JPH0725922A - Energy ray-curing composition and its cured material - Google Patents

Abstract

PURPOSE:To obtain an energy ray-curing composition useful for printing ink, etc., having excellent compatibility, transparency, curing properties and a slight smell, providing a cured coating film having excellent luster, comprising an effective amount of a photopolymerization initiator composed of a specific onium salt and a cationically polymerizable substance. CONSTITUTION:(A) A photopolymerization initiator composed of an onium salt of formula I [X is group of formula II (R1 to R10 are H, halogen, nitro, alkoxy, phenyl, phenoxy, phenylcarbonyl, thiophenoxy which may be replaced with 1-25C aliphatic group or 6-18C substituent group, etc. ; R is group except aromatic group; (a) is >=1 numerical value; (b) is 0 or >=1 numerical value; al-b is >=1 numerical value; (n) is >=1 numerical value; Z is group of the formula MQm (M is B, P, As or Sb; Q is halogen; (m) is 4-6) or the formula MQm-1OH] is mixed with (B) a cationically polymerizable substance (e.g. triethylene glycol divinyl ether) to give the objective composition for printing ink, coating compound, etc., having excellent compatibility, transparency, curing properties and a slight smell, providing a cured coating film having excellent luster.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an energy ray-curable composition containing a photopolymerization initiator which is a new onium salt having a specific structure and curable by irradiation with energy rays, 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 and save space and have been examined for practical use. However, most of these studies were based on the radical polymerization reaction of double bonds. Cationic polymerizable substances, such as epoxy resin,
Although it is a material excellent in physical properties, it is difficult to photopolymerize it, and so far, a material in which a double bond is introduced by acrylic modification has been mainly used.

[0003]

In curing an epoxy resin by light, for example, US Pat. No. 3,794,576 is used.
In JP-A-2003-242, there is proposed a method in which a photosensitive aromatic diazonium salt is used as a photopolymerization initiator and the photopolymerization initiator is decomposed by light irradiation to release a Lewis acid, thereby polymerizing an epoxy resin. 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. Furthermore, the mixture with the epoxy resin has a problem in storage stability such as progressive 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 studies have been made, and as a technique for improving thick coating property and storage stability, aromatic sulfonium salt-based initiators and aromatic iodonium salt-based initiators and Curable resin compositions containing them are disclosed in JP-B-52-14278, 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.

[0005]

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 (particularly compatibility with various vinyl ethers and photopolymerization initiators) and curability, and the cured product thereof has little odor. That is, the present invention provides a photopolymerization initiator (A) which is an onium salt represented by the formula (1).

[0006]

[Chemical 6]

{Wherein X is a sulfonio group represented by the formula (2)

[0008]

[Chemical 7]

(R _{1 to} R ₁₀ are each a hydrogen atom, a halogen atom, a nitro group, an alkoxy group, a C _{1 to} C ₂₅ aliphatic group, or a phenyl group which may be substituted with a C _{6 to} C ₁₈ substituent. , Phenoxy group, phenylcarbonyl group, or thiophenoxy group, C ₁ having at least one hydroxyl group
~ C ₂₅ aliphatic group,

[0010]

[Chemical 8]

A group selected from any of C ₃ -C ₂₅ aliphatic groups including a group represented by R ₁₁ is a hydrogen atom or a methyl group. ) R is a group other than an aromatic group, a is 1 or more, b is 0 or 1 or more, a + b is 1 or more, n is 1 or more, Z is formula (3) or formula (4) ) Indicated by

[0012]

[Chemical 9]

[0013]

[Chemical 10]

M is a boron atom, phosphorus atom, arsenic atom or antimony atom, Q is a halogen atom, and m is 4-6. } And a cationically polymerizable substance (B) are contained in the energy ray-curable composition and a cured product thereof.

The photopolymerization initiator (A), which is an onium salt used in the present invention, is a sulfide compound represented by the formula (5) as a starting material (1).

[0016]

[Chemical 11]

(Wherein C is a numerical value of 1 or more, R is the same as in the above formula (1)) and a substituted or unsubstituted diphenyl sulfoxide compound are used to produce a known sulfonium salt. Method (hereinafter, referred to as (1) method), (2) a method of previously synthesizing a corresponding substituted or unsubstituted sulfonium salt, and then converting or introducing a substituent (hereinafter referred to as (2) method) It can be synthesized by

First, the method (1) will be described in detail. Specific examples of the sulfide compound represented by the formula (5) include acetic acid, methoxyacetic acid, 2-methoxybenzeneacetic acid,
3,4-dimethoxybenzeneacetic acid, propionic acid, 2-
Chloropropionic acid, 2-methylpropionic acid, 1-naphthylacetic acid, 1-naphthoxyacetic acid, 2 (N, N-dimethylamino) acetic acid, stearic acid, aliphatic monocarboxylic acids such as lauric acid, malonic acid, itaconic acid , Adipic acid, trimethyladipic acid, fumaric acid, methylfumaric acid, thiodiglycolic acid, azelaic acid, cyclohexanedicarboxylic acid, butanetetracarboxylic acid, aliphatic polycarboxylic acids such as tris (2-carboxyethyl) isocyanurate, Acrylic acid, methacrylic acid, cinnamic acid, α-cyanocinnamic acid, (meth) acrylic acid dimer,
Unsaturated group-containing carboxylic acids such as crotonic acid, β-furfuryl acrylic acid, and polybutadiene dicarboxylic acid, polyester polycarboxylic acids (eg, ethylene glycol, propylene glycol, polyethylene glycol, neopentyl glycol, 1,6-hexanediol, 3 -Methyl-1,5-pentanediol, trimethylolpropane, ethylene oxide adduct of trimethylolpropane, polyhydric alcohol such as polyethoxydiol of bisphenol A and succinic acid, maleic acid, fumaric acid, adipic acid, azelaic acid, Cyclohexanedicarboxylic acid, a reaction product of a polyvalent aliphatic polycarboxylic acid such as cyclohexenedicarboxylic acid or an anhydride thereof), a polymerization type polycarboxylic acid (for example, a homopolymer of acrylic acid or methacrylic acid, or Carboxylic acids formed by bonding to groups other than aromatic groups such as ethylene, α-methylstyrene, ethyl (meth) acrylate, butyl (meth) acrylate, etc., and copolymers with unsaturated group-containing compounds, and diphenyl It can be obtained by reacting 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. Regarding the use ratio of the carboxylic acid and the diphenyl sulfide, it is preferable to react about 1 mol of diphenyl sulfide with respect to 1 equivalent of the carboxylic acid in the carboxylic acid. } And a substituted or unsubstituted diphenyl sulfoxide compound (for example, 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'-dimethyldiphenyl sulfoxide, 4,4'-diethyldiphenyl sulfoxide, 4,4'-dimethoxydiphenyl sulfoxide, 4-methylthiodiphenyl sulfoxide, 4-phenylthiodiphenyl sulfoxide, 4-phenylcarbonyldiphenyl sulfoxide, 4-benzyloxydiphenyl sulfoxide, etc.) are known methods. , In a dehydrating agent (eg, phosphorus pentoxide, concentrated sulfuric acid, acetic anhydride, etc.),
The condensation reaction is carried out at room temperature to 150 ° C., and then these reaction solutions are subjected to formula (3) or formula (4) (for example, NaSbF ₆ , NaPF ₆ , Na
AsF ₆ , NaBF ₄ , NaSbF ₅ OH, KSbF ₆ , KPF ₆ , KAsF ₆ , KSbF
₍₅ OH, etc.) to obtain an onium salt which is a sulfonium salt.

The preferred method of the method (1) for producing the photopolymerization initiator used in the present invention is the above-mentioned substitution or substitution based on 1 equivalent of the terminal sulfide group in the diphenyl sulfide compound represented by the formula (5). The substituted diphenyl sulfoxide compound is preferably reacted in the range of 0.1 to 1.2 mol, particularly preferably 1.0 to 1.1 mol.

The method (2) will be described in detail below.
A sulfonium salt synthesized by the method (1), for example, the formula (6)

[0021]

[Chemical 12]

(Wherein R, a, b, n and Z are the same as those in the above formula (1), and A is a fluorine atom or a bromine atom) and other halide compounds known in the art. Method, for example, in the presence of a basic compound (eg, sodium hydroxide, potassium hydroxide, etc.), a large excess of mono- or polyalcohols (eg, methanol, ethanol, carbitol, ethylene glycol, polyethylene glycol, propylene glycol, glycerin) , Trimethylolpropane, 1,4-butanediol, cyclohexanediol, monohydroxyethylthiol, etc.) at room temperature to 150 ° C.

[0023]

[Chemical 13]

[0024]

[Chemical 14]

[0025]

[Chemical 15]

[0026]

[Chemical 16]

[0027]

[Chemical 17]

It is possible to obtain an onium salt converted into a substituent such as. In addition, a compound obtained by the method (2), in which the substituent is converted into a substituent having a hydroxyl group, further has a lactone group (for example, ε-caprolactone) in the hydroxyl group.
Alternatively, onium salts obtained by reacting an acid (for example, acetic acid, acetic anhydride, etc.) by a known method are also included in the present invention.

Examples of the cationically polymerizable substance (B) used in the present invention include cationically polymerizable vinyl ether compounds such as epoxy resin, styrene and vinyl ether, as well as spiroorthoester, bicycloorthoester and spiroorthocarbonate. Cyclic ethers. Examples of the epoxy resin 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. Also, as an alicyclic epoxy resin,
Specific examples 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 Examples include polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides (ethylene oxide, propylene oxide) to alcohol. It is. 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

[0033]

[Chemical 18]

[0034]

[Chemical 19]

And urethane polyvinyl ether (for example, VECtomer201 manufactured by ALLIED-SIGNAL)
0) and the like. Further, these cationically polymerizable organic materials are used alone or as a mixture of two or more kinds. 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 (B). The photopolymerization initiator (A) of the onium salt as an essential component is used as an essential component, but an appropriate ratio is the nature of the cationically polymerizable substance, the type of energy rays, the irradiation dose, the desired curing time, the temperature, the humidity, the coating film thickness, etc. It is determined by considering various factors.
In order to facilitate the dissolution of the photopolymerization initiator in the cationically polymerizable substance, it is necessary to dissolve the photopolymerization initiator in a solvent (for example, propylene carbonate, carbitol, carbitol acetate, γ-butyrolactone) before use. You can also The curable composition of the present invention can be prepared by a method such as mixing, dissolving or kneading the cationically polymerizable substance (B) and the photopolymerization initiator (A).

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 an energy ray 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. Electromagnetic wave energy having a wavelength of angstrom and high energy rays such as electron beam, X-ray, and radiation are used. 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 the irradiation with energy rays, most of the compositions are dried by touch by cationic polymerization, but it is also preferable to use heating in combination in order 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 epoxy resins and (meth) acrylic acid reaction products such as epoxy (meth) acrylate, urethane (meth) acrylate, polyester poly (meth) acrylate and other oligomers, 2-hydroxy (Meta)
Acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate and other monomers are blended. be able to. 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 use, it may be an inert pigment, dye, filler, antistatic agent, flame retardant, defoaming agent, flow control agent. It is also used by mixing 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 resist inks, adhesives, molding materials, casting materials, putties, glass fiber impregnating agents, and sealing agents.

[0039]

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

(Synthesis Example of Sulfide Compound Represented by Formula (5)) Synthesis Example 1 161.7 parts of methanesulfonic acid and 16.2 parts of phosphorus pentoxide are completely dissolved, and diphenyl sulfide 18.6 is dissolved therein.
And 7.3 parts of adipic acid were charged, the reaction was carried out at 80 ° C. for 10 hours, and it was confirmed by liquid chromatography that the reaction was completed. The reaction mixture was mixed with 1000 parts of potassium hydroxide aqueous solution (800 parts of water). (200 parts of potassium hydroxide dissolved therein) was added dropwise, the precipitate was separated and dried, and then heated to 200 parts of ethanol (60 ° C).
After dissolution and cooling to -5 ° C, the precipitate was separated and dried to give 17 parts of a waxy product. The structural formula of the product is:

[0041]

[Chemical 20]

Synthesis Example 2 161.7 parts of methanesulfonic acid and 16.2 parts of phosphorus pentoxide were completely dissolved, and diphenyl sulfide 18.6 was dissolved therein.
And 16.6 parts of 2-methoxybenzeneacetic acid were charged 8
The reaction was carried out at 0 ° 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 to obtain 23 parts of an oily product.
The structural formula of the product is:

[0043]

[Chemical 21]

Synthesis Example 3 161.7 parts of methanesulfonic acid and 16.2 parts of phosphorus pentoxide were completely dissolved, and diphenyl sulfide 18.6 was dissolved therein.
And 5.8 parts of fumaric acid were charged, the reaction was carried out at 80 ° C. for 10 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 to give a white mixture. 15 parts of solid were obtained. The structural formula of the product is:

[0045]

[Chemical formula 22]

Synthesis Example 4 161.7 parts of methanesulfonic acid and 16.2 parts of phosphorus pentoxide were completely dissolved, and diphenyl sulfide 18.6 was dissolved therein.
Parts and 1 mol of trimethylolpropane and succinic anhydride 3
14.67 parts of the reactant was charged and reacted at 80 ° C. for 15 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 to produce an oil. 20.5 parts were obtained. The structural formula of the product is:

[0047]

[Chemical formula 23]

(Synthesis Example of Photopolymerization Initiator as Onium Salt Represented by Formula (1)) Synthesis Example 5 24.1 parts of the product obtained in Synthesis Example 1, 20.2 parts of diphenyl sulfoxide, 100 parts of acetic anhydride. , 10 parts of sulfuric acid were charged, the reaction was carried out at 50 ° C. for 3 hours with stirring, and then the reaction mixture was stirred at 5 ° C. with an aqueous solution of NaSbF ₆ 4
31.1 parts (25.8 parts of NaSbF ₆ dissolved in 405.3 parts of water) were added dropwise little by little, the white solid deposited was filtered off, dried and then heated to 650 parts of isopropanol ( 70 ° C.), dissolved, cooled to 0 ° C., filtered and separated to obtain 45 parts of a white solid after drying. The structural formula of the product is:

[0049]

[Chemical formula 24]

Synthesis Example 6 33.4 parts of the product obtained in Synthesis Example 2, 23.8 parts of 4,4'-difluorodiphenyl sulfoxide and 180 parts of concentrated sulfuric acid were charged, and the reaction was carried out at room temperature for 24 hours, and then this reaction was carried out. While stirring the mixture, it was slowly added dropwise to 432 parts of an aqueous solution of NaSbF ₆ at 5 ° C. (25.9 parts of NaSbF ₆ dissolved in 406.1 parts of water), and an oily substance was separated, dried and oiled. 62 parts of product are obtained. The structural formula of the product is:

[0051]

[Chemical 25]

Synthetic Example 7 22.6 parts of the product obtained in Synthetic Example 3, 36 parts of 4,4'-dibromodiphenyl sulfoxide and 240.6 parts of concentrated sulfuric acid were charged, and the reaction was carried out at room temperature for 24 hours, and then the reaction was carried out. While stirring the reaction mixture, an aqueous solution of NaSbF ₆ 431.1 at 5 ° C was added.
Part (25.8 parts of NaSbF ₆ dissolved in 405.3 parts of water) was added dropwise little by little, a white solid was filtered off, dried and then heated to 650 parts of isopropanol (70 ° C.).
Dissolve, cool to 0 ° C., filter and dry, then white solid 6
I got 7 parts. The structural formula of the product is:

[0053]

[Chemical formula 26]

Synthesis Example 8 66.5 parts of the product obtained in Synthesis Example 4, 46.1 parts of 4,4'-dimethyldiphenylsulfoxide, concentrated sulfuric acid 233.4.
The reaction mixture was stirred at room temperature for 24 hours, and the reaction mixture was stirred at 0 ° with an aqueous solution of NaPF ₆ 560.
Part (33.6 parts of NaPF ₆ dissolved in 526.4 parts of water) was added dropwise little by little, the precipitate was separated, dried and then dissolved in 650 parts of isopropanol by heating (70 ° C.), − After cooling to 5 ° C., filtering and drying, 95 parts of a waxy product was obtained. The structural formula of the product is:

[0055]

[Chemical 27]

Synthesis Example 9 39.5 parts of the product obtained in Synthesis Example 6, sodium hydroxide 4
And 100 parts of 1,4-butanediol were charged and reacted at room temperature for 24 hours, and then poured into water to separate an oily substance and dried to obtain 33 parts of a pale yellow liquid product. The structural formula of the product is:

[0057]

[Chemical 28]

Synthesis Example 10 39.5 parts of the product obtained in Synthesis Example 6 and sodium hydroxide 4
And ethylene glycol 200 parts were charged, and at room temperature 24
React for hours, then pour into water to separate oil,
Drying gave an oily product. Then the above product 8
7.4 parts, ε-caprolactone 45.6 parts, and stannous chloride 0.04 parts were charged and reacted at 120 ° C. for 15 hours.
-It was confirmed that caprolactone was 1% or less in the reaction mixture, and the reaction was terminated to obtain 133 parts of a liquid product.
The structural formula of the product is:

[0059]

[Chemical 29]

(Examples of Compositions) Examples 1 to 12 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 coated on an aluminum test panel in a thickness of 5 μm and cured by irradiation with ultraviolet rays from a distance of 8 cm with a high pressure mercury lamp (80 W / cm). 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 judged. ○ ・ ・ ・ ・ Completely transparent △ ・ ・ ・ ・ Slightly turbid × ・ ・ ・ ・ White dull XX ・ ・ ・ ・ Separation immediately (storage stability): 40 ° C. It was stored at 3 months for 3 months and stability was investigated. ○ ・ ・ ・ ・ No change △ ・ ・ ・ ・ Slightly thickened × ・ ・ ・ ・ Gelified (touch-drying property): Irradiation dose until touch-drying (mJ / cm ² )
Was measured. (Mitsuzawa): 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

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

[0063]

[Table 1] Table 1-1 Example 1 2 3 4 5 6 Photopolymerization initiator obtained in Synthesis Example 5 1.5 Photopolymerization initiator obtained in Synthesis Example 6 1.5 Photopolymerization initiator obtained in Synthesis Example 7 1.5 Photopolymerization Initiator 1.5 Obtained in Synthesis Example 8 Photopolymerization Initiator Obtained in Synthesis Example 9 1.5 Photopolymerization Initiator Obtained in Synthesis Example 10 Compound 1 * 1 Compound 2 * 2 Compound 3 * 3 Celoxide 2021 * 480 80 80 80 80 80 EHPE-3150 * 5 20 20 20 20 20 20 Transparency ○ ○ ○ ○ ○ ○ Storage stability ○ ○ ○ ○ ○ ○ Touch dryness (mJ / cm ² ) 23 23 23 69 23 30 Hikari Sawa ○ ○ ○ ○ ○ ○ Odor ○ ○ ○ ○ ○ ○

Note * 1 Compound 1: triphenylsulfonium hexafluorophosphate * 2 Compound 2: diphenyl-4-thiophenoxyphenylsulfonium hexafluorophosphate * 3 Compound 3: 4,4'-bis [bis (P-2-hydroxy) Ethoxyphenyl) sulfonio] phenyl sulfide bishexafluorophosphate * 4 Celoxide 2021: Daicel Chemical Industry Co., Ltd., alicyclic epoxy resin * 5 EHPE-3150: Daicel Chemical Industry Co., Ltd.
Made, alicyclic epoxy resin

[0065]

[Table 2] Table 2-1 Examples 7 8 9 10 11 12 Photopolymerization initiator obtained in Synthesis Example 5 1.0 Photopolymerization initiator obtained in Synthesis Example 6 1.0 Photopolymerization initiator obtained in Synthesis Example 7 1.0 Photopolymerization Initiator 1.0 Obtained in Synthesis Example 8 Photopolymerization Initiator 1.0 Obtained in Synthesis Example 9 Photopolymerization Initiator 1.0 Obtained in Synthesis Example 10 Compound 1 Compound 3 VEctomer2010 * 6 25 25 25 VEctomer 4020 * 7 60 60 25 25 25 60 Triethylene glycol divinyl ether 10 10 10 Transparency ○ ○ ○ ○ ○ ○ Storage stability ○ ○ ○ ○ ○ ○ Touch dryness (mJ / cm ² ) 12 12 12 25 12 12 Hikarizawa ○ ○ ○ ○ ○ ○ Odor ○ ○ ○ ○ ○ ○

Note * 6: VEctomer2010: ALLIED
-SIGNAL aromatic urethane vinyl ether * 7: VEctomer4020: ALLIED-SIGNAL aliphatic ester vinyl ether having the following structural formula

[0067]

[Chemical 30]

* 8: The composition had poor compatibility, separated immediately after mixing, and did not cure even when irradiated with ultraviolet rays of 1000 mJ / cm ² or more.

As is clear from the results of Tables 1 and 2, the photopolymerization initiator of the present invention and the composition containing the same have excellent compatibility, are transparent and have excellent curability, and have a gloss of a cured coating film. Good and little odor of cured coating.

[0070]

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 is also small and gives a cured product with excellent physical properties.

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[Procedure amendment]

[Submission date] May 23, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be amended] Title of invention

[Correction method] Change

[Correction content]

Patent application title: Energy ray curable composition and cured product thereof

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location G03F 7/029

Claims (2)

[Claims] 1. A photopolymerization initiator (A) which is an onium salt represented by the formula (1): {Wherein X is a sulfonio 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 ₂₅ aliphatic group, and a C _{6 to} C group.
_A phenyl group optionally substituted by ₁₈ substituents, a phenoxy group, a phenylcarbonyl group or a thiophenoxy group, a C ₁ -C ₂₅ aliphatic group having at least one hydroxyl group, A group selected from any of C _{3 to} C ₂₅ aliphatic groups including a group represented by and R ₁₁ is a hydrogen atom or a methyl group. ) R is a group other than an aromatic group, a is a number of 1 or more, b is 0 or a number of 1 or more, a + b is a number of 1 or more, and n is 1
The above numerical value, Z, is represented by equation (3) or equation (4): [Chemical 5] M is a boron atom, a phosphorus atom, an arsenic atom or an antimony atom, Q is a halogen atom, and m is 4-6. } And a cationically polymerizable substance (B) are contained, The energy ray-curable composition characterized by the above-mentioned. 2. A cured product of the composition according to claim 1.