KR100301239B1 - An energy ray curing composition containing a novel onium salt, a photopolymerization initiator, a crosslinking agent and a curing agent - Google Patents

Abstract

The composition of the present invention is excellent in miscibility, transparency and curability, has excellent gloss of the cured coating material, has almost no odor, and a cured product having such excellent properties can be prepared by curing the composition.

The present invention relates to an onium salt represented by the following structural formula (1).

In the above formula, Ar is a monovalent to tetravalent aromatic group, X is a bisphenylsulfonio group which may have a substituent, a is a number of 1 to 4, b is 0 or a number of 1 to 3, a + b is 1 to 4, n is a number of 1 to 4, and Z is a halide represented by the following general formula (3).

Wherein M is a boron atom, phosphorus atom, arsenic atom or antimony atom, Q is a halogen atom, m is a number of 3 to 6, Is 0 or 1, m + Is 4 to 6.

The present invention also relates to a photopolymerization initiator containing the onium salt as an active ingredient, an energy ray curable composition containing the initiator, and a cured product thereof.

Description

[Title of the Invention]

A novel onium salt, a photopolymerization initiator, an energy ray curable composition containing the initiator, and a cured product

DETAILED DESCRIPTION OF THE INVENTION [

The present invention relates to a novel onium salt having a specific structure, a photopolymerization initiator containing the onium salt as an active ingredient, an energy ray containing the initiator and cured by irradiating the energy ray, And a cured product thereof.

The photopolymer composition has been thoroughly studied in the fields of ink, paint, coating, liquid resist ink, etc. in order to save energy, to save space, and to prevent environmental pollution. However, the majority of these studies are based on the radical polymerization of double bonds. Cationic polymeric materials such as epoxy resins have excellent properties but are difficult to photopolymerize. Therefore, so far, materials having such double bonds introduced by acrylic denaturation have been mainly used.

As a method of curing an epoxy resin by exposing it to light, US Pat. No. 3,794,576 proposes to use a photosensitive aromatic diazonium salt as a photopolymerization initiator. However, the aromatic diazonium salt is decomposed by light to generate nitrogen gas, and when the coating thickness of the epoxy resin is 15 mu or more, the coating film is bloomed, so that the initiator is not suitable for thick coating . Furthermore, since the mixture with epoxy resin gradually cures even in the presence of light, there is a problem in storage stability and can not be used as a one-pack type composition.

Various attempts have been made to solve the drawbacks of the diazonium salt photopolymerization initiator. As a result, it has been found that an initiator such as an aromatic sulfonium salt or an aromatic iodonium salt and a curable resin composition containing the initiator improve the thick coating thickness and improve the storage stability JP-B-52-14278 and JP-B-52 14277, U.S. Pat. Nos. 4, 161, 478 and U.S. Pat. No. 4,273,688). However, compositions containing these aromatic onium salts have poorer curability than compositions containing diazonium salts. Furthermore, the aromatic sulfonium salts have a problem of odor in the cured product. To address these problems, US Pat. No. 4,374,066 proposes the use of aromatic sulfonium salts with specific groups. However, this problem has not yet been sufficiently solved. Furthermore, as the field of use of the photopolymerizable composition is expanded, the development of a novel photopolymerization initiator and a composition containing the same is important to meet market demand.

As a result of intensive research, the inventors of the present invention have developed a novel photopolymerization initiator which has excellent storage stability and compatibility (in particular, miscibility between the photopolymerization initiator of the present invention and various vinyl ethers) ≪ / RTI > to provide a radiation curable composition that produces a cured product that does not have a cured product.

That is, the present invention relates to an onium salt as described below, a photopolymerization initiator containing the onium salt as an active ingredient, an energy ray curable composition, and a curing method of the composition.

(1) an onium salt represented by the following general structural formula (I):

[Wherein Ar is a monovalent to tetravalent aromatic group, X is a bisphenylsulfonio group which may have a substituent, a is a number of 1 to 4, b is 0 or a number of 1 to 3, a + b is a number from 1 to 4, n is a number from 1 to 4, and Z is a halide represented by the following general formula (3):

Wherein M is a boron atom, phosphorus atom, arsenic atom or antimony atom, Q is a halogen atom, m is a number of 3 to 6, Is 0 or 1, m + Is 4 to 6].

(2) Ononium salts defined in (1) above as:

Ar is the following aromatic groups,

These aromatic groups may be substituted with a group selected from the group consisting of (C ₁ -C ₅ ) alkyl groups, (C ₁ -C ₅ ) alkyloxycarbonyl groups, (C ₁ -C ₅ ) alkylcarbonyloxy groups, benzoyl groups, cyano groups, _{1 to 5} ) alkyldiio group and a halogen atom;

The bisphenylsulfonio group which may have a substituent is a group represented by the following structural formula (2)

Wherein each of R ₁ -R ₁₀ is a hydrogen atom, a halogen atom, a nitro group, an alkoxy group, a C ₁ -C ₂₅ alkyl group, a phenyl group which may have a substituent of C ₆ -C ₁₈ , a phenoxy group, a phenyl Carbonyl group, alkylthio group, phenylthio group, benzyloxy group, a C ₁ -C ₂₅ aliphatic group having at least one hydroxyl group, or a C ₃ -C ₂₅ aliphatic group having one group represented by the following structural formula .

(Wherein R < ₁₁ > is a hydrogen atom or an alkyl group)];

a is a number from 1 to 4; b is 0 or a number from 1 to 3; a + b is 1 to 4; n is a number from 1 to 4; And z is a halide represented by the following formula (3):

(In the above formula, M is a boron atom, phosphorus atom, arsenic atom or antimony atom, Q is a halogen atom, m is a number of 3 to 6, Is 0 or 1, and m + Is 4 to 6].

(3) In the above (2), Ar , Each of R ₁ -R ₁₀ is a hydrogen atom, a halogen atom, an alkoxy group or a (C ₁ -C ₅ ) alkyl group, and M is a phosphorus atom or an antimony atom.

4 and 3, wherein in the rest of the R ₁ -R ₅ is a halogen atom and at least one of R ₁ -R ₅ is a hydrogen atom of the above, R ₆ -R ₁₀ is at least one halogen atom, and R ₆ - And the remainder of R ₁₀ is a hydrogen atom.

(5) In the above (2), Ar R ₃ and R ₈ are halogen atoms and R ₁ , R ₂ , R ₄ -R ₇ , R ₉ and R ₁₀ are hydrogen atoms, a is 2, b is 0, n is 2, M is phosphorus atom Or an antimony atom, m is 6, and Lt; / RTI >

(6) The onium salt in which the halogen atom in the above (5) is a fluorine atom.

(7) An onium salt represented by the following structural formula.

(8) An onium salt represented by the following structural formula.

(9) A photopolymerization initiator comprising the onium salt of the above (1) to (8) as an active ingredient.

(10) An energy ray-curable composition containing a cationic polymerization material and the onium salt of the above (1) to (8).

(11) The composition of (10) above, wherein the cationic polymerization material is an epoxy compound, a vinyl ether compound or a cyclic ether compound.

(12) The composition according to item (11) above, wherein the epoxy compound is an alicyclic (alicyclic) epoxy resin.

(13) The positive resist composition according to item (11) above, wherein the vinyl ether compound is at least one compound selected from the group consisting of triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, cyclohexane-1,4-dimethylol divinyl ether,

Or urethane polyvinyl ether.

(14) The composition according to item (10) above, wherein the onium salt is the onium salt of the above (7) or (8).

(15) The composition according to item (10) above, wherein the energy ray is ultraviolet ray.

(16) The composition according to item (10) above, which comprises 100 parts by weight of a cationic polymeric material and 0.01 to 20 parts by weight of an onium salt.

(17) An ultraviolet curing composition comprising 100 parts by weight of an alicyclic epoxy resin and 0.1 to 10 parts by weight of an onium salt of the above (7) or (8).

(18) An ultraviolet curing composition comprising 100 parts by weight of a vinyl ether compound and 0.1 to 10 parts by weight of an onium salt of the above (7) or (8).

(19) The positive resist composition according to item (18) above, wherein the vinyl ether compound is at least one compound selected from the group consisting of triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, cyclohexane-1,4-dimethylol divinyl ether,

Or urethane polyvinyl ether.

(20) A cured product of the composition of (10) to (19) above.

(21) A method of curing a composition according to any one of (10) to (19) above, wherein the composition is irradiated with ultraviolet light.

Examples of the monovalent to tetravalent aromatic group represented by Ar in the structural formula (1) include the following.

Among these, preferred are m-phenylene group , m-naphthylene group And the like at the m-position (1,3-position). The monovalent to tetravalent aromatic groups include, for example, (C ₁ -C ₄ ) alkyl groups such as methyl, ethyl, propyl and butyl, (C ₁ -C ₄ ) alkylcarbonyloxy groups, halogen atoms such as fluorine, chlorine, bromine and iodine), (C ₁ -C ₄₎ alkoxy group, benzoyl group, phenyl group, phenylthio group, (C ₁ -C ₄₎ may have at least one substituent from the alkylthio group, and cyano group, .

Examples of the bisphenylsulfonyl group (X) which may have one substituent include the group represented by the above formula (2). In the structural formula (2), the halogen atom of the substituent group R ₁ -R ₁₀ is F, Cl, Br and I, and F is preferable. Examples of the alkoxy group include a C ₁ -C ₂₅ alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group and a pentoxy group, and a C ₁ -C ₅ alkoxy group is preferable. Examples of the alkyl group include a C ₁ -C ₂₅ alkyl group such as a methyl group, an ethyl group, a propyl group and a pentyl group, preferably a C ₁ -C ₅ alkyl group. As the substituent of the phenyl group which may have one of the substituents C ₆ -C ₁₈ , there is a C ₆ -C ₁₈ alkyl group, for example, a nonyl group, and the substituent is preferably a para position. Examples of the alkylthio group include C ₁ -C ₅ alkylthio groups such as methylthio group, ethylthio group, propylthio group, butylthio group and pentylthio group. Examples of C ₁ -C ₂₅ aliphatic groups having at least one hydroxyl group include groups represented by the following structural formulas.

(Wherein Y is O or S, R is C ₁ -C ₂₅ polymethylene or C ₃ -C ₁₀ cycloalkylene such as methylene, dimethylene, trimethylene or tetramethylene, and R is methyl or ethyl C ₁ -C ₅ alkyl group, and h is 1 to 3.)

A concrete example is as follows.

-O-CH ₂ CH ₂ CH ₂ CH ₂ -OH

Examples of C ₃ -C ₂₅ aliphatic groups having the group represented by the structural formula (a) below include

And groups represented by Structural Formulas (b) and (c).

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

(Wherein j is an integer of 1 to 10, k is 1 or 2, and R < ₁₁ > is as defined above)

Examples of the group of the structural formula (b)

And the like, and examples of the group of the structural formula (c)

.

Examples of R ₁₁ include C ₁ -C ₅ alkyl groups such as methyl group, ethyl group, propyl group, butyl group and pentyl group.

Among these groups, preferred are (1) a halogen atom, (2) an alkyl group, (3) an alkoxy group, (4) a C ₁ -C ₂₅ aliphatic group having at least one hydroxyl group, and (5) a C ₃ -C ₂₅ Aliphatic group.

Those substituents in the structural formula (2) above that belongs to a combination of R ₁ -R ₁₀ as (a) R ₁ -R ₁₀ all being of a hydrogen atom, (b) R ₁ -R ₁₀ are hydrogen atoms from 9-6 dogs (C) 3 to 4 of R _{1 to} R ₅ are hydrogen atoms, 1 to 2 are groups other than hydrogen atoms, and 3 to 5 of R _{6 to} R ₁₀ are hydrogen And 0 to 2 are atoms other than hydrogen atoms, and the above combination (c) is preferred in combination (b). (D) one of R ₁ , R ₂ and R ₃ , preferably R ₁ or R _3, is a group other than a hydrogen atom and the remainder is a hydrogen atom, and (e) ) One or two of R ₁ , R ₂ and R ₃ and one or two of R ₆ , R ₇ and R ₈ are the groups of the above (1) to (3), and the remainder is a hydrogen atom. (e), R ₃ and R ₈ are groups of the above (1) to (3), preferably a halogen atom and the remainder are hydrogen atoms.

In the above structural formula (1), a is preferably 1 to 2, b is preferably 0, and n is preferably 1 to 2.

In the structural formula (3) used in the structural formula (1), preferred as M is a phosphorus atom or an antimony atom, and a halogen atom is preferably a fluorine atom. m is preferably from 5 to 6, It is 0, and preferably, a preferred example PF ₆ and SbF _6.

Examples of onium salts of the present invention represented by the structural formula (1) include the following sulfonium salt compounds.

The onium salt of the present invention can be synthesized by the following synthesis method (1) or (2).

Synthesis method (1):

The onium salt is prepared according to a known method for preparing a sulfonium salt using a diphenyl sulfide compound of the following structural formula (5) and a substituted or unsubstituted diphenyl sulfoxide compound of the following structural formula (4) as starting materials.

(Wherein Ar and C are as defined above)

(Wherein R &_lt; ₁ > -R < ₁₀ > is as defined above)

Synthesis method (2):

The onium salt is prepared by previously preparing a corresponding substituted or unsubstituted sulfonium salt, and then converting or introducing the substituent.

The synthesis method (1) will be specifically described below.

The diphenyl sulfide compound represented by the structural formula (5) can be reacted with a substituted or unsubstituted diphenyl sulfoxide compound represented by the structural formula (4) in the presence of a dehydrating agent such as phosphorus pentoxide, concentrated sulfuric acid, acetic anhydride ) At room temperature to 150 캜, and then the reaction mixture is added dropwise to the aqueous solution of the compound represented by the following structural formula (3 ').

(Wherein B is an alkali metal and M, Q, m and Lt; / RTI >

In the above reaction, the substituted or unsubstituted diphenyl sulfoxide compound of the structural formula (4) is preferably used in an amount of 0.25 to 1.2 mol, more preferably 0.25 to 1.2 mol, per equivalent of the terminal sulfide group of the diphenyl sulfide compound of the structural formula (5) And the condensation reaction is carried out in an amount of 1.0 to 1.1 moles.

Examples of compounds of formula (5) are as follows.

Examples of the compound represented by the structural formula (4) include diphenylsulfoxide, 4,4'-difluorodiphenylsulfoxide, 2,2'-difluorodiphenylsulfoxide, 3,3'-difluorodiphenylsulfoxide , 4,2'-difluorodiphenyl sulfoxide, 4,4'-dibromodiphenyl sulfoxide, 4,4'-dichlorodiphenyl sulfoxide, 2,2'-dichlorodiphenyl sulfoxide, 2,2 ', 4,4'-tetrachlorodiphenylsulfoxide, 4,4'-dimethyldiphenylsulfoxide, 4,4'-diethyldiphenylsulfoxide, 4,4'-dimethoxydiphenylsulfoxide, 4 4-phenyldiphenyl sulfoxide, 4-phenyldiphenyl sulfoxide, 4-phenyldiphenyl sulfoxide, 4-phenyldiphenyl sulfoxide, 4-phenyldiphenyl sulfoxide, 4-phenylpyridine, 4-phenylpiperidine, 4-phenylpiperidine, 4- (p-nonylphenyl) diphenylsulfoxide and 4-phenyloxydiphenylsulfoxide.

In the above structural formula (3 '), B is an alkali metal such as Na or K.

Examples of the compound of the structural formula (3 ') include NaSbF ₆ , NaPF ₆ , NaAsF ₆ , NaBF ₄ , NaSbF ₅ OH, KSbF ₆ , KPF ₆ , KAsF ₆ and KSbF ₅ OH.

The compound of formula (5) can be prepared by reacting an aromatic carboxylic acid compound with diphenylsulfide. As the reaction solvent, a solution prepared by dissolving phosphoric anhydride in an alkylsulfonic acid such as methanesulfone is preferable. The reaction temperature is preferably room temperature to 130 ° C, and the reaction time is preferably 0.5 to 15 hours. The ratio of the aromatic carboxylic acid compound to the diphenyl sulfide is preferably about 1 mole of diphenyl sulfide relative to one equivalent of the carboxylic acid of the aromatic carboxylic acid compound.

Examples of the aromatic carboxylic acid compound include monocarboxylic acid or polycarboxylic acid shown below. Examples of the aromatic monocarboxylic acid include benzoic acid, o-methylbenzoic acid, m-methylbenzoic acid, p-methylbenzoic acid, 3,5-dimethylbenzoic acid, p-ethylbenzoic acid, Chlorobenzoic acid, p-chlorobenzoic acid, 2,4-dichlorobenzoic acid, o-fluorobenzoic acid, m-fluorobenzoic acid, 2,4-difluorobenzoic acid, p Benzoic acid, p-phenylbenzoic acid, naphthalene-2-carboxylic acid, p-phenylthiobenzoic acid, o-cyanobenzoic acid, p-cyanobenzoic acid and p- Examples of the carboxylic acid include isophthalic acid, terephthalic acid, benzene-1,2,4-tricarboxylic acid, naphthalene-1,4,5,8-tetracarboxylic acid, naphthalene-2,6-dicarboxylic acid,

.

Next, the synthesis method (2) will be described in detail.

The synthesis method (2) is a method wherein at least one of R ₁ -R ₁₀ in the structural formula (2) is an alkoxy group, a C ₁ -C ₂₅ aliphatic group having at least one hydroxyl group, or C _Are suitable for the preparation of compounds of formula (1) which are _{3 to 25} aliphatic groups.

This method is a method in which a sulfonium salt synthesized in the above synthesis method (1), for example, a halide compound which is a compound of the following structural formula (6) and an alcohol are reacted with each other in a known manner, for example, in the presence of a basic compound such as sodium hydroxide or potassium hydroxide At room temperature to 150 ° C.

(Wherein A is a halogen atom and Ar, a, b, n and Z are the same as defined above)

Examples of the alcohol include methanol, ethanol, carbitol, ethylene glycol, polyethylene glycol, propylene glycol, glycerin, trimethylolpropane, 1,4-butanediol, cyclohexanediol and monohydroxyethylthiol.

According to the synthesis method (2), an onium salt in which the halide moiety of the above-mentioned halide is converted into the following substituent can be produced.

The present invention relates to a process for synthesizing a hydroxyl group and a lactone (for example,? -Caprolactone) or an acid (for example, acetic acid, acetic anhydride) of the compound obtained in the synthesis method (2) in which a substituent is converted into a substituent having a hydroxyl group And the like.

Next, the energy ray hardening composition of the present invention will be described.

Examples of the cationic polymerization material used in this composition include epoxy compounds, styrene and vinyl ethers, and cyclic ether compounds, preferably spirocyclic ether compounds such as spiro-orthoester, bicyclo-orthoester and spiro-orthocarbonate Cationic polymerizable vinyl ether compounds.

Examples of the epoxy compound include conventionally known aromatic epoxy resins, alicyclic epoxy resins, aliphatic epoxy resins, and further, epoxide monomers and episulfide monomers.

Examples of the aromatic epoxy resin include polyhydric phenol having at least one aromatic nucleus or polyglycidyl ether of the alkylene oxide adduct thereof, for example, bisphenol compounds such as bisphenol A, bisphenol F and bisphenol S, Glycidyl ethers prepared by reaction of an alkylene oxide (e.g., ethylene oxide, propylene oxide or butylene oxide) adduct of a compound with epichlorohydrin, novolak type epoxy resins (e.g., phenol-novolak Cresol-novolak-type epoxy resin, and brominated phenol-novolak-type epoxy resin) and trisphenol methane triglycidyl ether.

Examples of the alicyclic epoxy resin include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, bis- (3,4-epoxycyclohexylmethyl) adipate, 2- (3,4- Bis (2,3-epoxycyclopentyl) ether and EHPE-3150 (a cycloaliphatic epoxy resin having a softening point of 71 ° C manufactured by Daicel Co., Ltd.) Resin).

Examples of aliphatic epoxy resins include aliphatic polyhydric alcohols or polyglycidyl ethers of alkylene oxide adducts thereof. Representative examples thereof include diglycidyl ether of 1,4-butanediol, diglycidyl ether of 1,6-hexanediol, triglycidyl ether of glycerin, triglycidyl ether of trimethylol propane, diglycidyl ether of polyethylene glycol A polyether polyol prepared by adding at least one alkylene oxide (e.g., ethylene oxide and propylene oxide) to an aliphatic polyhydric alcohol such as ethylene glycol, propylene glycol and glycerin, Polyglycidyl ether, and the like.

Examples of epoxide monomers include monoglycidyl ethers of aliphatic higher alcohols and polyglycidyl ethers of polyether alcohols or butyl phenols prepared by the addition of phenol, cresol or alkylene oxide.

Examples of the cationically polymerizable vinyl ether compound include triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, cyclohexane-1,4-dimethylol vinyl ether, 1,4-butanediol divinyl ether, , And urethane polyvinyl ethers (e.g., VECtomer 2010 from Allied-Signal).

These cationic polymerization materials may be used singly or as a mixture of two or more thereof.

The curing composition of the present invention contains as essential components 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, of a photopolymerization initiator containing 100 parts by weight of a cationic polymerization substance and an onium salt of the structural formula (1) as an active ingredient. The characteristic ratios of these components are determined by the properties of the cationic polymeric material, the type of energy ray, the amount of irradiation of the energy ray, and the curing time and temperature, humidity and thickness of the curing material. In order to easily dissolve the photopolymerization initiator in the cationic polymerization material, the photopolymerization initiator is dissolved in a solvent (e.g., propylene carbonate, carbitol, carbitol acetate or -Butyrolactone). ≪ / RTI >

The curing composition of the present invention can be prepared by mixing, dissolving, or kneading a cationic polymerization material with a photopolymerization initiator.

The curing composition of the present invention can be irradiated with an energy ray such as ultraviolet rays for 0.1 seconds to several minutes to be cured in a solvent insoluble state or in a tackified state. Any suitable energy ray may be used as long as it has energy capable of decomposing the photopolymerization initiator. Electron wave energy of a wavelength of 2000 to 7000 angstroms or high energy radiation such as electron beam, X-ray, and radiation obtained from a high-pressure or low-pressure mercury lamp, xenon lamp, Ultraviolet rays are preferred. Exposure to the energy beam depends on the intensity of the energy beam, but typically about 0.1 to 10 seconds is sufficient. However, in the case of a relatively thick film, it is preferable to increase the exposure time. Most of the compositions are dried to the solidified tactile state due to the cationic polymerization reaction within 0.1 seconds to several minutes after irradiation with the energy ray, but in some cases, it is preferable to accelerate the cationic polymerization reaction by heating.

The composition of the present invention may contain a diluting solvent as long as it does not inhibit the cationic polymerization reaction. For the modification, a non-reactive resin and a (meth) acrylate ester compound [such as bisphenol A type epoxy, novolak type epoxy resin Oligomers such as epoxy (meth) acrylate, urethane (meth) acrylate and polyester poly (meth) acrylate which are reaction products of epoxy resin of (meth) acrylic acid with 2-hydroxy , Monomers such as 6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, trimethylol propane tri (meth) acrylate, pentaerythritol tri . When a (meth) acrylate compound is used, it is preferably used together with a photo-radical polymerization initiator such as 1-hydroxycyclohexyl phenyl ketone, acetophenone dimethyl ketal or benzoyl methyl ether. Further, the organic characteristics may be improved by using an organic carboxylic acid or an acid anhydride, or rubber elasticity may be imparted by adding a polyol and other flexible prepolymer.

The composition of the present invention is coated on the surface of a base material to a thickness of, for example, 1 to 200 m, preferably 3 to 50 m, and is generally used as a transparent liquid. In some applications, inert pigments, dyes, fillers, antistatic agents, flame retardants, antifoaming agents, flow control agents, sensitizers, accelerators, light stabilizers and the like may be added to the composition of the present invention. The composition of the present invention can be applied to metals, wood, rubber, plastic, glass, ceramics and the like. Among the particular applications of the present invention are paints, coatings, inks, resists, liquid resists, adhesives, molding materials, casting materials, putty, glass fiber impregnants, sealants and the like.

The present invention will be described with reference to the following examples. In the examples and the synthesis examples, all parts are parts by weight.

Synthesis Example of Dimethylsulfide Compound of Structural Formula (5)

Synthesis Example 1 [Synthesis of Compound of Structural Formula (i)

16.2 parts of phosphorus pentoxide was completely dissolved in 161.7 parts of methanesulfonic acid, 18.6 parts of diphenylsulfide and 12.2 parts of benzoic acid were added to this solution, and the mixture was reacted at 80 DEG C for 1 hour. The completion of the reaction was confirmed by liquid chromatography. The reaction mixture was added dropwise to 1000 parts of an aqueous solution of potassium hydroxide (prepared by dissolving 200 parts of potassium hydroxide in 800 parts of water), and the resulting precipitate was collected by filtration, dried and heated in 400 parts of ethanol After dissolution, it was cooled to 5 캜. The precipitate was collected by filtration and dried to obtain 20.3 parts of a target compound (i) as a white solid. The melting point of this product was 69 to 70 占 폚.

Synthesis Example 2 [Synthesis of Compound of Structural Formula (ii)

After 18.3 parts of phosphorus pentoxide was completely dissolved in 180.3 parts of methanesulfonic acid, 18.6 parts of diphenyl sulfide and 13.6 parts of p-methylbenzoic acid were added to this solution, and the mixture was reacted at 80 ° C for 1 hour. The completion of the reaction was confirmed by liquid chromatography. This reaction mixture was treated in the same manner as in Synthesis Example 1 to obtain 20.2 parts of a target compound (ii) as a white solid. The melting point of this product was 117 to 118 占 폚.

Synthesis Example 3 [Synthesis of Compound of Structural Formula (iii)

After 20.8 parts of phosphorus pentoxide was completely dissolved in 208.2 parts of methanesulfonic acid, 18.6 parts of diphenylsulfide and 15.7 parts of p-chlorobenzoic acid were added to this solution, and the mixture was reacted at 80 DEG C for 1 hour. The completion of the reaction was confirmed by liquid chromatography. This reaction mixture was treated in the same manner as in Synthesis Example 1 to obtain 21.6 parts of the desired compound (iii) as a white solid. The melting point of this product was 134 to 135 占 폚.

Synthesis Example 4 [Synthesis of compound of structural formula (iv)] [

After 23.9 parts of phosphorus pentoxide was completely dissolved in 238.6 parts of methanesulfonic acid, 18.6 parts of diphenylsulfide and 18.0 parts of p-methyloxycarbonylbenzoic acid were added to the solution, and the mixture was reacted at 80 DEG C for 1 hour. The completion of the reaction was confirmed by liquid chromatography. This reaction mixture was treated in the same manner as in Synthesis Example 1 to obtain 21.6 parts of the desired compound (iv) as a white solid. The melting point of this product was 145 to 148 占 폚.

Synthesis Example 5 [Synthesis of Compound of Structural Formula (V)

22.0 parts of phosphorus pentoxide was completely dissolved in 220.1 parts of methanesulfonic acid, 37.2 parts of diphenyl sulfide and 16. 6 parts of isophthalic acid were added to this solution, and the mixture was reacted at 80 DEG C for 6 hours. The completion of the reaction was confirmed by liquid chromatography. This reaction mixture was treated in the same manner as in Synthesis Example 1 to obtain 35.2 parts of the aimed compound (V) as a white solid. The melting point of this product was 147 to 152 占 폚.

Synthesis Example 6 [Synthesis of Compound of Structural Formula (vi)

28.6 parts of phosphorus pentoxide was completely dissolved in 286.4 parts of methanesulfonic acid, 37.2 parts of diphenyl sulfide and 21.6 parts of naphthalene-2,6-dicarboxylic acid were added to this solution, and the mixture was reacted at 80 ° C for 6 hours. The completion of the reaction was confirmed by liquid chromatography. This reaction mixture was treated in the same manner as in Synthesis Example 1 to obtain 37.0 parts of a target compound (vi) as a white solid. The melting point of this product was 195 to 200 占 폚.

Synthesis of onium salt of structural formula (1):

[Example 1] Synthesis of Compound (a)

29.0 parts of the compound (4-benzoyl-diphenylsulfide) prepared in Synthesis Example 1, 23.9 parts of 4,4'-difluorodiphenylsulfoxide, 39.8 parts of phosphorus pentoxide and 398 parts of methanesulfonic acid as a solvent were added and heated to 80 ° C And reacted for 3 hours while stirring. While stirring, this reaction mixture was slowly added to 280.0 parts of an aqueous solution of NaPF ₆ (prepared by dissolving 16.8 parts of NaPF _{6 in} 263.2 parts of water) at 5 ° C, dropwise. The precipitate of the white solid was filtered, dried and dissolved in 650 parts of isopropanol while heating (70 DEG C), followed by cooling to 0 DEG C, filtration and drying to obtain 46.0 parts of the target compound (a) as a white solid. The melting point of this product was 131 to 139 占 폚. The result of the elemental analysis was almost the same as the calculated value.

[Example 2] Synthesis of compound (b)

30.4 parts of the compound [4- (p-methylbenzoyl-diphenylsulfide)] prepared in Synthesis Example 2, 20.2 parts of diphenylsulfoxide and 179.8 parts of concentrated sulfuric acid were added and reacted at room temperature for 24 hours. ₆ aqueous solution (prepared by dissolving 25.8 parts of NaSbF _{6 in} 405.3 parts of water) was slowly added dropwise at 5 ° C. The precipitate of the white solid was filtered and dried, and dissolved in 650 parts of isopropanol while heating (70 ° C.) , The solution was cooled to 0 deg. C, filtered and dried to obtain 50.8 parts of the desired compound (b) as a white solid. The melting point of the product was 110 to 118 DEG C. The result of elemental analysis was almost the same as the calculated value.

[Example 3] Synthesis of compound (c)

32.5 parts of the compound [4- (p-chlorobenzoyl) -diphenylsulfide] prepared in Synthesis Example 3, 36 parts of 4,4'-dibromodiphenylsulfoxide and 240.6 parts of concentrated sulfuric acid were added and the mixture was reacted at room temperature for 24 hours . While stirring, this reaction mixture was gradually added to 431.1 parts of an aqueous solution of NaSbF ₆ (prepared by dissolving 25.8 parts of NaSbF _{6 in} 405.3 parts of water) at 5 ° C, dropwise. The precipitate of the white solid was filtered, dried and dissolved in 650 parts of isopropanol while heating (70 ° C). The solution was cooled to 0 ° C and filtered, and the residue was dried to obtain 63.3 parts of the target compound (c) as a white solid . The melting point of this product was 125 to 129 占 폚. The result of the elemental analysis was almost the same as the calculated value.

[Example 4] Synthesis of Compound (d)

34.8 parts of the compound prepared in Synthesis Example 4, 20.2 parts of diphenylsulfoxide, and 173.1 parts of concentrated sulfuric acid were added and reacted at room temperature for 24 hours. While stirring, this reaction mixture was gradually added to 431.1 parts of an aqueous solution of NaSbF ₆ (prepared by dissolving 26.8 parts of NaSbF _{6 in} 405.3 parts of water) at 0 ° C, dropwise. The precipitate of the white solid was filtered, dried and dissolved in 650 parts of isopropanol while heating (70 ° C). The solution was cooled to 0 ° C and filtered, and then the residue was dried to obtain 53.9 parts of the desired compound (d) . The result of the elemental analysis of this product was almost the same as the calculated value.

[Example 5] Synthesis of Compound (e)

50.3 parts of the compound prepared in Synthesis Example 5, 40.4 parts of diphenylsulfoxide and 208.1 parts of a concentrated sulfuric acid were added and reacted at room temperature for 24 hours. While stirring, this reaction mixture was slowly added to 862.3 parts of an aqueous NaSbF ₆ solution (prepared by dissolving 51.7 parts of NaSbF _{6 in} 810.6 parts of water) at room temperature. The precipitate of the white solid was filtered, dried and dissolved in 650 parts of isopropanol while heating (70 ° C). The solution was cooled to 0 ° C and filtered. The residue was dried to obtain 94.1 parts of the target compound (e) as a white solid . The melting point of this product was 152 to 162 ° C. The result of the elemental analysis was almost the same as the calculated value.

[Example 6] Synthesis of Compound (f)

55.3 parts of the compound prepared in Synthesis Example 6, 46.1 parts of 4,4'-dimethyldiphenylsulfoxide, and 233.4 parts of concentrated sulfuric acid were added and reacted at room temperature for 24 hours. While stirring, this reaction mixture was slowly added dropwise at room temperature to 862.3 parts of an aqueous solution of NaSbF ₆ (prepared by dissolving 51.7 parts of NaSbF _{6 in} 810.6 parts of water). The precipitate of the white solid was filtered and dried to dissolve 650 parts of isopropane while heating (70 ° C). The solution was cooled to 0 ° C and filtered, and the residue was dried to obtain the target compound (f) I got wealth. The melting point of this product was from 201 to 205 ° C. The result of the elemental analysis was almost the same as the calculated value.

[Example 7] Synthesis of Compound (g)

50.3 parts of the compound prepared in Synthesis Example 5, 47.6 parts of 4,4'-difluorodiphenylsulfoxide, and 225.4 parts of concentrated sulfuric acid were added and reacted at room temperature for 24 hours.

While stirring, this reaction mixture was slowly added to 862.3 parts of an aqueous NaSbF ₆ solution (prepared by dissolving 51.7 parts of NaSbF _{6 in} 810.6 parts of water) at room temperature. The precipitate of the white solid was filtered, dried and dissolved in 650 parts of isopropanol while heating (70 ° C). The solution was cooled to 0 ° C and filtered, and the residue was dried to obtain 94.1 parts of the target compound (g) as a white solid . The melting point of this product was 163 to 172 占 폚. The result of the elemental analysis was almost the same as the calculated value.

[Example 8] Synthesis of Compound (h)

32.8 parts of the compound prepared in Example 1, 4.0 parts of sodium hydroxide and 100 parts of 1,4-butanediol were added and reacted at room temperature for 24 hours. Subsequently, the reaction mixture was poured into water, and the resulting oily substance was separated and dried to obtain 41.8 parts of the target compound (h) as a pale yellow liquid. The result of the elemental analysis of this product was almost the same as the calculated value.

[Example 9] Synthesis of compound (j)

70.8 parts of the compound prepared in Example 7, 4.0 parts of sodium hydroxide and 200 parts of ethylene glycol were added and reacted at room temperature for 24 hours. The reaction mixture was poured into water, and the precipitated white solid precipitate was filtered, A solid product was obtained. Subsequently, 78.2 parts of this product, 48.5 parts of? -Caprolactone and 0.04 part of stannous chloride were added and reacted at 120 ° C for 15 hours.

When it was confirmed that the content of? -Caprolactone in the reaction mixture was 1% or less, the reaction was terminated to obtain 126.7 parts of a liquid product (compound (j)). The result of the elemental analysis was almost the same as the calculated value.

[Example 10] Synthesis of Compound (k)

50.3 parts of the compound prepared in Synthesis Example 5, 47.6 parts of 4,4'-difluorodiphenylsulfoxide, and 225.4 parts of concentrated sulfuric acid were added and reacted at room temperature for 24 hours. While stirring, the reaction mixture was gradually added to 559.8 parts of an NaPF ₆ aqueous solution (prepared by dissolving 33.6 parts of NaPF _{6 in} 5.62 parts of water) at room temperature. The precipitate of the white solid was filtered, dried and dissolved in 650 parts of isopropanol while heating (70 ° C). The solution was cooled to 0 ° C and filtered, and the residue was dried to obtain 104.9 parts of the target compound (k) as a white solid . The melting point of this product was 154 to 163 占 폚. The result of the elemental analysis was almost the same as the calculated value.

[Examples 11 to 30 and Comparative Examples 1 to 6]

(Experiment on each composition)

Each of the components shown in Table 1 and Table 2 was mixed and dissolved to prepare an energy ray curable composition. Each composition was coated on an aluminum test plate to a thickness of 5 mu and irradiated with ultraviolet rays by a high-pressure mercury lamp (80 W / cm) installed at a distance of 8 cm from the surface of the cortex to cure the cortex. The prepared composition was tested for transparency, storage stability, tactile sensation, luster and smell of cured coating film and the like. The results are shown in Table 1 and Table 2.

Test Methods :

Transparency: The transparency of the composition was visually evaluated.

: Totally transparent.

: Slightly cloudy.

X: Cloudy.

XX: Separated immediately into each component.

Storage stability: The composition was stored at 40 占 폚 for 3 months and its stability was examined.

: No change.

: Slightly tacky.

X: Gelled.

Solidification tactile sensation: The amount of irradiation (amount of irradiation) (mJ / cm ² ) required to reach the solidified tactile state was determined and determined.

Gloss: The amount of ultraviolet light (mJ / cm ² ) required to reach the tacky state of the coating material was irradiated to the coating material, and the surface of the cured material was visually judged.

: Good gloss.

: Slightly cloudy.

X: Matte.

Odor: The surface of the coating material was irradiated with ultraviolet rays of 1000 mJ / cm ² to examine the surface of the cured coating material.

: No odor.

: There is a little odor.

X: There is considerable smell.

××: There is a lot of smell.

[Table 1]

[Table 2]

As can be seen from the results of Tables 1 and 2, the compositions containing the photopolymerization initiator of the present invention are excellent in compatibility, transparency and curability, have excellent gloss of the cured coating material, have little odor, It is also excellent in adhesiveness.

Claims (21)

Onium salts represented by the following general structural formula (1): Wherein Ar is a monovalent to tetravalent aromatic group, X is a bisphenylsulfonio group which may have a substituent, a is 1 to 2, b is 0 or 1, a + b is 1 to 2, n is 1 to 2, and Z is a halide represented by the following general formula (3); (In the above formula, M is a boron atom, phosphorus atom, arsenic atom or antimony atom, Q is a halogen atom, m is 3 to 6, Is 0 or 1, m + Is 4 to 6). The onium salt according to claim 1, which is defined as follows: Ar is the following aromatic groups, [These aromatic groups may have at least one substituent selected from a (C ₁ -C ₅ ) alkyl group, a (C ₁ -C ₅ ) alkyloxycarbonyl group and a halogen atom]; The bisphenylsulfonio group which may have a substituent is a group represented by the following structural formula (2) [Wherein each of R ₁ -R ₁₀ is a hydrogen atom, a halogen atom, an alkyl group, or a C ₁ -C ₅ aliphatic group having at least one hydroxyl group]; a is 1 to 2; b is 0 or 1; a + b is 1 to 2; n is 1 to 2; And Z is a halide represented by the following formula (3). (Wherein M is a boron atom, phosphorus atom, arsenic atom or antimony atom, Q is a halogen atom, m is from 3 to 6, Is 0 or 1, and m + Is 4 to 6). The compound according to claim 2, wherein Ar is , Each of R ₁ -R ₁₀ is a hydrogen atom, a halogen atom, or a (C ₁ -C ₅ ) alkyl group, and M is a phosphorus atom or an antimony atom. The compound 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, at least one of R _{6 to} R ₁₀ is a halogen atom, and the remainder of R _{6 to} R ₁₀ is a hydrogen atom . The compound according to claim 2, wherein Ar is R ₃ and R ₈ are halogen atoms and R ₁ , R ₂ , R ₄ -R ₇ , R ₉ and R ₁₀ are hydrogen atoms, a is 2, b is 0, n is 2, M is phosphorus atom Or an antimony atom, m is 6, and Lt; / RTI > The onium salt according to claim 5, wherein the halogen atom is a fluorine atom. Onium salt represented by the following structural formula. Onium salt represented by the following structural formula. A photopolymerization initiator comprising the onium salt of any one of claims 1 to 8 as an active ingredient. An energy ray curable composition comprising a cationic polymeric material and the onium salt of any one of claims 1 to 8. 11. The composition of claim 10 wherein the cationic polymeric material is an epoxy compound, a vinyl ether compound or an alicyclic ether compound. The composition according to claim 11, wherein the epoxy compound is an alicyclic epoxy resin. 12. The composition of claim 11, wherein the vinyl ether compound is selected from the group consisting of triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, cyclohexane-1,4-dimethylol divinyl ether, , Or urethane polyvinyl ether. 11. The composition of claim 10, wherein the onium salt is the onium salt of claim 7 or claim 8. 11. The composition of claim 10 wherein the energy beam is ultraviolet. 11. The composition of claim 10 comprising 100 parts by weight of the cationic polymeric material and 0.01 to 20 parts by weight of the onium salt. 100 parts by weight of an alicyclic epoxy resin and 0.1 to 10 parts by weight of an onium salt of claim 7 or 8. 100 parts by weight of a vinyl ether compound and 0.1 to 10 parts by weight of an onium salt of claim 7 or 8. 19. The composition according to claim 18, wherein the vinyl ether compound is selected from the group consisting of triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, cyclohexane-1,4-dimethyltolvinyl ether, 1,4-butanediol divinyl ether, Or urethane polyvinyl ether. A cured product of the composition of any one of claims 10 to 19. A method of curing a composition according to any one of claims 10 to 19, wherein the composition is irradiated with ultraviolet light.