TW201120022A - Novel episulfide compounds, curable resin compositions containing the episulfide compounds, and cured products thereof - Google Patents

Abstract

Provided are: compounds which exhibit excellent curability and transparency and are useful particularly for optical use; and curable resin compositions using the compounds. Specifically provided are episulfide compounds represented by general formula (I) or (II). In general formula (I), A1 and A2 are each an oxygen atom or a sulfur atom (with the proviso that A1 and A2 are not both oxygen atoms); Cy is C3-10 cycloalkyl; X and Z are each independently C1-10 alkyl or the like; n is 0 to 10; p is 0 to 5; and r is an integer of 0 to 4. In general formula (II), Y1 and Y2 are each C1-10 alkyl or the like; A1, A2, Z, n and r are each as defined for general formula (I); n is 0 to 10, q is 0 to 4, and q' is 0 to 8 (with the proviso that q' is equal to or below (x+y)2); and x is a number of 0 to 4 and y is a number of 0 to 4, with the sum of x and y being 2 to 4.

Description

201120022 VI. Description of the Invention: [Technical Field] The present invention relates to a novel episulfide compound, a curable resin composition containing the episulfide compound and a hardener and/or an energy ray-sensitive cationic initiator And its hardened matter. [Prior Art] * The first, transparent and high refractive index hardened material is used for optical materials such as lenses. In particular, it is actively developed in the fields of electronic materials and optical materials due to excellent electrical properties, heat resistance, adhesion, optical properties, and the like of a cured resin in combination with a curing agent. For example, a semiconductor sealing material, an antireflection film such as a liquid crystal display, a protective film of a color filter, a lens, a mirror surface, and an edge of an optical device such as an optical waveguide, a camera, etc., are reported to have a branched alkyl sulfide. The compound type episulfide compound is reported in Patent Document 2 as a direct bond-based sulfide-type cyclic compound compound. The patent discloses that there are (iv) (iv) episulfide compounds. However, the heat resistance of the yttrium is problematic. Further, in Patent Document 4, there is an episulfide compound having a skeleton having a high resistance to sputum, which is a precursor material. However, there is a problem that the clams are poorly soluble in the thinner, and it is impossible to produce a resin composition for obtaining a cured product of the refractive index of the present invention. [Patent Document 1] Japanese Patent Laid-Open Publication No. Hei 9- No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. SUMMARY OF THE INVENTION PROBLEM TO BE SOLVED BY THE INVENTION The object of the present invention is to provide a compound which is excellent in curability, transparency, and the like, particularly useful in optical applications, and a compound which uses the same. A curable resin composition. The inventors of the present invention have found that the epoxy sulfide compound having a specific structure is excellent in solubility, and further, the curable resin composition containing the episulfide compound is excellent in storage stability. The cured product has a high refractive index and is excellent in transparency, and the above problems are solved by using it. The present invention is based on the above findings and provides a novel episulfide compound represented by the following general formula (I) or (II):

(wherein A1 and A2 represent an oxygen atom or a sulfur atom (wherein at least one of A1 and A2 represents a sulfur atom), 〇 represents a cycloalkyl group having a carbon number of 3 to 1 Å, and XAZ independently represents a number of carbon atoms; An alkyl group of fluorene, an arylalkyl group having 7 to 20 carbon atoms and a carbon atom number of 2 to 20, a heterocyclic group having 2 to 20 carbon atoms, an alkyl group having 3 to 3 atomic groups or a halogen atom, In the alkyl and arylalkyl group 150139.doc 201120022 -S- or a double bond interrupt, the methylene group and the bonding portion of the aryl group may be further, Z may form an aromatic ring with each other adjacent Z; the alkyl group, The aryl group, the arylalkyl group, the heterocyclic group, the ring county, and the aromatic ring formed by the adjacent two are substituted by a fang atom, n represents an integer of 〇~1〇, and p represents a 〇~5=number, r An integer representing from 0 to 4; in addition, the optical isomer present when n is not ruthenium may be any isomer) [Chemical 2]

(Formula, A1 and A2 represent an oxygen atom or a sulfur atom (wherein, and at least one of 八 and 2 represent a sulfur atom)' γ丨, 丫2 and 2 each independently represent an alkyl group having a carbon number H〇, a carbon atom An aryl group having 6 to 20 aryl groups, an arylalkyl group having 7 to 2 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 1 ring of carbon atoms or a halogen atom; And the methylene group in the arylalkyl group and the bonding moiety of the aryl group may be interrupted by -0-, -S. or a double bond, and adjacent to each other may be bonded to each other to form a %, s-alkyl group, an aryl group, The arylalkyl group, the heterocyclic group and the cycloalkyl group may be substituted by a halogen atom, η represents an integer of 〇10, q represents an integer of 〇~4, and 纩 represents an integer of 0-8 (where 'q is (χ+γ) ) χ 2 or less), r represents an integer of 〇~4, X represents an integer of 0 to 4, y represents an integer of 〇~4, and the total of 乂 and 丫 is 2 to 4; and the case where 'π is not 0 The optical isomer can be any isomer). Further, the present invention provides a curable resin composition comprising the novel episulfide compound represented by the above formula (I) or (II) and a curing agent. Further, the present invention provides a curable resin composition which contains the novel episulfide compound represented by the above formula (1) or (II) and an energy ray-sensitive cation initiator. Further, the present invention provides a cured product which is obtained by heating and/or irradiating an energy ray to the curable resin composition. Advantageous Effects of Invention The epoxy sulfide compound of the present invention is excellent in solubility, and further, the curable resin composition containing the cyclic cucurbitide compound is excellent in curability and storage stability, and can provide a cured product having a high refractive index and excellent transparency. [Embodiment] 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 formula (1) or (ι). First, the episulfide compound represented by the above formula (1) will be described. Examples of the alkyl group having 3 to 10 carbon atoms represented by cy 'X and z in the above formula (1) include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, and a ring. Heptyl, cyclooctyl, cyclodecyl, cyclodecyl and the like. The oxime is an alkyl group having 1 to 10 carbon atoms represented by the above formula (1) and 2, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptylene group, and a fluorene group. The base, the thiol group, etc., as the group of the fluorene group in the alkyl group, which is interrupted by -0, may, for example, be a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a methoxy group or an ethoxy group. The base group &, 2-methoxyethyl group, etc., as the base group of the alkylene group in the alkyl group interrupted by -s- can be exemplified by methylthio group, ethyl sulfide 150139.doc 201120022 group, butylthio group, pentane The thio group or the like 'as a group in which the methylene group in the alkyl group is interrupted by a double bond' may, for example, be an allyl group, a 3-butenyl group or the like. Examples of the aryl group having 6 to 2 carbon atoms represented by X and Z in the above formula (I) include a phenyl group, a naphthyl group, a 2-naphthyl group, a fluorenyl group, and a fluorenyl group. O-tolyl, m-tolyl, p-tolyl, 3 fluorenyl, 9-fluorenyl, 1-tetrahydronaphthyl, 2-tetrahydronaphthyl, anthracene-dihydroindenyl, diterpene, 2_ In the case of an indane group, a biphenyl group, etc., as a group in which the bonding moiety of the aryl group is interrupted, a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a diterpeneoxy group, or a phenoxy group is mentioned. , o-tolyloxy, m-nonyloxy, p-tolyloxy, 9-decyloxy, 1-indenyloxy, 2-indolyloxy, etc., as the bonding moiety of the aryl group by _s_ The base of the interruption is exemplified by phenylthio group! _Naphthylthio, 2_naphthylthio, i 蒽 thio, 1-phenanthyl, o-tolylthio, m-tolylthio, p-tolylthio, 9-thiol, 1-tetrahydronaphthalene The base '2-tetrahydronaphthylthio group, phenanthrenylthio group, 2-membered thio group, etc.' is a group in which the bonding moiety of the aryl group is interrupted by a double bond, and examples thereof include a styryl group and the like. Examples of the arylalkyl group having 7 to 2 carbon atoms represented by the above formula (1) and 2 are exemplified by a benzyl group, a phenethyl group, a 2-phenylpropyl 'diphenyl group, a triphenyl group. The methyl group or the like 'as a methylene group in the arylalkyl group is a group of -cm, and an oxy group, a phenoxymethyl group, a phenoxyethyl 'mercaptomethoxy 2-naphthyl anthracene The oxy group, the decyl fluorenyl group, etc., as a group in which the methylene group in the aryl group is interrupted, a sulfhydryl group and a benzene sulfide are mentioned! A methyl group, a phenylthioethyl group or the like is used as a group in which the methylene group in the aryl group is interrupted by a double life, and examples thereof include a phenallyl group. As a group of a carbon atom having a carbon number of 2 to 2 Å represented by MZ in the above formula (1), for example, a pyrrolyl group, a pyridyl group, a pyrimidinyl group, a ruthenium group, a piperylene group, or a piperidinyl group can be mentioned. , pyranyl, pyrazolyl, tri-nurgical, pyrrolidinyl, quinolyl, isoquinolyl, imidazolyl, benzimidazolyl, triazolyl, furyl 'furanyl, Benzofuranyl, thienyl, thiophenyl, benzothienyl, thiadiazolyl, thiazolyl, benzothiazolyl, oxazolyl, benzoxazolyl, isothiazolyl, iso Carbazolyl, fluorenyl, pyrrolidinyl, morpholinyl, thiomorpholinyl, 2-pyrrolidone, phenyl, 2-piperidone, 2,4-dioxoimidazole Acridine-3-yl, 2,4-dioxosoxazol-3-yl, and the like. The aromatic ring formed by the adjacent Z in the above formula (I) may, for example, be a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring or an anthracene ring. a halogen atom represented by X and Z in the above formula (1), and an alkyl group, an aryl group, an arylalkyl group, a hetero-alkyl group, a cycloalkane which may be substituted for X and Z in the above formula (I). Fluorine, gas, bromine, and iodine can be cited as the elemental atom of the aromatic ring formed by the base and the adjacent z. The aromatic ring formed by the alkyl group, the aryl group, the arylalkyl group, the heterocyclic group, the cycloalkyl group and the Z represented by the above X and z in the above formula (I) may have a substituent, and examples thereof include a mercapto group. , ethyl, propyl, isopropyl, cyclopropyl, butyl, second butyl, tert-butyl, isobutyl, pentyl, isopentyl, tert-amylcyclopentyl, hexyl, 2 -hexyl, 3-hexyl, cyclohexyl, bicyclohexyl, 1-decylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, isoheptyl, third heptyl, n-octyl, isooctyl , an alkyl group such as a third octyl group, a 2-ethylhexyl group, a decyl group, an isodecyl group or a fluorenyl group; a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a second butoxy group Base, tert-butoxy, isobutoxy, 150139.doc -9- 201120022 pentyloxy, isopentyloxy, third pentyloxy, hexyloxy, cyclohexyloxy-heptyloxy, iso-heptane Alkoxy groups such as oxy, third heptyloxy, n-octyl decyl, isooctyloxy, trioctyloxy, 2-ethylhexyloxy, nonyloxy, decyloxy; thiol and ethylthio , propylthio, isopropylthio, butylthio, second butadiene, second Sulfur, isobutylthio, pentylthio, isopentylthio, third pentylthio, hexylthio, cyclohexylthio, heptylthio, isoheptylthio, third heptylthio, n-octyl sulfide Alkylthio such as isooctylthio, isooctylthio, 2-ethylhexylthio; vinyl, 1-mercaptovinyl, 2-methylvinyl, 2-propenyl, 1-methyl 3-ylpropenyl, 3-butenyl, indolyl 3-butenyl, isobutyl, 3-pentenyl, 4-hexenyl, cyclohexenyl, dicyclohexenyl, heptene Alkenyl group such as benzyl, octenyl, nonenyl, pentadecyl, eicosyl, and trisyl; benzyl, phenethyl, diphenylmethyl, triphenylmethyl, stupid An aryl group such as a dilute group or a phenylpropyl group; an aryl group such as a phenyl group or a naphthyl group; an aryloxy group such as a phenoxy group or a naphthyloxy group; an arylthio group such as a phenylthio group or a naphthylthio group; 2-oxetyl, propyl, octyl, acrylonitrile, mercaptopropyl, phenyl (phenyl phenyl), phthalic acid, 4-trimethyl decyl benzene Mercapto, trimethyl ethane, o-hydroxyphenyl fluorenyl, oxalyl, octadecyl, methoxycarbonyl, ethoxy a fluorenyl group such as a carbonyl group, a tert-butoxycarbonyl group, an n-octadecyloxycarbonyl group or an amine fluorenyl group; a decyloxy group such as an ethoxycarbonyl group or a benzhydryloxy group; an amine group, an ethylamino group and a dimethyl group; Amino, diethylamino, butylamino, cyclopentylamino, 2-ethylhexylamino, dodecylamino, anilino, phenylphenylamino, anthranilyl, A Oxanilide, anthracene-fluorenyl-anilino, diphenylamino, naphthylamino, 2-»-pyridylamino, methoxycarbonylamino, phenoxycarbonylamino, acetylamine Base, benzamidine amine 150139.doc -10- 201120022 base, guanylamino 'trimethyl ethinylamine, laurylamine, amine guanamine, N,N-dimethylaminocarbonyl Amine, N,N-diethylaminocarbonylamino, porphyrincarbonylamino, methoxycarbonylamino, ethoxycarbonylamino, tert-butoxycarbonylamino, n-octadecyloxy Alkylcarbonylamino, N-fluorenyl-methoxycarbonylamino, phenoxycarbonylamino, aminesulfonylamino, N,N-dimethylaminosulfonylamino, methylsulfonamide a substituted amine such as butylsulfonylamino, phenylsulfonylamino a group; a sulfonylamino group, a sulfonyl group, a carboxyl group, a cyano group, a sulfo group, a hydroxyl group, a nitro group, a decyl group, a quinone imine group, an amine sulfhydryl group, a sulfonylamino group, etc. . Further, in the case of substituting with a substituent having a carbon atom, an alkyl group, an aryl group, an aryl group, a heterocyclic ring represented by X and Z in the above formula (I) containing the substituent are used. The number of carbon atoms of the aromatic ring formed by the group, the cyclohexyl group and the adjacent Z satisfy the predetermined number of carbon atoms. In the case of the episulfide compound represented by the above formula (I) and the episulfide compound of the above formula (II), when n is not a quinone, an optical isomer may be present, which may be any difference. The structure, the compounds shown herein below are not limited to specific optical isomers. The episulfide compound represented by the above formula (1) is exemplified by the following compound N. The compound shown in Table 13. Further, in the following chemical formula, n represents a number of 0 to 10. However, the present invention is not limited by the following compounds. 150139.doc 201120022 [Chemical 3] Compound No.l

Compound No. 2

Compound No.3

Compound No. 4

Compound No. 5

150139.doc -12- 201120022 [Chemical 4] Compound No. 6

Compound No. 8

Compound No. 9

150139.doc -13- 201120022 [Chemical 5] Compound Ν〇.1()

Compound N〇<l2

Compound Κίο l3

In the above-mentioned cyclic sulfide compound of the above formula (1), in the above formula (1), the compound having a reverse atomic number of a stone or a carbon number of 6 to an aryl group is considered to be stable in storage of a compound of 〇2 and η of 〇5. Since it is good, it is preferable.) 150139.doc -]4·201120022 The compound of the following i) to iii) is more preferable because the raw material is easily obtained and the productivity is good. 〇 A compound represented by the following formula (ΠΙ). [Chemical 6]

(In the formula, A1, A2, Ζ are the same as the above formula (1). Further, the optical isomer present when 'n is not ruthenium may be any isomer) ϋ) X in the above formula (1) is a carbon atom The aryl group of 6 to 20, the compound of {) is hydrazine or 1, and η is 0 to 2. Iii) The compound of the above formula (III) wherein η is 〇~2. The method for producing the episulfide compound represented by the above formula (I) is not particularly limited. For example, by reacting the epoxy derivative oxime with thiourea as shown in the following reaction formula, the above-mentioned pass can be easily produced. An episulfide compound represented by the formula (1). [Chemistry 7]

150139.doc -15- 201120022 Further, by increasing or decreasing the amount of thiourea used in the reaction or the reaction time, the substitution of the oxygen atom in the oxirane ring in the epoxy derivative as a raw material can be arbitrarily controlled. The ratio of the sulfur atom (sulfur substitution ratio) may be used as the episulfide compound of the present invention in the state of remaining an epoxy derivative as a part of the raw material or an unsubstituted oxirane ring in the product, depending on the purpose. . The higher the sulfur substitution rate, the higher the refractive index of the cured product, so it is preferably 50% to 1%% and further preferably 8% to 1%. Next, the episulfide compound represented by the above formula (I) will be described. In the following description, the episulfide compound represented by the above formula (I) can be suitably used in the portion which is not particularly described. In the above formula (11), the number of carbon atoms represented by γ1, .2, and 2 in the above formula (11) and the fluorene group in the 'primary earth' and the halogen group are -0-, The base of the -S - or double bond interrupt is exemplified in the above description of the general formula (I). The carbon atom number 6 to 2 as shown in the above formula (Π), " and 2 The group in which the aryl group and the aryl group are interrupted by _〇·, _S_ or a double bond may be exemplified in the description of the above formula (I). The aryl group having 7 to 2 carbon atoms represented by γ2 and Z, and the group of the fluorene group in the arylalkyl group interrupted by -〇-, _S_ or a double bond can be exemplified by the above formula (1) The group exemplified in the above formula (1), wherein the heterocyclic group having 2 to 2 carbon atoms represented by Y丨, Y2 and Z in the above formula (Π) is exemplified in the description of the above formula (1) The basis. The cycloalkyl group having 3 to 1 ring carbon atoms represented by the above formula (II) and Y2 and Z may, for example, be exemplified in the description of the above formula (I). 150139.doc -16- 201120022 In addition to the exemplified γ Ι bond in the above formula (II), in addition to the exemplified as the aromatic ring in the above formula (1), the nucleus ring, the mu ring, the ring (tetra) ring κ ring, a ring of 5 to 7 members such as a ring of styrene, an internal vinegar ring, an inner guanamine ring, a condensed ring of a ring, a dangerous ring, a full ring, and a full ring. As the enthalpy in the above formula (11), a functional atom shown, and an alkyl group, an aryl group, an arylalkyl group, a heterocyclic group, a cycloalkyl group, and an adjacent γι bond which may be substituted for Y1, 丫2 and 2 in the above formula (II). Examples of the halogen atom of the fluorene structure formed by the nucleus include the groups exemplified in the description of the above formula (1). The alkyl group, the aryl group and the arylalkyl group represented by the oxime 1, oxime 2 and oxime in the above formula (II) a heterocyclic group, a cycloalkyl group, and a hydrazine adjacent thereto; the cyclic structure formed by the bonding may have a substituent, and examples of the substituents include the groups exemplified in the description of the above formula (1), and the groups Further, when it is substituted by a substituent having a carbon atom, the alkyl group, the aryl group, and the aryl group represented by the above formula (Π) containing the substituent are represented by γΐ, Υ2, and Ζ. The number of carbon atoms in the cyclic structure in which the alkyl group, the heterocyclic group, the cycloalkyl group and the adjacent fluorene form each other satisfies the predetermined number of carbon atoms. The episulfide compound represented by the above formula (II) For example, the compound represented by the following compound No. 14 to Νο_62 may be mentioned. Further, in the chemical formula, η represents a number of 0 to 10. However, the present invention is not limited to the following compounds. 150139.doc 17- 201120022 [Chemical 8] Compound No. 14

[Chem. 9] Compound No. 17

150139.doc -18- 201120022 Compound No. 19

Compound No. 22

-19- 150139.doc 201120022

Compound No.27

150139.doc -20- 201120022 Compound No.29

[Chem. 12] Compound No. 32

Si 150139.doc -21 201120022 Compound No.34

Compound No.37

150139.doc -22- 201120022 Compound No.39

Compound No.42 s^0

Compound No.43

150139.doc -23 201120022 Compound No.44

Compound No.46

-24- 150139.doc 201120022 Compound No.49

[Chem. 16] Compound No. 5 1

Compound No. 52

150139.doc -25- 201120022 Compound No.53

Compound No.54

[Chem. 17] Compound No. 55

Compound No. 5 7

150139.doc -26- 201120022 Compound No.58

Compound No. 60

Compound No. 62

150139.doc -27- 201120022 Among the episulfide compounds represented by the general formula (II), the following Q products of iv) to ix) are easily obtained from raw materials and have good productivity, and a cured product having a high refractive index can be obtained. Therefore, it is better. Iv) In the above formula (II), 乂 is 2 or 3, 〇, γ1 is an alkyl group having a carbon number, an aryl group having 6 to 20 carbon atoms, or a Jf formed by adjacency Y is an aromatic ring The base of Y/z is a compound having a carbon atom number of 1 (), an aryl group having a carbon number of 6 to 20, and q and r are 〇~2. V) a compound represented by the following formula (IV). [Chem. 19]

(IV) (wherein Y2' is the same as Y2 of the above formula („) or represents a hydrogen atom, X is or 2, and A1 and A2 are the same as those of the above-mentioned general formula, γ1, z, n, 仏 and The formula (Π) is the same. Further, the optical isomer present when η is not 〇 may be any isomer) vi) the compound of the above formula (II) or (ιν) wherein η is 〇~5 Νϋ) a compound of the above formula (II) or (IV) wherein γ2 is a phenyl group. The above formula (11) or (IVK "〇5t, when it is an alkyl group having 1 to 10 carbon atoms or a carbon atom a compound of the aryl group of 6 to 2 。, lx) wherein X in the above formula (II) is 2, y is 〇, Υ 2 is phenyl 'q is 〇, ^ is 〇, q is 1, and r is 0. η is a compound of 〇~2. The method for producing the episulfide compound represented by the above formula (II) is not specifically limited to 150139.doc • 28·201120022. For example, the epoxy derivative (7) is reacted with thiourea by the following reaction formula. The episulfide compound represented by the above formula („) can be easily produced.

The episulfide compound of the present invention can be used for concrete, in addition to the curable resin composition described below, and the use of the curable resin composition to heat or to obtain a cured product obtained by irradiating an energy ray. Cement sand, various metals, leather, glass, rubber, plastic, wood, cloth, paper, etc. Coatings or adhesives; packaging tape, point-and-stick, cold; East food labels, removable labels, p〇s 〇w Sale, point of sale label, sticky wallpaper, point Bodhi engage M cage + '') 言土,, (4) 荨 荨 黏 adhesive; coated paper, lightweight, cloth paper m coated cardboard, carbonless copy paper , such as processing such as impregnating paper, such as fiber, synthetic fiber, glass fiber, carbon fiber, metal fiber, precipitation inhibitor, processing agent, etc.; fiber mixture agent for sealing mixture, waterproof material; electronic equipment Use a wide range of applications. 150139.doc • 29-201120022 The curable resin composition of the present invention containing the novel episulfide compound represented by the above formula (1) or (II) and a curing agent (hereinafter, also referred to as first hardening) The resin composition) is explained. Further, in the following description, the contents described in the above episulfide compound can be suitably used in the portions which are not particularly described. Examples of the curing agent include polyalkyl polyamines such as diethylenetriamine, diethylenetriamine, and tetraethyleneamine; polyether polyamines such as polyoxypropylene diamine and polyoxypropylene triamine. ;丨, 2_diaminocyclohexane, hydrazine, 4-diamino-3,6-diethylcyclohexane, isophoronediamine, menthanediamine, norbornene diamine, double (4-Amino-3-methyldicyclohexyl)methane, diamine dicyclohexanane, bis(aminomethyl)cyclohexane, N-aminomercaptopiperazin, 3,9-bis ( Alicyclic polyamines such as 3-aminopropyl)-2,4,8,10-tetraoxaspiro(5,5)undecane; m-xylylenediamine, α_(m-/p-aminobenzene) Ethylamine, m-diamine, diaminodiphenylmethane, diaminodiphenyl sulfone, diaminodiethyldidecyldiphenyl decane, diaminodiethyl benzene Aromatic polyamines such as decane, dithiol toluenediamine, diethyl phenylenediamine, α,α, bis(4-aminophenyl)-diisopropyl bromide, dithiodiphenylamine Classes and the like (hereinafter, referred to as polyamines). Further, examples of the polyamines include glycidyl ethers such as phenyl glycidyl ether, butyl glycidyl ether, bisphenol hydrazine diglycidyl ether, and bisphenol F-glycidyl ether, or A polyepoxy addition modification produced by reacting various epoxy resins such as carboxylic acid glycidyl ester; the polyamines and phthalic acid, isophthalic acid, dimer acid are conventionally obtained The imidization modification produced by the reaction of a carboxylic acid; the polyamines are mixed with formaldehyde by a conventional method, and the benzene, formazan, xylene, 150139.doc -30· 201120022 A mannated butyl group or a benzoic acid-containing modified product obtained by reacting a phenol having at least one acid-reactive site in the core (hereinafter referred to as a modified product of a polyamine). Further, a latent curing agent such as an imidazole such as diaryldiamine, an acid anhydride or 2-ethyl-4·mercaptopimidazole can also be used. Particularly, the above-mentioned polyamines, modified polyamines and imidazoles are more preferably imidazoles in terms of stability and hardenability. In the first curable resin composition A, the content of the curing agent is preferably 〇 〇 1 2 2 〇 〇 by weight, more preferably 0·1 〜5 by weight based on 1 part by weight of the cyclized compound. Parts by weight. If the content of the hardener is less than 1 weight, the curing rate is slow or insufficient, and if it exceeds 20 parts by weight, the strength of the cured product is insufficient. Further, the first curable resin composition may contain a curing catalyst as needed; an epoxy compound, an oxetane compound, dioctyl phthalate, dibutyl phthalate, benzoquinone Reactive and/or non-reactive diluents (plasticizers) such as alcohol and coal tar; glass fiber, carbon fiber 'cellulose, quartz sand, cement, kaolin' clay, aluminum hydroxide, bentonite, talc, cerium oxide , fine powder of ceria, titanium dioxide, carbon black, graphite, iron oxide, asphalt materials and other fillers or pigments; γ-aminopropyl triethoxy decane, Ν-β-(aminoethyl)_γ-amine Propyltriethoxydecane, Νβ-(aminoethyl)-Ν'-β-(aminoethyl)_γ-aminopropyltriethoxydecane, γ-anilinopropyltriethyl Oxydecane, γ-glycidoxypropyltriethoxydecane, β-(3,4-epoxycyclohexyl)ethyltriethoxydecane, vinyltriethoxydecane, Ν-β -(Ν-vinylbenzylaminoethylaminopropyltriethoxydecane, γ-mercaptopropenyloxypropyltrimethoxydecane, 150139.doc 2011200 22 γ-gas propyl trimethoxy stone shallow, sulfhydryl propyl 锶 丨 丨. X and ω · 々丨 石 夕 夕 矽 矽 矽 矽 矽 偶 偶 矽 矽 矽 矽 矽 矽 ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; Wax, insect damage, bee soil, lanolin, record sacrifice, A 'snails, fatty acids, fat _, fat (four), aromatic spices, aromatic lying and other lubricants, · additives; thixotropic agents, · anti- An oxidizing agent; a photosensitizer; a light stabilizer ultraviolet absorber; a flame retardant; a defoaming agent; an anti-money agent; a storage stabilizer; a colloidal cerium oxide, a colloidal alumina, and the like, and a xylene resin, In the ninth curable resin composition, it is preferable that the additive is a total of 5 parts by mass or less based on 100 parts by mass of the episulfide compound. Examples of the epoxy compound which can be used as the above-mentioned reactive and/or non-reactive diluent (plasticizer) include hydrogenated bisphenol human diglycidyl ether and 3,4% oxygen% hexylmethyl_3,4. - Epoxy cyclohexane carboxylate, 3,4_epoxy_丨_methylcyclohexyl-3,4-epoxy_ 1_Methylcyclohexyl phthalate, 6_mercapto-3,4_epoxycyclohexyldecyl-6-methyl-3,4-epoxycyclohexanone, 3,4-ring Oxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate '3,4_epoxy_5-decylcyclohexyldecyl-3,4-ring Oxy-5-nonylcyclohexanecarboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-dioxane, bis ( 3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexylcarboxylate, methylene bis(3,4-epoxycyclohexane), two Cyclopentadiene diepoxide, exoethyl bis(3,4-epoxycyclohexanecarboxylate), epoxy hexahydrophthalic acid dioctyl vinegar, epoxy hexahydrophthalic acid di- 2-ethylhexyl ester, iota, 4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, triglycidyl ether of glycerol, triglycidyl ether of trishydroxypropyl propane , sorbitol four shrink 150139.doc -32- 201120022 κ glyceryl ether pentaerythritol hexahydroglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether and other polyols glycidol - ,: again in C Polyglycidol of a polyether polyol obtained by adding one or more kinds of alkylene oxides to an aliphatic polyol such as an alcohol, a dihydroxymethyl propyl group or a glycerin, and an aliphatic long-chain dibasic acid Diglycidyl acetonate, monoglycidyl hydrazide of aliphatic higher alcohol or (d), f19, butyl benzoquinone, monoglycidyl ether of polyether alcohol obtained by adding alkylene oxide, and shrinkage of higher fatty acid Glycerin-based, epoxidized soybean oil, epoxy succinate, octyl sulphate, oxidized polybutylene, etc., as a diluent that can be used as a reactive and/or non-reactive ( The oxetane compound of the plasticizer) may, for example, be 3-ethyl-3-hydroxymethyl oxetane or 3-(methyl)-dipoxyfluorenyloxybutane. (3-ethyl-3-3 oxetanylmethoxy)methylbenzene, 4-fluoro-[1-(3-ethyl_3_oxetanylmethoxy)methyl] Benzene, 4·methyllacyl-[1-(3-ethyl-3-oxetanylmethoxy)methyl]benzene, [h (3-ethyl-3-oxetanyl) Methoxy)ethyl]phenyl ether, isobutoxymethyl (3·ethyl·3·oxacyclobutane) Methyl)-, isobornyloxyethyl (3 ethyl-3-oxetanylmethyl)ether, isobornyl (3-ethyl-3-oxybenzobutanylmethyl) hydrazine , 2-ethylhexyl (3-ethyl-3 oxetanyl methyl) ether, ethyl diethylene glycol (3_ethyl_3_oxetanylmethyl) ether, Dicyclopentadiene (3-ethyl·3·oxetanylmethyl) shunt, dicyclopentenyloxyethyl (3-ethyl-3-oxetanylmethyl)ether , Dicyclopentenyl (3_ethyl· 3-oxetanyl decyl) ether, tetrahydrofuran methyl (3•ethyl _3 • oxetanylmethyl) ϋ, Si Mo. Phenyl (3_ethyl_3_oxetanylmethyl)ether, 2-tetrabromophenoxyethyl (3_ethyl_3_oxetanylmethyl)ether, I50139 .doc -33- 201120022 Tribromophenyl (3-ethyl-3.oxetanylmethyl)ether, 2·tribromophenoxyethyl (3-ethyl-3-oxetane) Alkylmethyl)ether, 2-hydroxyethyl (3_ethyl_3_oxetanylmethyl)ether, 2-hydroxypropyl (3_ethyl_3_oxetanyl) Ether, butoxyethyl (3_ethyl_3_oxetanylmethyl)ether , penta-phenyl (3-ethyl-3-oxetanylmethyl) ether, pentabromophenyl (3-ethyl-3-oxetanylmethyl) ether, borneol ( 3_ethyl_3_oxetanylmethyl)ether, 3,7-bis(3-oxetanyl)-5-oxydecane, 3,3,_ (1'3- (2-decenyl)propanediylbis(oxymethylene))bis-(3-ethyloxetane), 1,4-bis[(3-ethyl-3-oxocycle) Butyl methoxy) fluorenyl] benzene, 1,2-bis[(3-ethyl-3-oxetanyloxy)indolyl]ethane, hydrazine, 3_bis[(3-B) Benzyl-3-oxetanylmethoxy)indolyl]propane, ethylene glycol bis(3·ethyl-3-oxetanylmethyl)ether, dicyclopentenyl double ( 3_ethyl_3_oxetanylmethyl)ether, triethylene glycol bis(3_ethyl_3_oxetanylalkyl)ether, tetraethylene glycol double (3_ Ethyl_3_oxetanylmethyl)ether, tris: fluorenyl-methylene (3-ethyl-3-oxetanylmethyl) scale, tris-propyl propane Tris(3-ethyl-3-oxetanyl)alkyl, hydrazine, 4bis(3-ethyl-3-oxetanyloxy)butane, i, 6_bis(3_ethyl_3_oxetanylmethoxy)hexane, pentaerythritol tris(3_ethyl_3_oxetanylmethyl)ether, pentaerythritol tetrakis(3- Ethyl-3-oxetanylalkyl)ether, polyethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, dipentaerythritol hexa(3-ethyl-3) - Oxide 衣 烧 烧 ) ) 谜 谜 谜 、 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二Mercapto)ether, caprolactone modified dipentaerythritol hexa(3·ethyl_3_oxetanylmethyl)ether, caprolactone modified dipentaerythritol penta(3_ethyl_3_oxygen 150139 .doc -34- 201120022 Heterocyclic Dingsylmethyl Ether, Di-Tris-methyl-propyl 4-(3-ethyl-3-(oxetanylmethyl), EO (ethylene oxide, epoxy) Ethane) modified bisphenol a bis(3-ethyl-3-oxaxanthylene) fluorene, p〇(pr〇pyie.ne 〇xide, propylene oxide) modified bisphenol A double 3-ethyl-3·oxetanylmethyl)ether, hydrazine-modified hydrogenated bisphenol bis(3-ethyl-3-oxetanyl fluorenyl)ether, ρ〇 Modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanyl fluorenyl) ether, E 〇 modified bisphenol F (3-ethyl-3-oxetanyl fluorenyl) Ether, etc. The first curable resin composition may contain no solvent. In this case, the content of the solvent is preferably from 5 to 90% by mass, more preferably from 5 to 90% by mass, based on the total of the above-mentioned episulfide compound and the above-mentioned curing agent. It is a range of 1〇~5〇% by mass. Specific examples of the solvent include ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, decyl isobutyl ketone, and cyclohexanone. An ether solvent such as diethyl ether, dioxane, tetrahydrofuran, hydrazine, 2, dimethoxy ethane, 1,2-ethoxy ethane, dipropylene glycol dimethyl ether; decyl acetate, ethyl acetate, acetic acid An ester solvent such as n-propyl ester, isopropyl acetate or n-butyl acetate; a cellophane solvent such as ethylene glycol monoterpene ether, ethylene glycol monoethyl ether or propylene glycol monoterpene ether acetate; An alcohol solvent such as iso- or n-propanol, iso- or n-butanol or pentanol; a solvent such as benzene, toluene and xylene; hexane, heptane, octane, and Alkane and other aliphatic hydrocarbon solvents: 3⁄4 fuel, D-moneylene, terpene and other entrained hydrocarbon oils; mineral spirits, Swaz〇l #310 (C〇Sm〇Matsuyama Oil Co., Ltd.), s 〇lvess〇#1〇〇 (Exx〇n Chemical Co., Ltd.) and other stone bad solvents; four gasified carbon, chloroform, triethylene ethylene, two 150139.doc -35· 201120022 gas Halogenated aliphatic hydrocarbon solvent such as methane; halogenated aromatic hydrocarbon solvent such as chlorobenzene; carbitol solvent, aniline, triethylamine, pyridine, acetic acid, guess, carbon disulfide, N,N-dimethyl decylamine 'N-methylpyrrolidone and the like: Among them, a ketone or a celecoxime solvent is preferred. Further, the solvent used in the synthesis of the episulfide compound may not be removed and may be directly contained in the ninth curable resin composition. The first curable resin composition can be cured by heat treatment. The heat treatment is preferably carried out at a temperature of from 100 to 30 (the range of TC is from 1 Torr to 24 Torr.. Next, the new lysine sulfide compound represented by the above formula (1) or (11) and the energy ray sensitivity are contained. The sclerosing tree sputum of the present invention, which is a cationic polymerization initiator, and the following (also referred to as a second curable resin composition) will be described. In part, the above description of the episulfide compound and the curable resin composition can be suitably used. The upper slit line sensitivity initiator is irradiated by energy ray sensitivity, specifically, as described below. A compound capable of releasing a substance which initiates polymerization by irradiation of an energy ray. The above-mentioned energy ray-sensitive cationic polymerization initiator is particularly preferable as a Lewis acid released by energy ray-sensitive irradiation. The rust complex salt or its derivative 1 is a representative of the compound and can be listed as a salt of a cation and an anion represented by the formula [A] [B; p. Here, the cation [A]y+ is preferably Rust, its structure can be, for example, [(R)xQ]y+ The eight-foot scale has a carbon number of 1 to 60, and may contain an organic base other than a few carbons. The organic base of 150139.doc •36·201120022, x is an integer from 1 to 5. Each R is independent and can be the same. Further, it is preferred that at least one of the X R groups is an aromatic group. Q is selected from the group consisting of S, N, Se, Te, P, As, Sb, Bi, 〇, I, Br, ci, j? An atom or a group of atoms in a group consisting of N = N. Further, when the valence of Q in the cation [A]y+ is z, the relationship of y = xz is established. Further, the anion [B] Y- is a halide complex, and its structure can be represented, for example, by [LXs]y. Further, L is a metal ruthenium metal (Metalloid) which is a central atom of a halide complex, and is B, P, As, Sb, Fe, Sn, Bi, A1, Ca, In, Ti, Zn, Sc 'V, Cr, Μη, Co, etc. X is a halogen atom. s is an integer of 3 to 7. Further, an anion [B]y - In the case where the atomic valence of t is set to t, it is important that the relationship of y = s_t is established. Specific examples of the anion [LXs]y- of the above formula include tetrafluoroborate (BF4)··hexafluoro Phosphate (PL)-, hexafluoroantimonic acid (sbF6)., hexafluoroarsenate (AsF6)-, hexafluoroantimonate (sbcu)-, etc., preferably hexafluoroantimonate (SbF6)_. Also, as an anion [B]y·, can be used [ LXs-丨(〇H)]y- structure. L, X, and S are the same as above. Further, as other anions which can be used, perchloric acid ions (cl〇4)_, trifluoroantimony A sulfite ion (CFsSO3), a fluorosulfonate ion (FS〇3), a toluenesulfonic acid anion, a trinitrobenzenesulfonic acid anion, or the like. Further, tetrakis(pentafluorophenyl)borate can also be used as the anion [B]y·. In the present invention, the use of an aromatic rust salt in such an onium salt is particularly effective. Among them, the Japanese Patent Laid-Open No. 50-15, 1997, Sakamoto 150139.doc • 37-201120022 Lie Kaikai 5 (M5880 published in the bulletin No. 50-151997曰 专利 专利 专利 专利 专利 专利 专利 专利 专利 52 52 52 52 52 52 52 -30 -30 -30 -30 -30 -30 -30 -30 -30 -30 -30 -30 -30 -30 -30 -30 -30 -30 -30 -30 -30 -30 -30 -30 -30 -30 -30 -30 -30 -30 -30 -30 -30 -30 -30 -30 -30 -30 -30 -30 -30 Quaternary rust salt, the VA aromatic rust salt disclosed in Japanese Patent Laid-Open No. 5 (M58698), Japanese Patent Laid-Open Publication No. SHO 56-8428, Japanese Patent Laid-Open Publication No. SHO 56-149402, Japanese Patent Laid-Open The oxo-alked salt disclosed in the specification of the Japanese Patent No. 4139655, which is disclosed in the specification of the Japanese Patent No. 4139655, which is disclosed in the Japanese Patent Application Laid-Open No. Particularly preferred among aromatic iron salts is the following formula (ν), (νυ or (VII) [Chem. 21]

～K1 4 is a respective or a hydrocarbyl group which may contain an oxygen atom or a different hydrogen atom or a halogen atom, or an alkoxy group which may have a substituent 150139.doc •38·201120022, and Ar is one or more hydrogen atoms. a compound of a phosphonium cation represented by a substituted phenyl group; a compound containing a (triisopropylphenyl)phosphonium cation; a compound containing a bis(t-butylphenyl)phosphonium cation; and a triphenylphosphonium cation Compounds, etc. For example, 4-(4-phenylmercapto-phenylthio)phenyl-di-(4-fluorophenyl)phosphonium hexafluorophosphate; 4,4'-bis[double ((β-hydroxyl) Oxy)phenyl)indolyl] stupyl sulfide-bis-hexafluorophosphate, 4,4'-bis[bis((β-hydroxyethoxy)phenyl)indolyl]phenyl sulfide-bis-six Fluoride; 4,4'-bis[bis(fluorophenyl)) phenyl sulfide-bis-hexafluorophosphate, 4,4'-bis[bis(fluorophenyl)indenyl]benzenesulfide Ether-bis-hexafluoroantimonate; 4,4'-bis(diphenylfluorenyl) thioether-bis-hexafluorophosphate, 4,4'-bis(diphenylfluorenyl) phenyl sulfide - bis-hexafluoroantimonate; 4-(4-phenylmercaptophenylthio)phenyl-bis-(4-(β-hydroxyethoxy)phenyl)phosphonium hexafluorophosphate, 4-( 4-phenylmercaptophenylthio)phenyl-bis-(4-(β-hydroxyethoxy)phenyl)phosphonium hexafluoroantimonate; 4-(4-benzylidenebenzoyl)benzene -di-(4-fluorophenyl)phosphonium hexafluorophosphate, 4-(4-phenylmercaptophenylthio)phenyl-di-(4-fluorophenyl)phosphonium hexafluoroantimonate; -(4-Benzylmercaptophenylthio)phenyl-diphenylphosphonium hexafluorophosphate, 4-(4-benzylidenephenylthio)phenyl-diphenylphosphonium hexafluoroantimonate; 4 -(phenylthio)phenyl-bis-(4-(β-hydroxyethoxy)phenyl)phosphonium hexafluorophosphate, 4-(phenylthio)phenyl-di-(4-(β-hydroxyl) Ethoxy)phenyl)indole hexafluoroantimonate; 4-(phenylthio)phenyl-di-(4-fluorophenyl)phosphorus hexafluorophosphate, 4-(phenylthio)phenyl-di -(4-fluorophenyl)phosphonium hexafluoroantimonate; 4-(phenylthio)phenyl-diphenylphosphonium hexafluorophosphate, 4-(phenylthio)phenyl-diphenylphosphonium hexafluorophosphate Citrate; 4-(2-chloro-4-benzylidenephenylthio)phenylbis(4-fluorophenyl)phosphonium hexafluorophosphate, 4-(2- gas-4-phenylindole Phenylthio)phenylbis(4-fluorophenyl)phosphonium hexafluoroantimonate; 4-150139.doc -39· 201120022 (2-Ga-4-phenylmercaptophenylthio)phenyldiphenyl Hexafluorophosphate, 4-(2-chloro-4-phenylnonylphenylthio)phenyldiphenylphosphonium hexafluoroantimonate; 4-(2- gas-4-phenylmercaptobenzenesulfide Phenyl bis(4-hydroxyphenyl) hexafluorophosphate, 4-(2- gas-4-phenylmercaptophenylthio)phenyl bis(4-hydroxyphenyl) hexafluoroantimonic acid Salt; triphenylsulfonium hexafluorophosphate, triphenyl hexafluoroantimonate; (tolylcumyl) sulfonium hexafluorophosphate, Phenyl cumyl) hexafluoroantimonate; (tolyliso-propylphenyl) ruthenium tetrakis(pentafluorophenyl)borate; bis(t-butylphenyl)phosphonium hexafluorophosphate, double (t-butylphenyl)phosphonium hexafluoroantimonate; bis(t-butylphenyl)phosphonium tetrakis(pentafluorophenyl)borate; benzyl-4-hydroxyphenylindenylphosphonium hexafluorophosphate , benzyl 4-hydroxyphenyl fluorenyl hexafluoroantimonate; benzyl dimethyl sulfonium hexafluorophosphate, benzyl dimercapto hexafluoroantimonate; p-benzyl benzyl hydroxybenzene曱 曱 疏 六 氟 磷酸盐 、 对 对 对 对 对 对 对 对 -4- ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; Phenyl phenyl fluorenyl hexafluoroantimonate; 4-methoxycarbonyloxyphenyl dimethyl sulfonium hexafluorophosphate, 4-decyloxycarbonyloxyphenyl ruthenium hexafluoroantimonate a salt; 4-ethoxycarbonyloxyphenyldifluorenylphosphonium hexafluorophosphate, 4-ethoxycarbonyloxyphenyldifluorenylphosphonium hexafluoroantimonate; a-naphthylfluorenyldifluorenyl Hexafluorophosphate, α-naphthylmethyldifluorenyl hexafluoroantimonate; (X-naphthylfluorenyltetrahydrothiophosphonium hexafluorophosphate Α-naphthylmethyltetrahydrothiophosphonium hexafluoroantimonate; phenylallyldimethylhydrazine hexafluorophosphate, phenylallyldimethyl hexafluoroantimonate; phenylallyl tetrahydrogen Thiophosphonium hexafluorophosphate, phenallyl tetrahydrothiophosphonium hexafluoroantimonate; Ν-(α-phenylbenzyl)cyanoguanidine rust hexafluorophosphate, Ν-(α-phenyl Benzyl)-2-cyanoguanidine rust hexafluoroantimonate; fluorenyl-phenylallyl-2-cyano. Pyridine hexafluorophosphate, N-phenylallyl-2-cyano 150139.doc -40- 201120022 Pyridine rust hexafluoroantimonate; Ν_(α_naphthylmethyl)_2-cyanopyridinium Fluorophosphate, Ν_(α_naphthylmethyl)-2-cyano-pyridinium hexafluoroantimonate; Ν_knotyl-2-cyano. Pyridine hexafluorophosphate, Ν·benzyl-2-cyanopyrene pyridyl hexafluoroantimonate; (4-benzylidene phenylthio)phenyl bis(4-fluorophenyl)nickel tetra (3 Na-difluoro-4-methoxyphenyl) borate. Further, as other preferred ones, xylene-cyclopentadienyl iron (rhodium) hexafluoroantimonate, cumene-cyclopentadienyl iron (11) hexafluorophosphate, mono-toluene- An iron/aromatic hydrocarbon complex such as a cyclopentadienyl iron (π)-5 (trifluoromethylsulfonyl) decane compound, an aluminum complex/photodecomposition telluride initiator, and the like. The above-mentioned energy ray-sensitive cationic polymerization initiator may be used in combination or in combination of two or more. Further, a curing agent used in the ninth curable resin composition may be used in combination. The amount of the energy ray-sensitive cationic polymerization initiator to be used or the total amount of the energy ray-sensitive cationic polymerization initiator and the hardener to be used is 0.05 to 20 by mass based on 1 part by mass of the above episulfide compound. Share. When the amount of use is less than 5 parts by mass, the curing of the curable resin composition is insufficient, and deformation or unevenness or cracking occurs during heating, which is not preferable. In addition, when the amount of use exceeds 5 parts by mass, the content of the ionic substance in the adhesive layer formed by curing the curable resin composition increases, so that the hygroscopic property of the cured product becomes high, and durability cannot be sufficiently obtained. performance. The amount of the energy-sensitive cationic polymerization initiator to be used is preferably from 5 parts by mass to 15 parts by mass based on the mass of the episulfide compound i. Further, any of the additives exemplified in the description of the second modified resin composition may be added to the second curable resin composition. In the second curable resin group 150139.doc -41 - 201120022, the above-mentioned optional additives are preferably 500 parts by mass or less based on 100 parts by mass of the above-mentioned episulfide compound. The second curable resin composition may also contain a solvent. In this case, it is preferred that the amount of the bathing agent used is such that the above-mentioned episulfide compound, the above-mentioned 旎S: line-sensitive cationic polymerization initiator, and/or the above-mentioned hardener are in the second hardening. The resin composition is preferably in the range of 5 to 9 % by mass, more preferably 10 to 50% by mass. Specific examples of the solvent include the solvents exemplified in the first curable resin composition, and the oxime or celecoxime-based solvent. Further, the solvent used in the synthesis of the above episulfide compound may not be removed and may be directly contained in the second curable resin composition. The second curable resin composition can be cured to a dry state or a solvent-insoluble state by irradiating an energy ray such as ultraviolet rays for usually from 0.1 second to several minutes. As an appropriate energy line, any decomposition can be carried out as long as the decomposition of the cationic polymerization initiator is induced, and it is preferred to use an ultra high, high, medium and low pressure mercury lamp, a 4-gas lamp, a carbon arc lamp, a metal gutta lamp, Fluorescent lamps, crane lamps, excimer lamps, germicidal lamps, excimer laser 'nitrogen lasers, argon ion lasers, cadmium cadmium lasers, helium lasing lasers, helium ion lasers, various semiconductor lasers, YAG (Yttrium Aluminium Garnet, Aluminium Stone) Laser Electromagnetic Energy Line or Electron Beam with a wavelength of 2000 Å to 7000 Å obtained from a light-emitting diode, CRT (Cath〇de Ray Tube) source, etc. High-energy lines such as X-rays and radiation. Further, the second curable resin composition may be cured by heat treatment. It is preferred that if the heat treatment is properly performed before and after the irradiation of the energy ray, a cured product of good quality can be obtained 150139.doc • 42· 201120022. The first and second curable resin compositions described above can be used as an ink, a coating, a coating agent, an adhesive, and an insulation, in addition to the use of the cured product described below. The material, the structural material, the optical disk, the dense sealant, and the light-cured material, and the hardened material of the present invention obtained by energizing or irradiating the first and/or second curable resin composition, . In the following description, the contents of the above-described episulfide compound and the first and second curable resin compositions are used for the portions which are not particularly described. Conditions regarding heating and energy line irradiation, etc., as previously explained. 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 braid shape, and a plate shape. Further, other materials may be coated or sealed by hardening them on other materials. The cured product of the present invention is useful for optical components such as optical lenses, optical films, light guide plates, waveguides, optical elements, and optical connectors. EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples and comparative examples, but the invention is not limited to the examples and the like. EXAMPLES 丨 卜 卜 卜 表示 表示 表示 表示 表示 表示 表示 表示 表示 表示 表示 表示 表示 表示 表示 表示 表示 表示 表示 表示 表示 表示 表示 表示 表示 表示 表示 表示 表示 表示 表示 表示 表示 表示 表示 表示 表示 表示 表示 表示-7 shows a production example and a flat evaluation example of the comparative curable resin composition. (Example 1) A production example and evaluation example of the cured product obtained by hardening the sclerosing resin composition Comparative Example 3 _ 1 shows a comparison example and a evaluation example of the cured product of 150I39.doc • 43-201120022. Examples 4-1 and 4-2 show production examples and evaluation examples of the cured product obtained by curing the second curable resin composition, and Comparative Examples 4-1 to 4-3 show production examples and evaluation examples of the comparatively cured product. . [Example 1-1] An episulfide compound A-manufactured in a three-necked flask equipped with a stirring device and a thermometer, and 1,1 bis(4-(2,3-epoxypropoxy)phenyl) was added. _3•Phenylindene 1 〇〇〇g, tetrahydrofuran 2 brother g, and ethanol 60.0 g were thoroughly stirred to dissolve. 44.2 g of thiourea was added thereto, and the mixture was heated to 45 C and stirred for 18 hours. Thereafter, 3 〇〇 mL of hydrazine, 200 mL of ethyl acetate and 3 mL of water were added, and the mixture was washed with a separating funnel to discard the aqueous layer. Further, the organic layer was washed twice with 3 〇〇 mL of 1% aqueous saline, and then dried over anhydrous sulfuric acid to carry out desolvation to obtain a crude product. The crude product was subjected to (four) column chromatography (developing solvent: toluene) to obtain a result of various analyses of 73 g g of a colorless viscous solid (cyclosulfide compound (Α_1)) β in a yield of 69%. The viscous solid is a compound of the episulfide compound (4) of the present invention). Ethylene oxide ring substitution determined by elemental analysis value = sulfur substitution rate of thioethane ring is 98%»The analysis of the sister fruit is shown in [22], and the mouth is not; n=〇 compound) an episulfide compound (compound Ν〇.53)

(Analytical results) 150139.doc • 44- 201120022 (1) Chemical shift of W-NMR (DMSO-d6, 35 °C): (ppm) 2.42-2.45 (m: 2H), 2.49-2.73 (m: 3H) , 3.15-3.20 (m: 1H), 3.26-3.37 (m: 2H), 3.95-4.02 (m: 2H), 4.07-4.16 (m: 3H), 6.78 (d: 1H), 6.86-6.96 (m: 4H), 7.01-7.07 (m: 3H), 7.08-7.13 (m: 2H), 7.15-7.26 (m: 5H), 7.30-7.35 (m: 2H). (2) The sulfur content obtained by elemental analysis (measured by TOX-100 manufactured by DIA Instruments). Measured value: 12.1%, theoretical value: 12.3%. (3) IRCcm·1) 3027, 2868, 1605, 1579, 1507, 1468, 1454, 1397, 1292, 1245, 1181, 1118, 1032, 1011, 828, 779, 756 '736 > 701 [Example 1 - 2] Manufacture of episulfide compound a-2. In a three-necked flask equipped with a stirring device and a thermometer, 丨, ! bis(4_(2,3-epoxypropoxy)phenyl)-3,5-diphenylfluorene 5 〇.〇g 270 g of tetrahydrofuran and 30_0 g of ethanol were sufficiently stirred to dissolve. 14.8 g of thiourea was added thereto, and the mixture was stirred at room temperature for 48 hours. Thereafter, a solution of 1 〇〇〇 mL and 300 mL of water was added, and the waste water layer was cleaned by a separatory funnel. Further, the organic layer was washed twice with 300 mL of 10% saline solution, and sufficiently dried with anhydrous magnesium sulfate, and then subjected to solvent removal to obtain 5 〇2 in a yield of 95%. § Colorless solid (anthracene compound (Α- 2)) The results of various analyses of β confirmed that the colorless solid was the episulfide compound of the present invention (the compound of n = 0 in the compound 44. 44). From the elemental analysis value, the sulfur substitution rate of the N-oxygenethane ring substituted into the ring thioethane ring was 96%. The results of the analysis are shown below. 150139.doc -45- 201120022 [Chem. 23] an episulfide compound (a compound of n=0 in compound No. 44)

(Analytical results) (Chemical shift of l/H-NMR (DMSO-d6, 35. 〇: (ppm) 2.50 (d: 1H), 2.65 (d: 1H), 2.68-2.71 (m: 2H), 2.76- 2.82 (m: 1H), 3.21-3.36 (m: 3H), 3.80-3.86 (m: 1H), 4.00-4.03 (m: 1H), 4.10-4.15 (m: 1H), 4.18-4.24 (m: 1H ), 4.26-4.31 (m: 1H), 6.88-6.92 (m: 4H), 6.98 (s: 1H), 7.05-7.09 (m: 2H), 7.14-7.20 (m: 3H), 7.25-7.41 (m : 8H), 7.48-7.55 (m: 3H) (2) Sulfur content obtained by elemental analysis (measured by TOX-100 manufactured by dia Instruments) Measured value: 10.3%, theoretical value: 10.7 (3) IRCcm·1) 3027, 2925, 1604, 1579, 1508, 1475, 1298, 1245, 1181, 1035, 914, 830, 763, 701 [Example 1-3] episulfide compound A-3 Manufactured in a three-necked flask equipped with a stirring device and a thermometer, adding bis[4_(2,3-epoxypropoxy)phenyl]cyclohexyl(4-phenyl)methane, 3〇〇g, i ^ 150 g of dioxane and 30_0 g of ethanol were dissolved sufficiently to dissolve. 10.2 g of thiourea was added thereto, and stirred at 5 (TC for 24 hours, after which toluene was added 150139.doc • 46·201120022) 300 mL, 200 mL of ethyl acetate and 3 mL of water were washed with a separatory funnel to discard the aqueous layer. The organic layer was washed twice with 0% saline solution and dried thoroughly with anhydrous magnesium sulfate. Thereafter, the solvent was removed to precipitate a white powdery crystal. The crystal was washed with toluene and a house, and sufficiently dried to obtain 22 5 g of a colorless crystal (a sulfide compound (A-3) in a yield of 71%. )). As a result of various analyses, it was confirmed that the colorless crystal is the episulfide compound of the present invention (the compound of n=〇 in the compound *N〇1). The oxirane ring obtained by the elemental analysis value is substituted into a ring. The sulfur substitution rate of the thioethane ring is 92%. The results of the analysis are shown below. [Chemical 24] The episulfide compound (n=the compound of the compound No.!)

(Analysis results) (1) Chemical shift of 丨H-NMR (DMS〇_d6, 25〇c wide 0.99-1.10 1.30-1.52 (m:5H)j2.〇7 2.3〇(d: 2H), 2.51 (d : 2H), 3.14-3.22 (m: 2H)5 3.80 (dd: 2H), 3.86 (s: (five), 2H), 6.61_6.66 (m: 4H), 6 86 6 % (m: _, 7.2G .7.25 (m: 1H), 7.31_7.37 (m: 2H), 7 44 (d π), 7.57 (d: 2H) (7) Sulfur content obtained by elemental analysis (using τοχ-100 manufactured by insuu_ts) The measured content obtained) 150139.doc •47· 201120022 Measured value: 10.1%, theoretical value: 11.〇〇/. (3) IR(cm*') 2929, 2845, 1606 ' 1508, 1236, 1181, 1032 824, 764 '763 [Example 2-1-2-8 and Comparative Example 2·1 to 2-7] Curable resin composition Ν 1. 1 ~ Ν 〇 · 8 and comparative curable resin composition ν 〇 - 9~Ν〇. 15 Production The episulfide compound (Α-1)~(Α-3) and the diluent (C-1) produced in the above Production Examples 1 to 3 were prepared according to the blending ratio of [Table 1]. Or (C-2) mixing, heating to 100 ° C, stirring to dissolve, cooling to 60 ° C, adding thermal hardener (D-I) or cationic polymerization initiator (D_2) to stir 1 〇 Each of the curable resin compositions No. 1 to No. 8 was produced, and the comparative compounds (B - i) to (Β·3) shown below were used instead of the present invention according to the blending ratio of [Table 2]. The epoxy resin compound was subjected to the same operation to prepare a comparatively curable resin composition Νο·9~Νο.15. The solubility of the obtained composition was evaluated. The results are shown in [Table 1] and [Table 2]. Β-1) 2,2-bis(4-(2,3-cyclothiopropoxy)phenyl)propan ((-2)9,9-bis(4-(2,3-cyclothio) Propoxy)phenyl)indole (B-3), l-bis(4-(2,3-epoxypropoxy)phenyl)-3_phenylindan (Cl) Adeka Resin EP-4100E (Manufactured by ADEKA Co., Ltd.): Bisphenol A type epoxy resin): Diluent (C-2) Epoxypropyl phenyl ether: Diluent (D-1) 2-Ethyl-4-methylimidazole: Thermal Hardener (D-2) 4-(2-Ga-4-Benzylsulfonylphenylthio)phenylbis(4•fluorophenyl) hexafluoroantimonate (Adeka Optomer SP-172, ADEKA) Ltd. I50139.doc -48- 201120022

Made): energy line sensitive cationic polymerization from f 25J

<Solubility> The obtained curable resin was kneaded and Az Kr Λ ,. The mixture was stirred at 60 ° C for 10 minutes, and then cooled to room temperature to evaluate the solubility. Dan has a D sub-estimation standard, and even if it is cooled to room temperature, no precipitate is found as 〇. When it is dissolved while heating, but it is cooled to room temperature, the precipitate is found to be △', even if it is heated. The case of dissolution is set to X. [Table 1] Example 2-1 2-2 2-3 2-4 2-5 2-6 2-7 Hardening, raw resin composition No. 1 No. 2 No. 3 No. 4 Νο·5 Νο. 6 Νο.7 No 8 A-1 25 - • 25 50 33 A-2 - 25 - 33 Mixing A-3 - - 25 33 B-1 - # 看B-2 - - - 里量 W B-3 - - A C-1 75 75 1 75 75 50 C-2 ] - 67 67 67 D-1 1 1 1 1 1 1 D-2 - _ 2 2 Solubility 〇〇〇〇〇〇〇〇150139.doc •49· 201120022 [Table 2] Comparative Example 2-1 2-2 2-3 2-4. 2-5 2-6 2·7 Comparison < Curable resin composition No. 9 No. 10 No. 11 No. 12 No 13 No. 14 No. 15 A-1 - - - • A-2 • - - • Provisioning A-3 - - - B-1 - - 25 One quantity t bokeh B-2 25 - - 25 33 B-3 _ - - • 25 C-1 C-2 75 100 75 75 75 100 —:_ 67 D-1 1 1 - _ ] D-2 per - 2 2 2 2 Solubility X 〇〇X 〇〇Δ From [Table 1] and [Table 2], it is understood that the composition using the comparative compound (B_2) has poor solubility and storage stability, whereas the embodiment 2 _i~2 _ 8 of the episulfide compound of the present invention is used. Composition versus thin The release agent is excellent in solubility. Further, in Comparative Example 2_m4, it was not dissolved, and in the comparative example, the crystal was precipitated in the cold portion to room temperature. Thus, the curable resin composition was not obtained. [Examples 3 to 1 to 3 - 3 and Comparative Example 3 · 1 ] / The obtained curable resin composition Nq1 to Μ and comparatively hardenable gas enthalpy. The object Ν1·1 is not heated to (10) and applied to the glass substrate on which the mold release treatment has been carried out. Use the spacer of _·mm to sandwich and fit the other piece of glass, for example. Wide collection s soil 〇〇c heating for 1 hour, at i5〇t: heating! In the hour, the hardening is set to 〇, and the harder one is x, and the hardening is evaluated. Further, the refractive index and transparency of the person who was obtained as a cured product were evaluated. The results are shown in 150139.doc -50- 201120022 [Table 3]. <Refractive Index> For the obtained cured product, the refractive index of the D line and the e line at 25 ° C was measured using an Abbe refractometer DR-M2 manufactured by Atago Co., Ltd. [Table 3] Example 3-1 Example 3-2 Example 3-3 Comparative Example 3-1 Curable resin composition No. 1 No. 2 No. 3 No. 10 Curability 〇〇. 〇〇 refracting Rate (D line) 1.604 1.608 1.602 1.592 Refractive index (e-line) 1.611 1.614 1.607 1.596 According to [Table 3], it is apparent that the curable resin composition Νο·10 (Comparative Example 3-1) is contained in comparison with the diluent and the heat hardener. The cured product of the curable resin composition No. 1 to No. 3 (Examples 3-1 to 3-3) of the episulfide compound Α-1 to Α-3 of the present invention is used as compared with the cured product of the present invention. The refractive index is higher. [Examples 4-1 and 4-2 and Comparative Example 4-1-4-3] The obtained curable resin compositions Ν〇·4 and ν〇·5 and comparative curable resin composition No. ll, Νο·13&Ν〇14 is heated to 6〇. Thereafter, it is applied to a glass substrate which has been subjected to mold release treatment. Using a spacer of the crucible and another glass to sandwich and fit it, using a high-pressure mercury lamp to expose one side of the glass with a sample of 3 m (total 6000 mJ/cm 2 ), and then processing at 150 ° C 2 After hours, it was peeled off from the glass substrate after cooling to room temperature. The person who was obtained as the cured product was set to 〇, and the uncured person was set to 乂, and the hardenability was evaluated. Further, the refractive index and transparency were evaluated for those who obtained the cured product. The results are shown in [Table 4] 〇150139.doc •51 - 201120022 <Refractive Index> For the obtained cured product', using the Abbe refractometer DR-M2 manufactured by Atago Co., Ltd., D at 25 ° C Determination of the refractive index of the line and the e line!^ and 1. <Transparency> The total light transmittance of the obtained cured product was measured by a fog meter NDH5000' manufactured by Nippon Denshoku Industries Co., Ltd. [Example 4] Example 4-2 Comparative Example 4-1 Comparative Example 4-2 Comparative Example 4-3 Curable resin composition No. 4 No. 5 No. 11 No. 13 No 14 Curability 〇〇X 〇〇Refractive index (D line) 1.604 1.622 1,600 1 584 Refractive index (e-line) 1.608 1.629 1.606 1 589 Total light transmittance 88.9% 87.0% - 83.6% 42.9% According to [Table 4] Obviously, using comparative compounds The comparatively curable resin composition No. ll (bj) (Comparative Example 4 - 丨) has good solubility, but has poor curability, and a curable resin composition plate 13 of Comparative Compound (Β·3) was used (Comparative Example 4) -2) and a comparative curable resin composition containing a diluent and an energy ray-sensitive cationic polymerization initiator Ν〇. 4 (Comparative Example 4-3) has good curability, but has a poor refractive index and transparency. On the other hand, the curable resin compositions Νο·4 and 5 (Examples 4-4 and 4-5) of the episulfide compound A-ruthenium of the present invention are excellent in the refractive index and transparency. According to the above, the member of the present invention is excellent in the solubility of the episulfide compound of the present invention, and the curable resin group of the present invention characterized by containing the compound I50139.doc • 52· 201120022 can provide hardening. A cured product excellent in properties and transparency and having a high refractive index, useful in optical materials. 150139.doc -53-

Claims (1)

201120022 VII. Patent application scope: i.- species of ring-wholesale compound, the following ^^(1) [Chemical 1] Τ, A and A represent an oxygen atom or a sulfur atom (its, a small), dan t, A1 and A2 to > 'one represents a sulfur atom), and Cy represents a carbon number of 3 to = independently indicating the number of broken atoms ~ Base, broken original two j soil, carbon atom number 7~2〇 aryl base, carbon number WO miscellaneous number 3~Μ material base ◎Suco, 妓基和芳' meta-methane And the bonding moiety of the aryl group may be replaced by a = bond: ', z may form an aromatic ring from each other adjacent to each other. 2. The burnt earth, the aryl group, the arylalkyl group, the heterocyclic group, the yl group, and the adjacent 2 The formed aromatic ring may be replaced by a fang atom, n represents 〇~1〇, and the integer value of P is not an integer of 0 to 5, and r represents an integer of 〇~4; further, the optical difference existing when n is not 〇 The construct can be any isomer). 2. An episulfide compound represented by the following formula (Η). [Chemical 2] ’ I50139.doc 201120022 (wherein A1 and A2 represent an oxygen atom or a sulfur atom (wherein at least one of ... and ^ represents a sulfur atom), and Y and Yjz independently represent the number of carbon atoms and the number of carbon atoms An aryl group of 6 to 2G, an aryl group having 7 to 20 carbon atoms, a heterocyclic group having 2 to 2 carbon atoms, a ring-based group having a carbon number of 3 to 1 G, or a hydroxyl atom; The sub-f group in the arylalkyl group and the bond of the aryl group may be interrupted by _〇·, _S_ or a double bond, and adjacent to each other may form a ring, the alkyl group, the aryl group, the aryl group, and the heterocyclic group. And ring 2 is replaced by a fang atom, η represents an integer of 0 to 10, q represents a number of 〇~4, and q' represents an integer of 0 to 8 (where q is (,) χ2 is not 0~4 Integer, the integer of the final 4 of the X table, the integer of #林4, the total of X and y is 2~4; further, it can be any isomer). The optical isomers present at the time 3. The cyclic sulfide compound whose core is represented by the following formula (4) [Chemical 3] (m) 'A1, A: (wherein, 4., Ζ, η & Γ are the same as the above formula (1); the optical isomer present at the time of biting may be any isomer). 4 item 2 ring sulfide compounds, which are represented by the following formula (IV) 150139.doc •2- 201120022: [Chemical 4] [>-^〇 (W) (wherein Y2' is the same as or represented by Y: A _ , 2 of the above formula (II), or represents a hydrogen atom, ... or 2 'A and A are the same as the above formula (Π), γΐ, , + -, s B, n, q, and r are the same as above ==; in addition, the optical isomer present when I is not 0 is any isomer). 5. The episulfide compound of claim 4, wherein the oxime of the above-mentioned general formula is an episulfide 6. The curable resin composition 纟 contains the compound of claimant and a hardener. A curable resin composition which contains an episulfide compound as claimed in the claims and an energy ray-sensitive cationic polymerization initiator. 8. A hardened material obtained by adding a curable resin composition such as Snapdragon or 7 to a cured person. A cured product obtained by, for example, requesting a curable resin composition energy line of a ruler item 7. ... 150l39.doc 201120022 IV. Designated representative map: (1) The representative representative of the case is: (none) (2) The symbolic symbol of the representative figure is simple: 5. If there is a chemical formula in this case, please reveal the characteristics that can best show the invention. Chemical formula: ,(Χ)ρ (I ) v^+Q-〇X°--^+Q-°> (Z)r (Z)r n Wr (Z)r \_a2 150139.doc