KR101758726B1

KR101758726B1 - Novel episulfide compounds, curable resin compositions containing the episulfide compounds, and cured products thereof

Info

Publication number: KR101758726B1
Application number: KR1020117027059A
Authority: KR
Inventors: ?스케 타카히; 스케 타카히; 나오미 사토; 히로유키 이가라시
Original assignee: 가부시키가이샤 아데카
Priority date: 2009-09-18
Filing date: 2010-08-03
Publication date: 2017-07-31
Also published as: JP2011063776A; CN102421826B; WO2011033872A1; CN102421826A; CN103382250A; JP5501710B2; KR20120097458A; TW201120022A; TWI466878B

Abstract

The present invention provides a compound having excellent curability, transparency and the like, particularly useful for optical use, and a curable resin composition using the compound. Specifically, an episulfide compound represented by the following general formula (I) or (II) is provided.

(In the formula (I), A ¹ and A ² represent an oxygen atom or a sulfur atom (provided that at least one of A ¹ and A ² represents a sulfur atom), Cy represents a cycloalkyl group having 3 to 10 carbon atoms , X and Z each independently represent an alkyl group having 1 to 10 carbon atoms, etc., n is 0 to 10, p is 0 to 5, and r is an integer of 0 to 4. In the formula (II), Y ¹ and Y ² represents an alkyl group such as a carbon atom number ^{1~10, a 1, a 2,} Z, n and r are the same as the above general formula (ⅰ). n is 0~10, q is 0~4, q 'is 0 to 8 (provided that q 'is not more than (x + y) x 2), x represents 0 to 4, y represents 0 to 4, and the sum of the numbers of x and y is 2 to 4.)

Description

TECHNICAL FIELD [0001] The present invention relates to a novel episulfide compound, a curable resin composition containing the episulfide compound, and a cured product of the episulfide compound and a cured product thereof.

The present invention relates to a novel episulfide compound, a curable resin composition containing the episulfide compound and a curing agent and / or an energy ray-sensitive cationic initiator, and a cured product thereof.

BACKGROUND ART Hitherto, a cured product that is transparent and has a high refractive index has been used for an optical material such as a lens. In particular, due to excellent electrical properties, heat resistance, adhesiveness, optical properties and the like of a resin cured product combined with a curing agent, active development has been made in the fields of electronic materials and optical materials. For example, a semiconductor encapsulating material, an antireflection film such as a liquid crystal display, a protective film of a color filter, a lens used in optical devices such as an optical waveguide and a camera, a mirror, and a prism.

Patent Document 1 reports a branched alkyl sulfide type episulfide compound, Patent Document 2 discloses a straight chain alkyl sulfide type episulfide compound, and Patent Document 3 reports a bisphenol S type episulfide compound. However, these compounds were problematic in heat resistance. Patent Document 4 discloses an episulfide compound having a fluorene skeleton having high heat resistance as an optical material. However, there is a problem in that it is impossible to prepare a resin composition for obtaining a cured product having a poor solubility in a diluent or the like and exhibiting a high refractive index.

Japanese Patent Application Laid-Open No. 9-071580 Japanese Patent Application Laid-Open No. 9-110979 Japanese Patent Application Laid-Open No. 11-12273 Japanese Patent Application Laid-Open No. 2001-288177

It is an object of the present invention to provide a compound having excellent curability, transparency and the like, particularly useful for optical use, and a curable resin composition using the compound.

As a result of intensive studies, the present inventors have found that an episulfide compound having a specific structure is excellent in solubility, and that the curable resin composition containing the episulfide compound is excellent in storage stability, and the cured product has a high refractive index And found out that it is excellent in transparency, and found out that the above problems can be solved by using this.

The present invention has been made on the basis of the above finding, and provides a novel epithulfide compound represented by the following general formula (I) or (II).

(Wherein A ¹ and A ² represent an oxygen atom or a sulfur atom (provided that at least one of A ¹ and A ² represents a sulfur atom), Cy represents a cycloalkyl group having 3 to 10 carbon atoms, X and Z each independently represent an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, , The methylene group in the alkyl group and the arylalkyl group and the bond portion of the aryl group may be interrupted by -O-, -S-, or a double bond, and Z may form an aromatic ring adjacent to each other. , An aryl group, an arylalkyl group, a heterocyclic group, a cycloalkyl group and an aromatic ring formed adjacent to Z may be substituted with a halogen atom, n is 0 to 10, p is 0 to 5, and r is an integer of 0 to 4. , the light existing when n is not 0 Isomers may be either any isomer).

(Wherein A ¹ and A ² represent an oxygen atom or a sulfur atom, provided that at least one of A ¹ and A ² represents a sulfur atom), Y ¹ , Y ² and Z each independently represent a hydrogen atom, An aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or a halogen atom, The bonding group of the aryl group may be interrupted by -O-, -S- or a double bond, adjacent Y ¹ may be bonded to each other to form a ring, and the alkyl group, aryl group, arylalkyl group, heterocyclic group And q 'is 0 to 8 (provided that q' is not more than (x + y) x 2), and r is an integer of 0 to 4 , x is 0 to 4, y is an integer of 0 to 4, and the sum of x and y is 2 to 4. On the other hand, when n is not 0, A scholar is any isomer.)

The present invention also provides a curable resin composition containing a novel episulfide compound represented by the general formula (I) or (II) and a curing agent.

The present invention also provides a curable resin composition containing a novel episulfide compound represented by the general formula (I) or (II) and an energy ray-sensitive cationic initiator.

The present invention also provides a cured product obtained by heating and / or irradiating the above-mentioned curable resin composition with an energy ray.

The episulfide compound of the present invention has excellent solubility and the episulfide compound-containing curable resin composition provides a cured product excellent in curability, storage stability, high refractive index and excellent transparency.

Hereinafter, the episulfide compound, the curable resin composition and the cured product of the present invention will be described in detail based on preferred embodiments.

The episulfide compound of the present invention is a novel compound represented by the above general formula (I) or (II).

First, the episulfide compound represented by the above general formula (I) will be described.

Examples of the cycloalkyl group having 3 to 10 carbon atoms represented by Cy, X and Z in the general formula (I) include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, cycloheptyl, cyclooctyl, Cyclononyl, cyclodecyl, and the like.

Examples of the alkyl group having 1 to 10 carbon atoms represented by X and Z in the general formula (I) include methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, Examples of the group in which the methylene group in the alkyl group is interrupted by -O- include methoxy, ethoxy, propyloxy, isopropyloxy, methoxymethyl, ethoxymethyl, and 2-methoxyethyl. Examples of the group terminated with -S- include methylthio, ethylthio, butylthio and pentylthio. Examples of the group in which the methylene group in the alkyl group is interrupted by a double bond include allyl, 3-butenyl and the like.

Examples of the aryl group having 6 to 20 carbon atoms represented by X and Z in the above general formula (I) include phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, Tolyl, p-tolyl, 3-fluorenyl, 9-fluorenyl, 1-tetrahydronaphthyl, 2-tetrahydronaphthyl, 1-acenaphthenyl, 2-indanyl, and biphenyl. Examples of the group in which the bonding moiety of the aryl group is interrupted by -O- include phenoxy, 1-naphthoxy, 2-naphthoxy, 1-anthryloxy, -O-alkoxy, o-tolyloxy, m-tolyloxy, p-tolyloxy, 9-fluorenyloxy, 1-indanyloxy, 2-indanyloxy, Examples of the groups terminated with a halogen atom include phenylthio, 1-naphthylthio, 2-naphthylthio, 1-anthrylthio, 1-phenanthrylthio, o-tolylthio, m- 1-tetrahydronaphthylthio, 2-tetrahydronaphthylthio, 1- Thio carry, as the group 2 and the like indanyl alkylthio, stop junction part with the double bond of the aryl group include a styryl and the like.

Examples of the arylalkyl group having 7 to 20 carbon atoms represented by X and Z in the general formula (I) include benzyl, phenethyl, 2-phenylpropyl, diphenylmethyl, triphenylmethyl and the like. Examples of the group in which the methylene group in the arylalkyl group is interrupted by -O- include benzyloxy, phenoxymethyl, phenoxyethyl, 1-naphthylmethoxy group, 2-naphthylmethoxy group and 1-anthrylmethoxy group, Examples of the group in which the methylene group in the arylalkyl group is interrupted by -S- include benzylthio, phenylthiomethyl, phenylthioethyl and the like. Examples of the group in which the methylene group in the arylalkyl group is interrupted by a double bond include cinnamyl and the like .

Examples of the heterocyclic group having 2 to 20 carbon atoms represented by X and Z in the general formula (I) include pyrrolyl, pyridyl, pyrimidyl, pyridazyl, piperazyl, piperidyl, pyranyl Thiazolyl, furyl, furanyl, benzofuranyl, thienyl, thiophenyl, benzothiophenyl, thiazolyl, thiazolyl, thiazolyl, thiazolyl, thiazolyl, Pyrimidinyl, thiazolyl, thiazolyl, thiazolyl, benzothiazolyl, oxazolyl, benzoxazolyl, isothiazolyl, isoxazolyl, indolyl, , 2-piperidone-1-yl, 2,4-dioxiimidazolidin-3-yl, 2,4-dioxoxazolidin-3-yl and the like.

The adjacent aromatic rings formed in adjacent Z groups in the general formula (I) include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a pyrene ring.

A halogen atom represented by X and Z in the general formula (I), and an alkyl group, an aryl group, an arylalkyl group, a heterocyclic group, a cycloalkyl group and adjacent Z groups represented by X and Z in the general formula (I) Examples of the halogen atom which may be substituted for the aromatic ring to be formed include fluorine, chlorine, bromine and iodine.

The alkyl group, aryl group, arylalkyl group, heterocyclic group, cycloalkyl group represented by X and Z in the general formula (I) and an aromatic ring formed therebetween may have a substituent, and examples thereof include methyl, ethyl, But are not limited to, methyl, ethyl, propyl, cyclopropyl, butyl, sec. Butyl, tert.butyl, isobutyl, amyl, isoamyl, tertiary amyl, cyclopentyl, hexyl, An alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, isobutyl, But are not limited to, methyloxy, ethyloxy, propyloxy, isopropyloxy, butyloxy, sec-butyloxy, tert -butyloxy, isobutyloxy, amyloxy, isoamyloxy, tertiary amyloxy, hexyloxy, Alkoxy groups such as heptyloxy, isoheptyloxy, heptyloxy, n-octyloxy, isooctyloxy, tert-octyloxy, 2-ethylhexyloxy, nonyloxy and decyloxy; Examples of the alkylthio include methylthio, ethylthio, propylthio, isopropylthio, butylthio, tert-butylthio, tert-butylthio, isobutylthio, amylthio, isoamylthio, tertiary amylthio, hexylthio, cyclohexylthio, heptyl An alkylthio group such as thio, isoheptylthio, tert-pentylthio, n-octylthio, isooctylthio, tert-octylthio, or 2-ethylhexylthio; Propenyl, 1-methyl-3-propenyl, 3-butenyl, 1-methyl-3-butenyl, isobutenyl, 3-pentenyl, Alkenyl groups such as 4-hexenyl, cyclohexenyl, bicyclohexenyl, heptenyl, octenyl, decenyl, pentadecenyl, eicosenyl, and tricosenyl; Arylalkyl groups such as benzyl, phenethyl, diphenylmethyl, triphenylmethyl, styryl and cinnamyl; Aryl groups such as phenyl and naphthyl; An aryloxy group such as phenoxy, naphthyloxy and the like; Arylthio groups such as phenylthio and naphthylthio; Or a pharmaceutically acceptable salt thereof, wherein the compound is selected from the group consisting of acetyl, 2-chloroacetyl, propionyl, octanoyl, acryloyl, methacryloyl, phenylcarbonyl (benzoyl), phthaloyl, 4-trifluoromethylbenzoyl, pivaloyl, salicyloyl ), Acyl groups such as oxaloyl, stearoyl, methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl and carbamoyl; Acyloxy groups such as acetyloxy and benzoyloxy; Amino, ethylamino, dimethylamino, diethylamino, butylamino, cyclopentylamino, 2-ethylhexylamino, dodecylamino, anilino, chlorophenylamino, toluidino, anisidino, Or a pharmaceutically acceptable salt thereof, wherein R is selected from the group consisting of hydrogen, alkyl, alkenyl, alkynyl, alkynyl, alkynyl, alkynyl, alkynyl, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino, methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonyl Amino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino, phenoxycarbonylamino, sulfamoylamino, N, N-dimethylaminosulfonylamino, methylsulfonylamino, butylsulfonyl Amino, phenylsulfonyl Substituted amino groups such as a minnow; A sulfonamide group, a sulfonyl group, a carboxyl group, a cyano group, a sulfo group, a hydroxyl group, a nitro group, a mercapto group, an imide group, a carbamoyl group and a sulfonamide group. On the other hand, when it is substituted with a substituent having a carbon atom, an alkyl group, an aryl group, an arylalkyl group, a heterocyclic group, a cyclohexyl group and adjacent Z groups formed by X and Z in the general formula (I) The number of carbon atoms in the aromatic ring satisfies the range of the specified number of carbon atoms.

In the episulfide compound represented by the general formula (I) and the episulfide compound represented by the general formula (II) described below, when n is not 0, an optical isomer sometimes exists, And the compound shown in the following text is not limited to a specific optical isomer.

Examples of the episulfide compound represented by the above general formula (I) include compounds represented by the following compounds Nos. 1 to 13. On the other hand, n in the following formula represents a number of 0 to 10. However, the present invention is not limited at all by the following compounds.

Among the episulfide compounds represented by the general formula (I), X and Z in the general formula (I) are an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms, 2, and n is 0 to 5, are preferred because of good storage stability. Particularly, the compounds of i) to iii) are more preferable because they are easy to obtain from raw materials and have good productivity.

i) A compound represented by the following general formula (III).

In the formula, A ¹ , A ² , Z, r and n are as defined in the general formula (I), while optical isomers present when n is not 0 may be any isomer.

ii) a compound wherein X in the general formula (I) is an aryl group having 6 to 20 carbon atoms, p is 0 or 1, and n is 0 to 2;

iii) a compound wherein n is 0 to 2 in the general formula (III).

The episulfide compound represented by the above general formula (I) is not particularly limited. For example, as shown in the following reaction formula, by reacting the epoxy derivative (1) with thiourea, ) Can easily be produced.

It is also possible to arbitrarily control the substitution ratio (sulfur substitution ratio) of the sulfur atom of the oxygen atom in the oxirane ring in the epoxy derivative as the raw material by increasing or decreasing the amount of thiourea used in the reaction or the reaction time, Depending on the purpose, it may be used as an episulfide compound of the present invention, leaving an epoxy derivative as a raw material or an unsubstituted oxirane ring in the product. The higher the sulfur substitution ratio is, the higher the refractive index of the cured product becomes, so it is preferably 50% to 100%, and more preferably 80% to 100%.

Next, the episulfide compound represented by the formula (II) will be described. On the other hand, the description of the episulfide compound represented by the above general formula (I) is appropriately applied to a part not specifically described in the following description.

The alkyl group having 1 to 10 carbon atoms represented by Y ¹ , Y ² and Z in the general formula (II), and the group in which the methylene group in the alkyl group is interrupted by -O-, -S-, or a double bond, And the groups exemplified in the explanation of the formula (I).

The aryl group having 6 to 20 carbon atoms represented by Y ¹ , Y ² and Z in the general formula (II), and the group in which the bonding part of the aryl group is interrupted by -O-, -S- or a double bond, And the groups exemplified in the description of the general formula (I).

The arylalkyl group having 7 to 20 carbon atoms represented by Y ¹ , Y ² and Z in the general formula (II), and the group in which the methylene group in the arylalkyl group is interrupted by -O-, -S- or a double bond, And the groups exemplified in the description of the general formula (I).

Examples of the heterocyclic group having 2 to 20 carbon atoms represented by Y ¹ , Y ² and Z in the general formula (II) include the groups exemplified in the description of the general formula (I).

Examples of the cycloalkyl group having 3 to 10 carbon atoms represented by Y ¹ , Y ² and Z in the general formula (II) include the groups exemplified in the description of the general formula (I).

Examples of the ring structure formed by bonding adjacent Y ¹ in the general formula (II) include cyclopentane ring, cyclohexane ring, cyclopentane ring, cyclopentane ring, cyclopentane ring, A condensed ring such as a 5 to 7-membered ring such as a piperidine ring, a morpholine ring, a lactone ring and a lactam ring, a fluorene ring, an acenaphthene ring, an indane ring, and a tetralin ring.

A halogen atom represented by Y ¹ , Y ² and Z in the general formula (II), and an alkyl group, an aryl group, an arylalkyl group, a heterocyclic group represented by Y ¹ , Y ² and Z in the general formula (II) , The cycloalkyl group, and the halogen atom which may be substituted in the ring structure formed by bonding adjacent Y ¹ , include the groups exemplified in the description of the general formula (I).

The ring structure formed by combining the alkyl group, aryl group, arylalkyl group, heterocyclic group, cycloalkyl group and adjacent Y ¹ represented by Y ¹ , Y ² and Z in the general formula (II) may have a substituent, These substituents include the groups exemplified in the description of the general formula (I), and these groups may be further substituted. When substituted with a substituent having a carbon atom, an alkyl group, an aryl group, an arylalkyl group, a heterocyclic group, a cycloalkyl group, and a group represented by Y ¹ , Y ² and Z in the general formula (II) The number of carbon atoms of the ring structure formed between Z groups satisfies the range of the specified number of carbon atoms.

Examples of the episulfide compound represented by the above general formula (II) include compounds represented by the following compounds No. 14 to No. 62. On the other hand, n in the following formula represents a number of 0 to 10. However, the present invention is not limited at all by the following compounds.

Among the episulfide compounds represented by the above general formula (II), the following compounds iv) to xix) are preferable because they are easy to obtain raw materials, have good productivity, and have a cured product of a high refractive index.

iv) In the above formula (II), x is 2 or 3, y is 0, Y ¹ is an alkyl group having ¹ to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms or a ring formed of adjacent Y ^{1 s} Y ² and Z are an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms, and q and r are 0 to 2;

v) a compound represented by the following general formula (IV).

(Wherein, Y ^{2 '} is the same as Y ² or a hydrogen atom of the formula (II), x' is 1 or 2, A ¹ and A ² are the same as in the formula (II) ¹ , Z, n, q and r are the same as in the above general formula (II). On the other hand, an optical isomer present when n is not 0 may be any isomer.

vi) a compound wherein n in the general formula (II) or (IV) is 0-5.

vii) a compound wherein Y < ² > in the general formula (II) or (IV) is a phenyl group.

viii) a compound wherein Y ¹ is an alkyl group having ¹ to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms when q is 0 or 1 and q is 1 in the formula (II) or (IV)

ix) In the above formula (II), x is 2, y is 0, Y ² is a phenyl group, q is 0, q 'is 0, q is 1, r is 0, 2.

The episulfide compound represented by the general formula (II) is not particularly limited. For example, as shown in the following reaction formula, by reacting the epoxy derivative (2) with thiourea, ) Can easily be produced.

The episulfide compound of the present invention can be used as a curable resin composition to be described below and as a cured product obtained by heating and / or irradiating the above-mentioned curable resin composition with energy rays, and also can be used as a cement mortar, Paints or adhesives for leather, glass, rubber, plastic, wood, cloth and paper; Pressure-sensitive adhesives such as adhesive tapes for packaging, adhesive labels, frozen food labels, removable labels, POS labels, adhesive wallpaper, and adhesive flooring; Art paper, lightweight coated paper, cast coated paper, coated paperboard, carbonless copy paper, impregnated paper, and the like; Fiber treatment agents such as natural fibers, synthetic fibers, glass fibers, carbon fibers, metal fibers and the like, anti-fouling agents, and processing agents; Building materials such as sealants, cement admixtures, and waterproofing materials; And can be used in a wide range of applications such as encapsulants for electronic and electric devices.

Next, the curable resin composition of the present invention (hereinafter also referred to as a first curable resin composition) containing the novel episulfide compound represented by the above general formula (I) or (II) and a curing agent will be described. On the other hand, the contents of the above-mentioned episulfide compounds are suitably applied to the parts not specifically described in the following description.

Examples of the curing agent include polyalkylpolyamines such as diethylenetriamine, triethylenetriamine, and tetraethylenepentamine; Polyether polyamines such as polyoxypropylene diamine and polyoxypropylene triamine; Diaminocyclohexane, 1,4-diamino-3,6-diethylcyclohexane, isophoronediamine, mensen diamine, norbornene diamine, bis (4-amino-3-methyldicyclohexyl) (Aminomethyl) cyclohexane, N-aminomethylpiperazine, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro 5) alicyclic polyamines such as undecane; m-xylylenediamine,? - (m / p aminophenyl) ethylamine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiethyldimethyldiphenylmethane, diaminodiethyldiphenyl Aromatic polyamines such as methane, dimethylthiotoluenediamine, diethyltoluenediamine,?,? '-Bis (4-aminophenyl) -p-diisopropylbenzene and dithiodianiline ). Also, these polyamines and glycidyl ethers such as phenyl glycidyl ether, butyl glycidyl ether, bisphenol A-diglycidyl ether, and bisphenol F-glycidyl ether, or glycidyl esters of carboxylic acid A polyepoxy addition modified product prepared by reacting various epoxy resins such as polyether polyol, Amide modification products prepared by reacting these polyamines with carboxylic acids such as phthalic acid, isophthalic acid and dimeric acid by a conventional method; By reacting these polyamines with aldehydes such as formaldehyde and phenols having at least one aldehyde reactive site in the nuclei such as phenol, cresol, xylenol, t-butylphenol, resorcin and the like by a conventional method (Hereinafter referred to as modified materials of polyamines), and the like. Further, latent curing agents such as dicyandiamide, acid anhydride and imidazoles such as 2-ethyl-4-methylimidazole can be used. Particularly, polyamines, modified products of the above-mentioned polyamines and imidazoles are preferable, and imidazoles are more preferable in terms of storage stability and curability.

In the first curable resin composition, the content of the curing agent is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the epithulfide compound. When the content of the curing agent is less than 0.01 parts by weight, the curing rate is slow or the curing is insufficient. When the content is more than 20 parts by weight, the strength of the cured product is insufficient.

The first curable resin composition may further contain, if necessary, a curing catalyst; Reactive and / or non-reactive diluents (plasticizers), such as epoxy compounds, oxetane compounds, dioctyl phthalate, dibutyl phthalate, benzyl alcohol, coal tar; A filler such as glass fiber, carbon fiber, cellulose, silica sand, cement, kaolin, clay, aluminum hydroxide, bentonite, talc, silica, fine powder silica, titanium dioxide, carbon black, graphite, iron oxide, bitumen or the like Pigments; aminopropyltriethoxysilane, N -? - (aminoethyl) -? - aminopropyltriethoxysilane, N-? - (aminoethyl) -N'- (3,4-epoxycyclohexyl) ethyltriethoxysilane, vinyltriethoxysilane, N (trimethylsilyl) ethane, N, N-dimethylaminopropyltriethoxysilane, ? - (N-vinylbenzylaminoethyl) -? - aminopropyltriethoxysilane,? -methacryloxypropyltrimethoxysilane,? -chloropropyltrimethoxysilane,? -mercaptopropyltrimethoxysilane Silane coupling agents such as; Surfactants; Such as candelilla wax, carnauba wax, Japanese wax, white wax, beeswax, lanolin, spermaceti, montan wax, petroleum wax, fatty wax , Fatty acid esters, fatty acid ethers, aromatic esters, aromatic ethers and the like; Thickener; Chisel tropic; Antioxidants; Photosensitizers; Light stabilizer; Ultraviolet absorber; Flame retardant; Defoamer; Anti-rust agent; Storage stabilizer; Colloidal silica, colloidal alumina, and the like. Further, viscous resins such as xylene resin and petroleum resin may be used in combination. In the first curable resin composition, these optional additives are preferably not more than 500 parts by mass, based on 100 parts by mass of the epithulfide compound.

Examples of the epoxy compound which may be used as the reactive and / or non-reactive diluent (plasticizer) include hydrogenated bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, Epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylcyclohexanecarboxylate, 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4- Epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl- Epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-methadioxane, bis (3,4-epoxycyclohexyl Methylcyclohexylcarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylenebis (3,4-epoxy Cyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl hexahydrophthalate, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol Triglycidyl ether of trimethylolpropane, tetraglycidyl ether of sorbitol, hexaglycidyl ether of dipentaerythritol, diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol , Polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as propylene glycol, trimethylol propane and glycerin, polyglycidyl ethers of aliphatic long chain Diglycidyl esters of dibasic acids, monoglycidyl ethers of aliphatic higher alcohols, phenols, cresols, butylphenols, Monoglycidyl ether of polyether alcohol obtained by adding an alkylene oxide to one of them, glycidyl ester of higher fatty acid, epoxidized soybean oil, octyl stearate, butyl stearate, epoxylated polybutadiene, etc. (3-ethyl-3-hydroxymethyloxetane, 3- (meth) allyloxymethyl-3-ethyloxetane, (3- Ethyl-3-oxetanylmethoxy) methylbenzene, 4-methoxy- [1- (3-ethyl- (3-ethyl-3-oxetanylmethyl) benzene, [1- (3-ethyl-3-oxetanylmethoxy) ethyl] phenyl ether, isobutoxymethyl Ethyl-3-oxetanylmethyl) ether, isobornyl (3-ethyl-3-oxetanylmethyl) ether, 2-ethylhexyl , Ethyldiethylene glycol (3-ethyl-3-oxetanylmethyl) ether, dicyclopentadiene (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyloxyethyl Ethyl-3-oxetanylmethyl) ether, dicyclopentenyl (3-ethyl-3-oxetanylmethyl) ether, tetrahydrofurfuryl Ethyl-3-oxetanylmethyl) ether, 2-tetrabromophenoxyethyl (3-ethyl-3-oxetanylmethyl) ether, tribromophenyl (3-ethyl-3-oxetanylmethyl) ether, 2-tribromophenoxyethyl (3-ethyl- Ethyl-3-oxetanylmethyl) ether, butoxyethyl (3-ethyl-3-oxetanylmethyl) ether, pentachlorophenyl 3-oxetanylmethyl) ether, boron (3-ethyl-3-oxetanylmethyl) ether, (3-oxetanyl) -5-oxa-nonane, 3,3 '- (1,3- (2-methylenyl) propanediylbis (oxymethylene) , [1,3-bis (3-ethyl-3-oxetanylmethoxy) methyl] benzene, Ethyl 3-oxetanylmethyl) ether, dicyclopentenylbis (3-ethyl-3-oxetanylmethyl) propane, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tricyclodecanediyldimethylene (3-ethyl-3-oxetanylmethyl) ether, trimethylolpropane tris (3-ethyl-3-oxetanylmethyl) ether, 1,4- (3-ethyl-3-oxetanylmethoxy) hexane, pentaerythritol tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexaquis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol pentaquis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexaquis (3-ethyl-3-oxetanylmethyl) ether, diphenylacetyltetrakis Ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropane tetrakis 3-oxetanylmethyl) ether, PO-modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, EO modified hydrogenated bisphenol A bis Hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, and EO-modified bisphenol F (3-ethyl-3-oxetanylmethyl) ether.

The first curable resin composition may contain a solvent. In this case, the amount of the solvent used is such that the total content of the episulfide compound and the curing agent is preferably in the range of 5 to 90 mass%, more preferably 10 to 50 mass%, in the first curing resin composition do. Specific examples of the solvent include ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, and cyclohexanone; Ether solvents such as ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane and dipropylene glycol dimethyl ether; Esters such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, and n-butyl acetate; Cellosolve solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and propylene glycol monomethyl ether acetate; Alcohol-based solvents such as methanol, ethanol, iso-or n-propanol, iso- or n-butanol, and amyl alcohol; BTX type solvents such as benzene, toluene and xylene; Aliphatic hydrocarbon solvents such as hexane, heptane, octane and cyclohexane; Terpene-based hydrocarbon oils such as terphenyl oil, D-limonene, and pinene; Paraffin solvents such as Mineral Spirit, Swazor # 310 (Kosomo Matsuyama Sekiyu Co., Ltd.), Solvesso # 100 (Exxon Chemical Co., Ltd.); Halogenated aliphatic hydrocarbon solvents such as carbon tetrachloride, chloroform, trichlorethylene and methylene chloride; Halogenated aromatic hydrocarbon solvents such as chlorobenzene; N, N-dimethylformamide, N-methylpyrrolidone, etc. Among them, a ketone or a cellosolve solvent may be used as the solvent, and the solvent may be selected from the group consisting of acetone, acetonitrile, desirable. The solvent used in the synthesis of the episulfide compound may be directly added to the first curing resin composition without being removed.

The first curable resin composition can be cured by heat treatment. The heat treatment is preferably performed at a temperature in the range of 100 to 300 占 폚 for 10 to 240 minutes.

Next, a description will be given of the curable resin composition of the present invention (hereinafter also referred to as a second curable resin composition) containing the novel episulfide compound represented by the general formula (I) or (II) and the energy ray- do. On the other hand, the contents of the above-described episulfide compound and the first curing resin composition are appropriately applied to parts not specifically described in the following description.

The energy ray-sensitive initiator is a compound capable of emitting a substance that initiates cationic polymerization by irradiation of energy ray sensitivity, more specifically, irradiation of an energy ray as described later.

Particularly preferable examples of the energy ray-sensitive cationic polymerization initiator include double salts, such as an onium salt which releases Lewis acid by irradiation with energy ray sensitivity, or derivatives thereof. Representative examples of such a compound include a salt of a cation and an anion represented by the general formula [A] ^{y +} [B] ^y- .

The cation [A] ^{+ y} is preferably an onium, and its structure, for example, can be expressed as _{^{[(R) x Q] y}} +.

R is an organic group having 1 to 60 carbon atoms and may contain several atoms other than carbon, and x is an integer of 1 to 5. x Rs may be the same or different independently from each other. It is also preferred that at least one of x Rs is an aromatic group. Q is an atom or atomic group selected from the group consisting of S, N, Se, Te, P, As, Sb, Bi, O, I, Br, Cl, F and N = When the valence of Q in the cation [A] ^{y +} is z, it is necessary that the relation y = xz is established.

The anion [B] ^y- is preferably a halide complex, and its structure can be represented, for example, by [LX _s ] ^y- .

In addition, L is a metal or a metalloid, which is a central atom of a halide complex, and B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, Mn, and Co. X is a halogen atom. s is an integer from 3 to 7; Also, when the valence of L in the anion [B] ^y- is t, it is important that the relation y = st holds.

A, hexafluorophosphate (PF ₆₎ ^{- -} anion of the general formula [LX _s] borate (BF ₄₎ tetrafluoroethylene Specific examples of ^y-, antimonate hexafluorophosphate (SbF ₆₎ ^-, aralkyl-hexafluoro (AsF ₆ ) ^- , hexachloroantimonate (SbCl ₆ ) ^- , and the like, preferably hexafluoroantimonate (SbF ₆ ) ^- .

Further, as the anion [B] ^y- , those having a structure represented by [LX _s ^-1 (OH)] ^y- can also be used. L, X, and s are the same as described above. Examples of other anions that can be used include perchlorate ion (ClO ₄ ) ^- , trifluoromethyl sulfite ion (CF ₃ SO ₃ ) ^- , fluorosulfonate ion (FSO ₃ ) ^- , toluenesulfonate anion, trinitrobenzenesulfonate anion .

Tetrakis (pentafluorophenyl) borate may also be used as the anion [B] y-.

Among the onium salts, the use of an aromatic onium salt is particularly effective in the present invention. Among them, the aromatic halonium salts described in JP-A-50-151997, JP-A-50-158680, JP-A-50-151997, JP-A-52-30899 , Japanese Patent Laid-Open Publication No. 56-55420, Japanese Unexamined Patent Publication No. 55-125105, and the like, the VA group aromatic onium salts described in JP-A-50-158698, Oxosulfuronium salts disclosed in JP-A-56-8428, JP-A-56-149402, JP-A-57-192429, etc., aromatic compounds described in JP-A-49-17040 Diazonium salts, and thiopyrylium salts described in U.S. Patent No. 4,139,655 are preferred.

Particularly preferred among these aromatic onium salts are those represented by the following general formula (V), (VI) or (VII)

(Wherein R1 to R14 are each a hydrogen atom, a halogen atom, a hydrocarbon group which may contain an oxygen atom or a halogen atom, an alkoxy group which may be substituted, and a phenyl group which may be substituted with at least one hydrogen atom A compound having a sulfonium cation represented by the formula: (Tricumyl) iodonium cation; A compound having a bis (t-butylphenyl) iodonium cation; A compound having a triphenylsulfonium cation and the like.

For example, 4- (4-benzoyl-phenylthio) phenyl-di- (4-fluorophenyl) sulfonium hexafluorophosphate; Bis [bis ((? -Hydroxyethoxy) phenyl) sulfonio] phenylsulfide-bis-hexafluorophosphate, 4,4'-bis [bis ) Phenyl) sulfonio] phenylsulfide-bis-hexafluoroantimonate; Bis [bis (fluorophenyl) sulfonio] phenylsulfide-bis (bis (fluorophenyl) sulfonio] phenylsulfide-bis-hexafluorophosphate, 4,4'- - hexafluoroantimonate; 4,4'-bis (diphenylsulfonio) phenylsulfide-bis-hexafluorophosphate, 4,4'-bis (diphenylsulfonio) phenylsulfide-bis-hexafluoroantimonate; 4- (4-benzoylphenylthio) phenyl-di- (4- (? - hydroxyethoxy) phenyl) sulfonium hexafluorophosphate, 4- ? -hydroxyethoxy) phenyl) sulfonium hexafluoroantimonate; (4-benzoylphenylthio) phenyl-di- (4-fluorophenyl) sulfonium hexafluorophosphate, 4- Fluoroantimonate; 4- (4-benzoylphenylthio) phenyl-diphenylsulfonium hexafluorophosphate, 4- (4-benzoylphenylthio) phenyl-diphenylsulfonium hexafluoroantimonate; 4- (phenylthio) phenyl-di- (4- (beta -hydroxyethoxy) phenyl) sulfonium hexafluorophosphate, 4- ) Phenyl) sulfonium hexafluoroantimonate; 4- (phenylthio) phenyl-di- (4-fluorophenyl) sulfonium hexafluoroantimonate; 4- (phenylthio) phenyl-di- (4-fluorophenyl) sulfonium hexafluorophosphate; 4- (phenylthio) phenyl-diphenylsulfonium hexafluorophosphate, 4- (phenylthio) phenyl-diphenylsulfonium hexafluoroantimonate; (2-chloro-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluorophosphate, 4- ) Sulfonium hexafluoroantimonate; 4- (2-chloro-4-benzoylphenylthio) phenyldiphenylsulfonium hexafluorophosphate, 4- (2-chloro-4-benzoylphenylthio) phenyldiphenylsulfonium hexafluoroantimonate; (4-hydroxyphenyl) sulfonium hexafluorophosphate, 4- (2-chloro-4-benzoylphenylthio) phenylbis ) Sulfonium hexafluoroantimonate; Triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate; (Tolylcumyl) iodonium hexafluorophosphate, (tolylcumyl) iodonium hexafluoroantimonate; (Tolylcumyl) iodonium tetrakis (pentafluorophenyl) borate; Bis (tertiary butylphenyl) iodonium hexafluorophosphate, bis (tertiary butylphenyl) iodonium hexafluoroantimonate; Bis (tert-butylphenyl) iodonium tetrakis (pentafluorophenyl) borate; Benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate; Benzyldimethylsulfonium hexafluorophosphate, benzyldimethylsulfonium hexafluoroantimonate; p-chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, p-chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate; 4-acetoxyphenyldimethylsulfonium hexafluorophosphate, 4-acetoxyphenyldimethylsulfonium hexafluoroantimonate; 4-methoxycarbonyloxyphenyldimethylsulfonium hexafluorophosphate, and 4-methoxycarbonyloxyphenyldimethylsulfonium hexafluoroantimonate; 4-ethoxycarbonyloxyphenyldimethylsulfonium hexafluorophosphate, and 4-ethoxycarbonyloxyphenyldimethylsulfonium hexafluoroantimonate; ? -naphthylmethyldimethylsulfonium hexafluorophosphate,? -naphthylmethyldimethylsulfonium hexafluoroantimonate; alpha -naphthylmethyltetrahydrothiophenium hexafluorophosphate, alpha -naphthylmethyltetrahydrothiophenium hexafluoroantimonate; Cinnamyl dimethylsulfonium hexafluorophosphate, cinnamyl dimethylsulfonium hexafluoroantimonate; Cinnamyltetrahydrothiophenium hexafluorophosphate, cinnamyltetrahydrothiophenium hexafluoroantimonate; < RTI ID = 0.0 > N- (α-phenylbenzyl) cyanopyridinium hexafluorophosphate, N- (α-phenylbenzyl) -2-cyanopyridinium hexafluoroantimonate; N-cinnamyl-2-cyanopyridinium hexafluorophosphate, N-cinnamyl-2-cyanopyridinium hexafluoroantimonate; N- (α-naphthylmethyl) -2-cyanopyridinium hexafluorophosphate, N- (α-naphthylmethyl) -2-cyanopyridinium hexafluoroantimonate; N-benzyl-2-cyanopyridinium hexafluorophosphate, N-benzyl-2-cyanopyridinium hexafluoroantimonate; (4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium tetrakis (3,5-difluoro-4-methoxyphenyl) borate.

Further preferable examples include xylene-cyclopentadienyl iron (II) hexafluoroantimonate, cumene-cyclopentadienyl iron (II) hexafluorophosphate, xylene-cyclopentadienyl iron (II) -tris Iron / allene complexes such as fluoromethylsulfonyl) methanamide, and aluminum complex / photodegradable silicon compound-based initiators.

The energy ray-sensitive cationic polymerization initiator may be used singly or in combination of two or more. The curing agent used in the first curable resin composition may also be mixed and used. The amount of the energy ray-sensitive cationic polymerization initiator used or the total amount of the energy ray-sensitive cationic polymerization initiator and the curing agent is 0.05 to 20 parts by mass based on 100 parts by mass of the episulfide compound. When the amount is less than 0.05 parts by mass, curing of the curable resin composition becomes insufficient, which causes deformation and unevenness, or cracks during heating, which is not preferable. When the amount is more than 50 parts by mass, the content of the ionic substance in the adhesive layer formed by curing the curable resin composition is increased, so that the hygroscopic property of the cured product is increased and the durability performance can not be sufficiently obtained. More preferably, the energy ray-sensitive cationic polymerization initiator is used in an amount of 0.5 to 15 parts by mass based on 100 parts by mass of the episulfide compound.

The second curable resin composition may contain any of the additives exemplified in the description of the first curable resin composition. In the second curable resin composition, these optional additives are preferably not more than 500 parts by mass in total, based on 100 parts by mass of the epithulfide compound.

The second curable resin composition may contain a solvent. In this case, the amount of the solvent to be used is preferably 5 to 90 mass%, more preferably 10 to 90 mass%, and more preferably 10 to 20 mass%, based on the total amount of the episulfide compound, the energy ray-sensitive cationic polymerization initiator and / To 50% by mass. Specific examples of the solvent include solvents exemplified in the first curable resin composition, among which ketones or cellosolve solvents are preferred. The solvent used in the synthesis of the episulfide compound may be contained in the second curable resin composition as it is without being removed.

The second curable resin composition can be cured in a contact dry state or in a solvent insoluble state after irradiation of an energy ray such as ultraviolet ray, usually in 0.1 seconds to several minutes. Suitable energy lines include any of those which cause the decomposition of the cationic polymerization initiator. Preferred examples thereof include metal halide lamps, fluorescent lamps, tungsten lamps such as ultrahigh, high, medium and low pressure mercury lamps, xenon lamps, 2000 angstroms obtained from an excimer lamp, a sterilizing lamp, an excimer laser, a nitrogen laser, an argon ion laser, a helium cadmium laser, a helium neon laser, a krypton ion laser, various semiconductor lasers, a YAG laser, Electromagnetic energy having a wavelength of 7000 angstroms, or high-energy radiation such as electron beam, X-ray, and radiation.

The second curable resin composition can also be cured by a heat treatment. Preferably, a heat treatment is appropriately performed before and after the energy ray irradiation to obtain a cured product having good quality.

The first and second curable resin compositions described above can be used as an ink, a protective film, a paint, a coating agent, an adhesive, an insulating material, a structural material, an optical disk, a sealing agent, and an optical brightener in addition to the cured product described below.

Next, the cured product of the present invention obtained by heating and / or irradiating the first and / or second curable resin composition with energy rays will be described. On the other hand, the contents of the episulfide compound and the first and second curable resin compositions are appropriately applied to parts not specifically described in the following description.

The conditions such as heating and energy ray irradiation are as described above.

The shape of the cured product of the present invention is not particularly limited, and examples thereof include a lens shape, a film shape, a prism shape, and a plate shape. The material may be coated or encapsulated by curing it on another material.

The cured product of the present invention is useful for optical parts such as an optical lens, an optical film, a light guide plate, a waveguide, an optical element, and an optical connector.

[Example]

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples and the like. Examples 1-1 to 1-3 show production examples of the novel episulfide compounds of the present invention, Examples 2-1 to 2-8 show production examples and evaluation examples of the first and second curable resin compositions , And Comparative Examples 2-1 to 2-7 show production examples and evaluation examples of the comparative curable resin composition. Examples 3-1 to 3-3 show production examples and evaluation examples of cured products obtained by curing the first curable resin composition, and Comparative Example 3-1 shows production examples and evaluation examples of comparative cured products. Examples 4-1 and 4-2 show production examples and evaluation examples of cured products obtained by curing the second curable resin composition, and Comparative Examples 4-1 to 4-3 show production examples and evaluation examples of comparative cured products.

[Example 1-1] Preparation of episulfide compound A-1

100 g of 1,1-bis (4- (2,3-epoxypropyloxy) phenyl) -3-phenylindan, 250 g of tetrahydrofuran and 60.0 g of ethanol were charged into a three-necked flask equipped with a stirrer and a thermometer And dissolved well by stirring. Thereto was added 44.2 g of thiourea, and the mixture was heated to 45 캜 and stirred for 18 hours. Thereafter, 300 mL of toluene, 200 mL of ethyl acetate and 300 mL of water were added, the mixture was washed with a separating funnel, and the aqueous layer (aqueous layer) was discarded. Further, the organic layer was washed twice with 300 mL of 10% brine, dried well with anhydrous magnesium sulfate, and desolvated to obtain a crude product. The crude product was separated and purified by silica gel column chromatography (developing solvent: toluene) to obtain 73.0 g of a colorless viscous solid (episulfide compound (A-1)) in a yield of 69%. As a result of various analyzes, it was confirmed that the colorless viscous solid was the episulfide compound (compound No. 53 in which n = 0) of the present invention. The substitution ratio of sulfur to the thiirane ring of the oxirane ring obtained from elemental analysis was 98%. The results of the analysis are shown below.

(Analysis)

(1) Chemical shift of ¹ H-NMR (DMSO-d 6, 35 ° C): (ppm)

2.42-2.45 (m: 2H), 2.49-2.73 (m: 3H), 3.15-3.20 2H), 7.15-7.26 (m, 5H), 7.30-7.35 (m, 3H) (m: 2H).

(2) Sulfur content by elemental analysis (content measured by TOX-100 manufactured by Dia Instruments)

Measured value: 12.1%, theoretical value: 12.3%.

(3) IR (cm ^-1 )

3027, 2868, 1605, 1579, 1507, 1468, 1454, 1397, 1292, 1245, 1181, 1118, 1032, 1011, 828, 779, 756, 736, 701

[Example 1-2] Preparation of episulfide compound A-2

A three-necked flask equipped with a stirrer and a thermometer was charged with 50.0 g of 1,1-bis (4- (2,3-epoxypropyloxy) phenyl) -3,5-diphenylindane, 270 g of tetrahydrofuran, And dissolved well by stirring. Thereto was added 14.8 g of thiourea, and the mixture was stirred at room temperature for 48 hours. Then, 1000 mL of toluene and 300 mL of water were added, and the mixture was washed with a separating funnel and the aqueous layer was discarded. The organic layer was washed twice with 300 mL of 10% aqueous sodium chloride, dried well with anhydrous magnesium sulfate, and then desolvated to obtain 50.2 g of a colorless solid (episulfide compound (A-2)) in a yield of 95%. As a result of various analyzes, it was confirmed that the above-mentioned colorless solid was the episulfide compound (compound No. 44 in which n = 0) of the present invention. The substitution ratio of sulfur to the thiiran ring of the oxirane ring obtained from elemental analysis was 96%. The results of the analysis are shown below.

(Analysis)

(1) Chemical shift of ¹ H-NMR (DMSO-d 6, 35 ° C): (ppm)

2H), 2.76-2.82 (m: 1H), 3.21-3.36 (m, 3H), 3.80-3.86 (m: 1H) (M: 1H), 6.88-6.92 (m, 4H), 6.98 (s, 1H), 4.00-4.03 ), 7.05-7.09 (m: 2H), 7.14-7.20 (m, 3H), 7.25-7.41 (m: 8H), 7.48-7.55

Measured value: 10.3%, theoretical value: 10.7%.

(3) IR (cm ^-1 )

3027, 2925, 1604, 1579, 1508, 1475, 1298, 1245, 1181, 1035, 914, 830, 763, 701

[Example 1-3] Preparation of episulfide compound A-3

A flask equipped with a stirrer and a thermometer was charged with 30.0 g of bis [4- (2,3-epoxypropyloxy) phenyl] cyclohexyl (4-biphenyl) methane, 150 g of 1,4-dioxane, And dissolved well by stirring. Thereto was added 10.2 g of thiourea, and the mixture was stirred at 50 DEG C for 24 hours. After that, 300 mL of toluene, 200 mL of ethyl acetate and 300 mL of water were added, and the mixture was washed with a separating funnel and the aqueous layer was discarded. Further, the organic layer was washed twice with 300 mL of 10% aqueous sodium chloride, dried well with anhydrous magnesium sulfate, and then desolvated to precipitate a white powdery crystal. The crystals were washed with toluene and hexane and dried well to obtain 22.5 g of colorless crystals (episulfide compound (A-3)) in a yield of 71%. As a result of various analyzes, it was confirmed that the colorless crystals were the episulfide compound (compound No. 1 in which n = 0) of the present invention. The substitution ratio of sulfur to the thiiran ring of the oxirane ring obtained from elemental analysis was 92%. The results of the analysis are shown below.

(Analysis)

(1) Chemical shift of ¹ H-NMR (DMSO-d 6 at 25 ° C): (ppm)

2H), 3.11-3.22 (m, 2H), 3.80 (m, 2H), 2.01 (d, (m, 2H), 3.86 (s, 1H), 3.96 m: 2H), 7.44 (d: 2H), 7.57 (d: 2H)

Actual value: 10.1%, theoretical value: 11.0%

(3) IR (cm ^-1 )

2929, 2845, 1606, 1508, 1236, 1181, 1032, 824, 764, 763

[Examples 2-1 to 2-8 and Comparative Examples 2-1 to 2-7] Production of Curable Resin Composition Nos. 1 to 8 and Comparative Curable Resin Composition Nos. 9 to 15

The episulfide compounds (A-1) to (A-3) and the diluent (C-1) or (C-2) prepared in Preparation Examples 1 to 3 were mixed according to the mixing ratios shown in Table 1, (D-1) or a cationic polymerization initiator (D-2) was added thereto, and the mixture was stirred for 10 minutes to obtain a curable resin composition No. 1 to No. 8 was prepared. (B-1) to (B-3) shown below were used instead of the episulfide compound of the present invention in accordance with the compounding ratio of [Table 2] to obtain Comparative Curable Resin Composition No. 9 &Lt; tb > The solubility of the obtained composition was evaluated. The results are shown in [Table 1] and [Table 2].

(B-1) 2,2-bis (4- (2,3-epithiopropyloxy) phenyl) propane

(B-2) 9,9-bis (4- (2,3-epithiopropyloxy) phenyl) fluorene

(B-3) 1,1-bis (4- (2,3-epoxypropyloxy) phenyl)

(C-1) ADEKA RESIN EP-4100E (manufactured by ADEKA Corporation): bisphenol A type epoxy resin): diluent

(C-2) glycidyl phenyl ether: diluent

(D-1) 2-ethyl-4-methylimidazole: Thermal curing agent

(ADEKA OPTOMER SP-172, manufactured by ADEKA Corporation) (D-2) 4- (2-chloro-4-benzoylphenylthio) phenylbis : Energy ray sensitive cationic polymerization initiator

The resulting curable resin composition was stirred at 60 캜 for 10 minutes, cooled to room temperature, and evaluated for its solubility. On the other hand, when the precipitates were not confirmed even when the solution was cooled to room temperature, the results were rated?, When the precipitates were observed after 1 day after cooling to room temperature,?, When the precipitates were not dissolved by heating.

As is clear from [Table 1] and [Table 2], while the composition using the comparative compound (B-2) had poor solubility and storage stability, the compositions of Examples 2-1 to 2- -8 is excellent in solubility in a diluent. In addition, in Comparative Examples 2-1 and 2-4, no curable resin composition was obtained because it was not dissolved, and in Comparative Example 2-7, crystals precipitated after cooling to room temperature.

[Examples 3-1 to 3-3 and Comparative Example 3-1]

The obtained curable resin compositions No. 1 to No. 3 and Comparative Curable Resin Composition No. 10 were each heated to 60 占 폚 and applied to a glass substrate subjected to releasing treatment. The specimens were put in a glass pan with a spacer of 1.00 mm and bonded together and heated at 100 占 폚 for 1 hour and at 150 占 폚 for 1 hour for curing and? For non-curing. The refractive index and transparency of the cured product were evaluated. The results are shown in Table 3.

The refractive indices n _d and n _e of D-line and e-line at 25 ° C were measured with an Abbe refractometer DR-M2 manufactured by Atago Co., Ltd. for the obtained cured product.

[Table 3] shows that the cured product of the comparative curable resin composition No. 10 (comparative example 3-1) comprising the diluent and the heat curing agent is superior in curability using the episulfide compounds A-1 to A-3 of the present invention It is clear that the cured products of Resin Compositions Nos. 1 to 3 (Examples 3-1 to 3-3) have a high refractive index.

[Examples 4-1 and 4-2 and Comparative Examples 4-1 to 4-3]

The obtained curable resin compositions No. 4 and No. 5 and the comparative curable resin compositions No. 11, No. 13, and No. 14 were each heated to 60 占 폚 and applied to a releasing-treated glass substrate. The glass substrate was exposed to light at 3000 mJ / cm 2 (total of 6000 mJ / cm 2) on a glass surface with a high-pressure mercury lamp, and then treated at 150 ° C for 2 hours and cooled to room temperature And peeled off from the glass substrate. The curability was evaluated as? For the cured product and? For the cured product. The refractive index and transparency of the cured product were evaluated. The results are shown in Table 4.

The total light transmittance of the resulting cured product was measured with a haze meter NDH5000 manufactured by Nihon Denshoku Kogyo Co., Ltd.

The comparative curable resin composition No. 11 (Comparative Example 4-1) using the comparative compound (B-1) exhibited good solubility but poor curability and the curable resin (B- The comparative curable resin composition No. 14 (Comparative Example 4-3) comprising the composition No. 13 (Comparative Example 4-2) and the diluent and the energy ray-sensitive cationic polymerization initiator had good curability but a poor refractive index and transparency.

On the contrary, the curable resin compositions Nos. 4 and 5 (Examples 4-4 and 4-5) using the episulfide compound A-1 of the present invention are excellent in curability, refractive index and transparency.

From the above, it can be seen that the episulfide compound of the present invention is excellent in solubility and further contains these compounds, and the curable resin composition of the present invention is obtained by providing a cured product having a high refractive index and excellent in curability and transparency, . &Lt; / RTI >

Claims

An episulfide compound characterized by being represented by the following general formula (I).

(Wherein, A ¹ and A ² are sulfur atoms, Cy is a cycloalkyl group having 3 to 10 carbon atoms, X is an aryl group having 6 to 20 carbon atoms, 10, p is 0 to 5, and r is an integer of 0. On the other hand, the optical isomer present when n is not 0 may be any isomer.

An episulfide compound characterized by being represented by the following general formula (II).

(Wherein in the formula (Ⅱ), A ¹ and A ² denotes a sulfur atom, Y ¹ and Y ² are each independently a methyl group or a carbon atom represent an aryl group of 6~20 atoms, n is 0~10, q is Q is 0 to 8 (provided that q 'is not more than (x + y) x 2), r is 0, x is 0 to 4, y is an integer of 0 to 4, x and y Is 2 to 4. On the other hand, the optical isomer present when n is not 0 may be any isomer.

The method according to claim 1,
An episulfide compound characterized by being represented by the following general formula (III).

(In the above general formula (III), A ¹ , A ² , n and r are the same as in the general formula (I).) On the other hand, an optical isomer present when n is not 0 may be any isomer.

3. The method of claim 2,
An episulfide compound characterized by being represented by the following general formula (IV).

(Wherein, in the general formula (IV), Y ^{2 '} is the same as or different from Y ² in the general formula (II), and x' is 1 or 2, and A ¹ and A ² are as defined in the general formula equals ⅱ), Y ^1, n, q and r are the same as the above general formula (ⅱ). On the other hand, optical isomers exist when n is not zero may be either any isomer).

5. The method of claim 4,
Wherein x 'in the general formula (IV) is 1.

A curable resin composition characterized by containing the episulfide compound according to any one of claims 1 to 5 and a curing agent.

A curable resin composition characterized by containing an episulfide compound according to any one of claims 1 to 5 and an energy ray-sensitive cationic polymerization initiator.

A cured product obtained by heating a curable resin composition,
The curable resin composition contains an episulfide compound and a curing agent or an episulfide compound and an energy ray-sensitive cationic polymerization initiator,
The curable resin composition according to any one of claims 1 to 5, wherein the episulfide compound is an episulfide compound.

A cured product obtained by irradiating the curable resin composition according to claim 7 with an energy ray.