or other flexible prepolymer may be mixed for the purpose of imparting rubber elasticity.

The composition of the present invention is usually used as a transparent liquid, but depending on the application, it is an inert pigment, dye, filler, antistatic agent, flame retardant, defoaming agent, flow control agent. Used as a mixture of agents, sensitizers, accelerators, light stabilizers and the like. The composition of the present invention can be used for metal, wood, rubber, plastic, glass, ceramic products and the like. Further, specific applications of the present invention include paints, coating agents, inks, resists, liquid resists, adhesives, molding materials, casting materials, putties, glass fiber impregnating agents, and sealing agents.

[0060]

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

(Synthesis Example of Sulfonium Salt Represented by Formula (1)) Example 1 Diphenyl sulfide compound represented by the following formula

[0062]

Embedded image

29 parts, 2,4'-difluorodiphenyl sulfoxide (23.9 parts), acetic anhydride (100 parts) and methanesulfonic acid (398 parts) were charged, heated to 80 ° C. and reacted for about 8 hours with stirring. The reaction mixture was mixed with 280 parts of an aqueous solution of NaPF ₆ (263.2 parts of water with 1 part of NaPF ₆
Dissolved 6.8 parts. ), And the precipitated white solid is filtered, washed with water and dried. A portion of the product, 13.1 parts, was dissolved in 30 parts butyrolactone. Then, 4 parts of 30% hydrogen peroxide was added and the reaction was carried out at 25 ° C. for about 18 hours. The mixture was then poured into 200 parts distilled water. The crude product obtained was washed with water and ethyl ether. 13 parts of white solid were obtained. The melting point of the product was 151 to 162 ° C, and the elemental analysis values were as follows. Element Measured value (wt%) Calculated value (wt%) Carbon 54.02 54.05 Hydrogen 3.01 3.07 Sulfur 9.27 9.32 Phosphorus 4.51 4.50 Fluorine 22.03 22.08 This production Structural formula based on the method

[0064]

[Chemical 38]

A sulfonium salt of was obtained.

Example 2.4- (p-chlorobenzoyl)
-Diphenyl sulfide 32.5 parts, 4,4'-dibromodiphenyl sulfoxide 36 parts, acetic anhydride 100
And 398 parts of methanesulfonic acid were charged, the reaction was carried out at 80 ° C. for about 8 hours, and then the mixture was dissolved in 431.1 parts of an aqueous solution of NaSbF ₆ (26.8 parts of NaSbF ₆ dissolved in 405.3 parts of water). .) Little by little, and the precipitated white solid was filtered, washed with water and dried. Part of the product 18.0
Parts were dissolved in 30 parts butyrolactone. Then, the mixture was cooled to 0 ° C., 2 parts of 30% hydrogen peroxide was added, and the reaction was carried out at 0 ° C. for 24 hours. Then, 200 parts of water was poured. The crude product obtained was washed with water and ethyl ether. 18 parts of white solid were obtained. The melting point of the product is 115-124 ° C.
The elemental analysis values are as follows. Element Measured value (% by weight) Calculated value (% by weight) Carbon 40.49 40.46 Hydrogen 2.15 2.19 Sulfur 7.01 6.97 Antimony 3.83 3.85 Fluorine 12.39 12.40 Bromine 17 .36 17.38 Chlorine 3.81 3.85 Based on this production method,

[0067]

[Chemical Formula 39]

A sulfonium salt of was obtained.

Example 3. 50.3 parts of diphenyl sulfide compound represented by the following formula

[0070]

[Chemical 40]

4,4'-Difluorodiphenyl sulfoxide (47.6 parts), acetic anhydride (200 parts) and methanesulfonic acid (796 parts) were charged and reacted at 80 ° C. for about 8 hours, and then the mixture was mixed with an aqueous solution of NaSbF ₆ (862.3 parts). Water 810.6
51.7 parts of NaSbF ₆ dissolved in 1 part. ) Was gradually added dropwise, and the precipitated white solid was filtered, washed with water and dried. Part 28.3 of the product was dissolved in 65 parts butyrolactone. Then, the mixture was cooled to 0 ° C., 4 parts of 30% hydrogen peroxide was added, and the reaction was carried out at 0 ° C. for 24 hours. Then water 20
It was injected at 0 part. The crude product obtained was washed with water and ethyl ether. 28.5 parts of white solid were obtained. The melting point of the product is 157 to 165 ° C, and the elemental analysis values are as follows. Element Measured value (wt%) Calculated value (wt%) Carbon 46.37 46.41 Hydrogen 2.52 2.50 Sulfur 8.82 8.86 Antimony 16.78 16.82 Fluorine 20.90 20.99 Production Structural formula based on the method

[0072]

Embedded image

A sulfonium salt of was obtained.

Example 4. 55.3 parts of diphenyl sulfide compound represented by the following formula

[0075]

Embedded image

4,4'-Dimethyldiphenyl sulfoxide (46.1 parts), acetic anhydride (200 parts), and methanesulfonic acid (796 parts) were charged and reacted at 80 ° C. for about 8 hours, and then the mixture was mixed with an aqueous solution of NaSbF ₆ (862.3 parts). (Water 810.6
51.7 parts of NaSbF ₆ dissolved in 1 part. ) Was gradually added dropwise, and the precipitated white solid was filtered, washed with water and dried. Part 29 parts of the product was dissolved in 68 parts butyrolactone. Then, it was cooled to 0 ° C., 4 parts of 30% hydrogen peroxide was added, and the reaction was carried out at 0 ° C. for 24 hours. Then water 20
It was injected at 0 part. The crude product obtained was washed with water and ethyl ether. 29 parts of a white solid was obtained. The melting point of the product is 190 to 202 ° C., and the elemental analysis values are as follows. Element Measured value (wt%) Calculated value (wt%) Carbon 51.76 51.81 Hydrogen 3.39 3.40 Sulfur 8.66 8.65 Antimony 16.39 16.43 Fluorine 15.34 15.38 This production Structural formula based on the method

[0077]

[Chemical 43]

A sulfonium salt of was obtained.

Example of Sulfoxonium Salt Represented by Formula (1) Example 5.4 4-Benzoyl-diphenyl sulfide 29
Part, 4,4'-difluorodiphenyl sulfoxide 2
3.9 parts, phosphoric anhydride 100 parts and methanesulfonic acid 3
98 parts were charged and reacted at 80 ° C. for about 8 hours, and then the reaction mixture was added to 280 parts NaPF ₆ aqueous solution (to 263.2 parts water).
Obtained by dissolving a NaPF ₆ 16.8 parts. ), And the white solid that has precipitated is filtered, washed with water and dried. A portion of the product (70 parts), sodium hydroxide (4 parts) and ethanol (200 parts) are charged and reacted at room temperature for 24 hours, then poured into water and the precipitated white solid is filtered, washed with water and dried. Part of the product was dissolved in 7.1 parts and 400 parts of dichloromethane. Then, 47.6 parts of p-toluenesulfonyl chloride was charged and cooled to 0 ° C., and an aqueous solution in which 48.4 parts of sodium peroxide was dissolved in 600 parts of water was added dropwise to this mixture in about 30 minutes while maintaining 0 ° C. Further, the reaction was carried out at the same temperature for about 2 hours. Then, let it stand,
Allow the two layers to separate. The lower organic layers are combined, dried and concentrated under reduced pressure. The obtained residue was washed with water and ethyl ether to obtain 7.0 parts of a white solid. The melting point of the product is 135 to 143 ° C., and the elemental analysis values are as follows. Element Measured value (wt%) Calculated value (wt%) Carbon 55.48 55.53 Hydrogen 4.10 4.13 Sulfur 8.46 8.48 Phosphorus 4.10 4.09 Fluorine 15.03 15.07 Production Structural formula based on the method

[0080]

[Chemical 44]

A sulfoxonium salt of was obtained.

Example 6. It was dissolved in 11.6 parts of the sulfonium salt obtained in Example 3 and 400 parts of dichloromethane. Then, 47.6 parts of p-toluenesulfonyl chloride was charged, the mixture was cooled to 0 ° C., and the mixture was mixed with sodium peroxide 4
An aqueous solution prepared by dissolving 8.4 parts in 600 parts of water is added dropwise in about 30 minutes while maintaining 0 ° C. Further, the reaction was carried out at the same temperature for about 2 hours. Then, it is left still and left to separate the two layers. The lower organic layers are combined, dried and concentrated under reduced pressure. The resulting residue is washed with water and ethyl ether,
12.0 parts of white solid were obtained. The melting point of the product is 195-
The elemental analysis values at 204 ° C. were as follows. Element Measured value (wt%) Calculated value (wt%) Carbon 44.47 44.44 Hydrogen 2.37 2.40 Sulfur 8.41 8.48 Antimony 15.95 16.10 Fluorine 20.13 20.10 This production Structural formula based on the method

[0083]

Embedded image

A sulfoxonium salt of was obtained.

(Examples of Compositions) Examples 7 to 12 and Comparative Examples 1 and 2 The energy ray-curable compositions were compounded according to the compounding compositions (numerical values are parts by weight) shown in Table 4 and mixed and dissolved. . This was applied on an aluminum test panel to a thickness of 5 μm, and was irradiated with ultraviolet rays from a high pressure mercury lamp (80 w / cm) at a distance of 8 cm to cure it. The prepared composition was tested for transparency, storage stability, dryness to the touch, gloss of cured coating, and odor. The results are shown in Table 4.

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 / cm ² ) It was measured. Gloss: The surface of the cured coating film was visually evaluated after irradiation with the irradiation amount (mJ / cm ² ) until the film was dried to the touch. ○ ・ ・ ・ ・ Gloss is good △ ・ ・ ・ ・ Slightly cloudy × ・ ・ ・ ・ No gloss

Odor: After the coated surface was irradiated with 1000 mJ / cm ² , the odor on the surface of the cured coating film was observed. ○ ・ ・ ・ ・ No odor △ ・ ・ ・ ・ Slight odor × ・ ・ ・ ・ Smelling XX ・ ・ ・ ・ Strong odor

[0088]

[Table 4] Table 4 Examples Comparative Examples 7 8 9 10 11 12 1 2 Photopolymerization initiator obtained in Example 1 1.5 Photopolymerization initiator obtained in Example 2 1.5 Photopolymerization initiation obtained in Example 3 Agent 1.5 Photopolymerization initiator obtained in Example 4 1.5 Photopolymerization initiator obtained in Example 5 1.5 Photopolymerization initiator obtained in Example 6 1.5 Compound 1 * 1 1.5 Compound 2 * 2 1.5 Celoxide 2021 * 3 80 80 80 80 80 80 80 80 EHPE-3150 * 4 20 20 20 20 20 20 20 20 Transparency ○ ○ ○ ○ ○ ○ ○ ○ Storage stability ○ ○ ○ ○ ○ ○ ○ ○ Touch dryness (mJ / cm ² ) 75 45 23 23 75 23 75 35 Gloss ○ ○ ○ ○ ○ ○ ○ ○ Odor ○ ○ ○ ○ ○ ○ △ ×

Note * 1 Compound 1: Diphenyl-4
-Thiophenoxyphenylsulfonium hexafluorophosphate * 2 Compound 2: 4,4'-bis [bisphenylsulfonio] phenyl sulfide bishexafluorophosphate * 3 Celoxide 2021: Daicel Chemical Industries, Ltd., alicyclic epoxy resin * 4 EHPE-3150: Daicel Chemical Industries, Ltd.
Made, alicyclic epoxy resin

As is clear from the results shown in Table 4, the composition containing the photopolymerization initiator of the present invention has excellent compatibility and storage stability, is transparent and has excellent curability, and has a gloss of a cured coating film. Good and little odor of cured coating.

[0091]

The energy ray-curable composition containing the photopolymerization initiator of the present invention is excellent in compatibility and storage stability, is transparent and has excellent curability, and has a good gloss of a cured coating film and is cured. The odor of the coating film is also small, giving a cured product with excellent physical properties.

Claims (4)

[Claims] 1. A formula (1): (In the formula, X is a group represented by the formula (2) (R _{1 to} R ₁₀ are each a hydrogen atom, a halogen atom, a nitro group, an alkoxy group, a C _{1 to} C ₁₈ aliphatic group, a phenyl group, a phenoxy group, a thiophenoxy group, and And Is a group selected from m and l are 1 to 5
And G is a sulfur atom or Is. ) Ar is a monovalent to tetravalent aromatic group, and Y is Or [Chemical 7] And a is 1 to 4, b is 0 or 1 to 3, and a + b is 1
˜4, n is 1 to 4, Z is the formula (3) or the formula (4) [Chemical 9] (In the formula, M is a phosphorus atom, a boron atom, an arsenic atom or an antimony atom, Q is a halogen atom, and p is an integer of 4 to 6.). ) The sulfonium salt or sulfoxonium salt represented by the formula (1). 2. A polymerization initiator comprising a sulfonium salt or sulfoxonium salt represented by the formula (1). 3. An energy ray curable composition comprising a cationically polymerizable substance (A) and the photopolymerization initiator (B) according to claim 1. 4. A cured product of the composition according to claim 2.