JPH09278813A - Photopolymerization initiator, energy radiation-curable composition containing the same and cured product thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an only slightly colored energy radiation-curable compsn. excellent in compatibility, storability, curing properties and gloss by incorporating a photopolymn. initiator comprising a specified sulfonium salt into a cationically-polymerizable substance. SOLUTION: A sulfonium salt of formula I (wherein X is a group represented by formula II; R<6> to R<15> are each H, a halogen, nitro group, an alkoxyl group, a 1-20C aliphatic group, phenyl group, phenoxy group or thiophenoxy group; R<1> to R<3> are each a 1-20C aliphatic group, cyclohexyl group, substituted phenyl group, benzyl group, a substituted benzyl group, or a group represented by formula III; R<16> is H, a 1-5C alkyl group, an alkoxyl group, nitro group or cyano group; R<4> and R<5> are the same as R<16> ; n is 1 to 10; m is 1 to 4: Z is a group represented by formula IV, V or VT; M is P, B, As or Sb; Q is a halogen; P is 4 to 6; a and b are each 0 to 4 and a+b is 4; Y is halogen or OH group; and R is CF3 , NO2 , CN or phenyl group substituted with at least two halogen atoms) is used as the photopolymn. initiator.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a novel sulfonium salt having a specific structure, a photopolymerization initiator comprising the same,
The present invention relates to an energy ray-curable composition containing the composition, which can be cured by irradiation with energy rays, and a cured product thereof.

[0002]

2. Description of the Related Art Photopolymerizable compositions have been actively studied in the fields of printing inks, paints, coatings, liquid resist inks, etc. from the demands of energy saving, space saving, and non-polluting properties, and their practical use has been studied. . However, most of these studies were based on radical polymerization reactions of double bonds. Cationic polymerizable substances, such as epoxy resins, are excellent materials in physical properties, but are difficult to photopolymerize. Until now, materials with double bonds introduced by acrylic modification have been mainly used. .

[0003]

In order to cure an epoxy resin by light, for example, US Pat. No. 3,794,576 discloses a method in which a photosensitive aromatic diazonium salt is used as a photopolymerization initiator and the photopolymerization initiator is irradiated with light. A method of polymerizing an epoxy resin by decomposing and releasing a Lewis acid has been proposed. However, aromatic diazonium salts release 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. Furthermore, the mixture with the epoxy resin has a problem in storage stability such that curing gradually proceeds even when no light is present, and cannot be said to be a one-part composition. In order to overcome the drawbacks of the above diazonium salt-based initiator, various studies have been made, and aromatic sulfonium salt-based or aromatic iodonium salt-based initiators and the like containing them as techniques for improving thick coating properties and storage stability The curable resin composition is disclosed in JP-B-52-14278, JP-B-5-14278.
These are disclosed in, for example, JP-A-2-14277, JP-A-54-53181, and JP-B-59-19581. However, compositions containing these aromatic onium salts have the disadvantage of being less curable 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 such a drawback, an aromatic sulfonium salt having a specific group is proposed in JP-A-56-55420 and the like. But,
The above disadvantages are somewhat eliminated but not sufficient. In addition, as the field of use of the photopolymerizable composition expands, it is important to provide a novel photopolymerization initiator and a composition containing the same in order to meet market requirements.

[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 having excellent compatibility and curability, and the cured product of which has little coloring. That is, the present invention provides:

[0005]

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In the formula, X is a group represented by the formula (2)

[0007]

[Chemical 6]

(In the formula, R _{6 to} R ₁₅ are each a hydrogen atom, a halogen atom, a nitro group, an alkoxy group, and C ₁ to C.
_In the structure of ₂₀ , selected from a hydroxyl group, an ether group, an ester group, a (meth) acryloyl group, an epoxy group or an aliphatic group which may have an allyl group, a phenyl group, a phenoxy group and a thiophenoxy group. It is a group that has been ) R ₁ , R ₂ and R ₃ are each an ether group, an ester group, an aliphatic group which may have a carbamoyl group in the structure of C _{1 to} C ₂₀ , a cyclohexyl group, a halogenated phenyl group and a cyanophenyl group. A group, a nitrophenyl group, an alkylphenyl group, an alkoxyphenyl group, a benzyl group, a halogenated benzyl group, a cyanobenzyl group, a nitrobenzyl group, an alkylbenzyl group, an alkoxybenzyl group and a group represented by the formula (3),

[0009]

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(Wherein R _{16 is} a hydrogen atom, a C ₁ -C ₅ alkyl group, a C ₁ -C ₅ alkoxy group, a nitro group or a cyano group, and X is a group The same as X in (1).), Wherein R ₄ and R ₅ are each a hydrogen atom. (2) A photopolymerization initiator (B) comprising these salts, (3) a cationically polymerizable substance (A), and the photopolymerization initiator (B) according to the item (2), which are 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 spiroorthoester, bicycloorthoester and spiroorthocarbonate.
Examples of the epoxy resin include conventionally known aromatic epoxy resins, alicyclic epoxy resins, aliphatic epoxy resins, epoxide monomers, and episulfide monomers. Here, when the aromatic epoxy resin is exemplified, it is a polyglycidyl ether of a polyhydric phenol having at least one aromatic nucleus or an alkylene oxide adduct thereof, for example, bisphenols such as bisphenol A, bisphenol F and bisphenol S. Glycidyl ethers produced by reacting an alkylene oxide (eg, ethylene oxide, propylene oxide, butylene oxide, etc.) adduct of a compound or 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.).

Further, examples of the aliphatic epoxy resin include polyglycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof, and typical examples thereof are diglycidyl ethers of 1,4-butanediol and 1,6. -Diglycidyl ether of hexanediol, 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 Examples of the polyglycidyl ether of a polyol obtained by adding one or more alkylene oxides (ethylene oxide, propylene oxide) to It is. Further, examples of the epoxide monomers include monoglycidyl ethers of aliphatic higher alcohols, phenol, cresol, butylphenol, and monoglycidyl ethers of polyether alcohols obtained by adding alkylene oxide thereto.

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,

[0014]

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And

[0016]

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And the like. These cationically polymerizable organic materials may be used alone or as a mixture of two or more.

The sulfonium salt represented by the general formula (1) used in the present invention is, for example, a phosphine compound represented by the general formula (6) or a phosphine oxide compound represented by the general formula (7).

[0019]

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(In the formula, R _{1 to} R ₅ are represented by the general formula (1)
It is the same as R _{1 to} R ₅ therein. )

[0021]

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(In the formula, R _{1 to} R ₅ are represented by the general formula (1)
R _{1 to} R ₅ are the same. ) And a substituted or unsubstituted diphenyl sulfoxide compound using a known reaction for forming a sulfonium salt (hereinafter referred to as method 1)), 2)
The corresponding substituted or unsubstituted sulfonium salt can be synthesized in advance, and then 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 specifically described. The phosphine compounds represented by the formulas (7) and (8) (as specific examples,
For example, 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane,
1,4-bis (diphenylphosphino) butane, 1,2
-Bis (n-butylphenylphosphino) ethane 1,3
-Bis (n-butylphenylphosino) propane, 1,
4-bis (n-butylphenylphosphino) butane),
1- (n-butylphenylphosphino) -4- (di-n
-Butylphosphino) butane, 1- (diphenylphosphino) -4- (dibenzylphosphino) butane, 1-
(Metarylphenylphenylphosphino) -4- (dimetarylphenylphosphino) butane, 1- (paratolylphenylphenylphosphino) -3- (paratolylphenylphosphino) propane, 1- (4-methoxyphenylphenyl Phosphino) -2- (4-methoxyphenylphenylphosphino) ethane, 1- (cyclohexylphenylphosphino) -2- (cyclohexylphenylphosphino) ethane, 1- (4-nitrophenylphenylphosphino) -4- (4-Nitrophenylphenylphosphino) butane, 1- (methacyaophenylphenylphosphino) -3- (methacyanophenylphenylphosphino) propane, 1- (4-methylbenzylphenylphosphino) -4- ( 4-methylbenzylphenylphosphino) butane) and Phosphine oxide compounds (specific examples include 1,2-ethanebis (diphenylphosphine oxide), 1,3-propanebis (diphenylphosphine oxide), 1,4-butanebis (diphenylphosphine oxide), 1,2-ethanebis (N-butylphenylphosphine oxide),
1,3-propanebis (n-butylphenylphosphine oxide), 1,4-butanebis (n-butylphenylphosphine oxide), butane-1-n-butylphenylphosphine oxide-4-din-butylphosphine oxide, butane -1-Diphenylphosphine oxide-4-dibenzylphosphine oxide, butane-1-metatrylphenylphenylphosphine oxide-4-dimetatrylphosphine oxide, propane-1-metatrylphenylphenylphosphine oxide-3-dimetatrylphosphine Oxide, 1,3
-Propanebis (paratolylphenylphenylphosphine oxide), 1,2-ethanebis (4-methoxyphenylphenylphosphine oxide), 1,2-ethanebis (cycloxylphenylphosphine oxide), 1,4-butanebis (4-nitrophenyl) Phenylphosphine oxide), 1,3-propanebis (methacyanophenylphenylphosphine oxide),
1,4-butanebis (4-methylbenzylphenylphenylphosphine oxide), 1,4-butanebis (N, N-diisobutylcarbamoylmethylphenylphosphine oxide, etc.) and a substituted or unsubstituted diphenylsulfoxide 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 ', 4,
4'-tetrachlorodiphenyl sulfoxide, 4,4 '
-Dimethyldiphenylsulfoxide, 4,4'-diethyldiphenylsulfoxide, 4,4'-dimethoxydiphenylsulfoxide, 4-methylthiodiphenylsulfoxide, 4-phenylthiodiphenylsulfoxide, etc.)
A known method, for example, a dehydrating agent (for example, phosphorus pentoxide,
(Acetic anhydride, concentrated sulfuric acid, etc.) and methanesulfonic acid, perfluoromethanesulfonic acid, etc. as a solvent are usually used at room temperature to
Condensation reaction is performed at 100 ° C., and then these reaction liquids are alkali metal salts (eg, NaSbF ₆ , NaPF ₆ , NaAsF ₆ , Na) whose formula (4), formula (5) or formula (6) is an anion moiety.
BF ₆ , NaSbF ₅ OH, KSbF ₆ , KPF ₆ , KAsF ₆ , KSbF ₅ OH, Li
B (C ₆ F ₅ ) ₄ , Li B (C ₆ H ₄ CF ₃ ) ₄ , Li BF ₂ (C ₆ F ₅ ) ₂ , Li B (C
_The sulfonium salt can be obtained by dropping it into an aqueous solution of ₆ H ₃ F ₂ ) ₄ etc.). In the step of obtaining the sulfonium salt described above, the phosphorus atom in the phosphine compound represented by the general formula (7) is oxidized to be phosphine oxide. In the step of obtaining a sulfonium salt from the phosphine compound represented by the general formula (7), a large amount of by-products are present, and the phosphine oxide compound represented by the general formula (8) is preferably used as a starting material.

2) The method will be specifically described. A sulfonium salt synthesized by the method 1), for example, the formula (9)

[0024]

[Chemical 12]

(However, in the formula, R _{1 to} R ₅ are R in the formula (1).
_The same as _{1 to} R ₅ , A is a halogen atom, n is 1 to 10, Z
Is represented by the above formula (4), formula (5) or formula (6). ) Known methods for compounds such as, for example, basic compounds (for example, sodium hydroxide, potassium hydroxide, potassium carbonate, etc.), in the presence of a large excess of mono- or polyalcohols (for example, methanol, 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.) is usually reacted at room temperature to 150 ° C. in the presence of an organic solvent such as dimethyl sulfoxide, if necessary, The halide part of the halide compound is, for example,

[0026]

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[0027]

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[0028]

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[0029]

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It is possible to obtain a borate converted into a substituent such as. As typical examples of the compound represented by the general formula (1), the compounds shown in Table 1 below can be mentioned, but the invention is not limited thereto.

[0031]

[Table 1]

The curable composition of the present invention is usually 0.01 to 20 with respect to 100 parts by weight of the cationically polymerizable substance (A).
More preferably, 0.1 to 10 parts by weight of the sulfonium salt (B) represented by the above formula (1) is used as an essential component, but a suitable ratio is a cationically polymerizable substance, the type of energy beam, and irradiation. It is determined by considering various factors such as amount, desired curing time, temperature, humidity, coating thickness. In order to facilitate the dissolution of the sulfonium salt in the cationically polymerizable substance, the sulfonium salt can be used by dissolving it in a solvent (eg, propylene carbonate, carbitol, carbitol acetate, butyrolactone) in advance. 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.

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. Suitable energy rays may be any as long as they have an energy that induces the separation of the sulfonium salt or the sulfoxonium salt, but are preferably high,
2000 angstrom to 7000 obtained from low-pressure mercury lamp, xenon lamp, germicidal lamp, laser beam, etc.
Electromagnetic energy having a wavelength of Å, high energy rays such as electron beams, X-rays, and radiations 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 to the touch by cationic polymerization,
In some cases, it is also preferable to use heating in combination to promote the cationic polymerization reaction. In the composition of the present invention, a solvent for dilution as far as the cationic polymerization is not impaired,
A non-reactive resin for modification or a (meth) acrylic acid ester compound (for example, an epoxy (meth) that is a reaction product of an epoxy resin such as a bisphenol A type epoxy resin or a novolac type epoxy resin and (meth) acrylic acid) Oligomer such as acrylate, urethane (meth) acrylate, polyester poly (meth) acrylate, 2-hydroxy (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate , Monomers such as trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, etc.) can be blended. When a (meth) acrylate compound is used, it is preferable to 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 specialty, 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 use, it may be an inert pigment, dye, filler, antistatic agent, flame retardant, antifoaming 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, coatings, inks, resists, liquid resists, adhesives, molding materials, casting materials, putties, glass fiber impregnating agents, fillers, and the like.

[0035]

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

(Synthesis Example of Sulfonium Salt Represented by Formula (1)) Example 1 9.4 parts of 1,4-butanebis (cyclohexanephenylphosphine oxide), 10 parts of 4,4'-difluorodiphenyl sulfoxide, acetic anhydride 10 parts and concentrated sulfuric acid 5
Charge 0 parts, heat to 60 ° C. and react for about 5 hours,
Then, the reaction solution was diluted with 800 parts of water, the insoluble matter was filtered off, and 11.5 parts of KSbF ₆ was added to the aqueous layer, and then 25% NaO was added.
The pH is neutralized to 7 with an aqueous H 2 solution and the white precipitate is filtered off.
The white precipitate was dissolved in 200 parts of a solvent (mixed solvent of 20 parts of acetone and 80 parts of methanol), 200 parts of water was added thereto, and the precipitate was filtered and dried to obtain 19.3 parts of a white solid. The melting point of the obtained product was 175 to 178 ° C, and the elemental analysis values were as follows. Element Measured value (% by weight) Calculated value (% by weight) Carbon 45.15 45.11 Hydrogen 3.95 3.93 Sulfur 4.62 4.63 Phosphorus 4.49 4.47 Antimony 17.56 17.59 Fluorine 21 .94 21.95 Structural formula based on this manufacturing method

[0037]

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A sulfonium salt of was obtained.

Example 2 Butane-1-n-butylphenylphosphine oxide-4-di-n-butylphosphine oxide 10 parts, 4,
4.0 parts of 4'-difluorodiphenyl sulfoxide and 50 parts of concentrated sulfuric acid were charged, the mixture was heated to 60 ° C. and reacted for 5 hours, then the reaction solution was diluted with 800 parts of water and the insoluble matter was filtered off to form an aqueous layer. Add 4.8 parts KPF ₆ then 25% NaO
The pH is neutralized to 7 with an aqueous H 2 solution and the white precipitate is filtered off.
The white precipitate was dissolved in 200 parts of a solvent (a mixed solvent of 20 parts of acetone and 80 parts of methanol), and 200 parts of water was added to this to obtain 13 parts of a white solid. The melting point of the obtained product is 1
The elemental analysis values at 56 to 159 ° C. were as follows. Element Measured value (wt%) Calculated value (wt%) Carbon 58.02 57.98 Hydrogen 6.85 6.81 Sulfur 4.57 4.55 Phosphorus 13.22 13.19 Fluorine 21.56 21.58 This production Structural formula based on method

[0040]

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A sulfonium salt of was obtained.

Example 3 10 parts of the compound obtained in Example 1, 0.8 sodium hydroxide
Part, 100 parts of ethylene glycol were charged, and 2 at 60 ° C
After reacting for 4 hours, it was poured into water and the precipitated white solid was filtered and dried to obtain a solid product at room temperature. The structural formula of the product is shown below, and the results of elemental analysis were in good agreement with the calculated values.

[0043]

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Example 4 20 parts of the sulfonium salt obtained in Example 2 was added to 200 parts of acetone.
A solution of 19.5 parts of lithium tetrakis (pentafluorophenyl) borate in 200 parts of acetone was added to the solution dissolved in 1 part of the mixture, and the mixture was stirred for 2 hours for 2 hours.
Stir at 5 ° C. and then filter to remove the LiPF ₆ formed. The acetone was evaporated to give 30 parts of a white solid. The melting point of the obtained product was 166 to 170 ° C., and the elemental analysis values were as follows. Element Measured value (wt%) Calculated value (wt%) Carbon 53.64 53.61 Hydrogen 3.72 3.69 Sulfur 2.45 2.47 Phosphorus 4.79 4.77 Boric acid 0.83 0.83 Fluorine 32 .13 32.16 Structural formula based on this manufacturing method

[0045]

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A sulfonium salt of was obtained. (Examples of Compositions) Examples 5 to 8 and Comparative Examples 1 to 4 The energy ray curable compositions were compounded according to the compounding compositions (numerical values are parts by weight) shown in Table 2, and mixed and dissolved.
Apply this to an aluminum test panel to a thickness of 5μ,
Ultraviolet rays were irradiated from a distance of 8 cm with a high-pressure mercury lamp (80 w / cm ² ) to cure. Transparency of the tuned composition,
The storage stability, the dryness to the touch, the gloss of the cured coating, and the coloring were tested. Table 2 shows the results.

Transparency: The transparency of the composition was visually determined. ○ ・ ・ ・ ・ It is completely transparent. △ ・ ・ ・ ・ Slightly cloudy. × ・ ・ ・ ・ White is dull. XX ・ ・ ・ ・ Separate immediately. Storage stability: The composition was stored at 40 ° C. for 3 months, and the stability was investigated. ○ ・ ・ ・ No change at all △ ・ ・ ・ ・ Slightly thickened × ・ ・ ・ ・ Gelled Touch dryness: The irradiation dose (mJ / cm ² ) until touch dryness It was measured. Gloss: The surface of the cured coating film was visually evaluated after irradiation with the irradiation amount (mJ / cm ² ) until it was dried to the touch. ○ ・ ・ ・ ・ Gloss is good △ ・ ・ ・ ・ Slightly cloudy × ・ ・ ・ ・ No gloss at all Coloring: After irradiating the coated surface at 1000 mJ / cm ² , observe the coloring state of the cured coating film did. ○ ・ ・ ・ ・ No coloration △ ・ ・ ・ ・ Slightly colored × ・ ・ ・ ・ Colored ×× ・ ・ ・ ・ Colored strongly

[0048]

Table 2 Examples Comparative Examples 5 6 7 8 1 2 3 4 Photopolymerization Initiator Obtained in Example 1.5 1.5 Photopolymerization Initiator Obtained in Example 2 1.5 Photopolymerization Initiator Obtained in Example 3 1.5 Photopolymerization initiator obtained in Example 4 1.5 Compound 1 * 1 1.5 1.5 Compound 2 * 2 1.5 1.5 Polyester divinyl ether * 3 50 50 50 50 Cyclohexane dimethylol divinyl ether 50 50 50 50 Celoxide 2021 * 4 80 80 80 80 EHPE-3150 * 5 20 20 20 20 Transparency ○ ○ ○ ○ ○ × × ○ × × Storage stability ○ ○ ○ ○ ○ ── ○ ── Dryness to the touch (mJ / cm ² ) 20 15 20 10 75 − 35-Gloss ○ ○ ○ ○ ○ ── ○ ── Coloring ○ ○ ○ ○ × ── × ──

Note) * 1 Compound 1: Diphenyl-4-
Thiophenoxyphenylsulfonium hexafluorophosphate * 2 Compound 2: 4,4'-bis [bisphenylsulfonio] phenyl sulfide bishexafluorophosphate * 3 Polyester divinyl ether: Structural formula

[0050]

[Chemical 21]

* 4 Celoxide 2021: Daicel Chemical Industries, Ltd., alicyclic epoxy resin * 5 EHPE-3150: Daicel Chemical Industries, Ltd.
Production, alicyclic epoxy resin As is clear from the results in Table 2, the composition containing the photopolymerization initiator of the present invention has excellent compatibility and storage stability, is transparent and has excellent curability, and is a cured coating. The gloss of the film is good and the coloring of the cured coating is small.

[0052]

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. Coloring of the coating film is also small, giving a cured product with excellent physical properties.

Claims (4)

[Claims] (1) Formula (1) Ｘwherein X is a group represented by the formula (2) (Wherein, R _{6 to} R ₁₅ each represent a hydrogen atom, a halogen atom, a nitro group, an alkoxy group, or a C _{1 to} C ₂₀ structure;
A group selected from a hydroxyl group, an ether group, an ester group, a (meth) acryloyl group, an epoxy group, or an aliphatic group which may have an allyl group, a phenyl group, a phenoxy group and a thiophenoxy group. . And R ₁ , R ₂ and R ₃ are each an ether group, an ester group, an aliphatic group which may have a carbamoyl group in the structure of C _{1 to} C ₂₀ , a cyclohexyl group and a halogenated phenyl group. , Cyanophenyl group, nitrophenyl group, alkylphenyl group, alkoxyphenyl group, benzyl group,
A halogenated benzyl group, a cyanobenzyl group, a nitrobenzyl group, an alkylbenzyl group, an alkoxybenzyl group and a group represented by the formula (3): (In the formula, R ₁₆ is a hydrogen atom, a C _{1 to} C ₅ alkyl group,
It is a group selected from a C _{1 to} C ₅ alkoxy group, a nitro group and a cyano group, and X is the same as X in the formula (1). ) Is a group selected from
₄ and R ₅ are each a group selected from a hydrogen atom, a C _{1 to} C ₅ alkyl group, a C _{1 to} C ₅ alkoxy group, a nitro group and a cyano group, and n is 1 to 10,
m is 1 to 4, Z is formula (4), formula (5) or formula (6) (In the formula, M is a phosphorus atom, a boron atom, an arsenic atom or an antimony atom, Q is a halogen atom, p is an integer of 4 to 6, B is a boron atom, and a and b are 0 to 0.
Is an integer in the range of 4, where a + b is 4, the symbol Y represents a halogen atom (chlorine or fluorine) when a is 0 to 3, and when a is 0 to 2 Is O
It can also represent an H group. R is CF ₃ , NO ₂ , CN
Represents a phenyl group substituted with at least one electron-withdrawing group or a phenyl group substituted with at least two halogen atoms (especially fluorine). )} The sulfonium salt shown by these. 2. A polymerization initiator (B) comprising a sulfonium 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 2. 4. A cured product of the composition according to claim 3.