TW201113305A - Curable resin composition and cured products thereof - Google Patents

Abstract

A curable resin composition which comprises both an epoxy compound represented by general formula (I) and an energy -ray-sensitive cationic-polymerization initiator. In general formula (I), X, Y and Z are each a C1-10 alkyl group which may be substituted with a halogen atom, a C6-20 aryl group, a C6-20 aryloxy group, a C6-20 arylthio group, a C8-20 arylalkenyl group, a C7-20 arylalkyl group, a C2-20 heterocyclic group, or a halogen atom; k is a number of 0 to 4; p is a number of 0 to 8; r is a number of 0 to 4; n is 0 to 10; 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; and when n is not 0, the epoxy compound can take the form of any optical isomer.

Description

[Technical Field] The present invention relates to a liquid curable resin composition which is suitable for the production of a cured product of a high refractive index resin and which is excellent in handleability and less colored after curing. [Prior Art] Epoxy resin (compound) has been widely used in the fields of electronic materials and optical materials due to its excellent electrical properties, heat resistance, adhesion, etc., which are combined with a hardener. Developed to this day. For example, in the field of electronic materials, semiconductor sealing materials and the like may be mentioned; in the field of optical materials, there may be mentioned an optical film such as an antireflection film such as a liquid crystal display, a protective film of a color light-emitting diode, an optical waveguide, or a camera. The used, brother, mirror and prism. In particular, in the use of optical materials, for the purpose of weight reduction, a high refractive index is sought. Further, in an attempt to obtain a refractive index having a target, in particular, a cured product having a high refractive index, the curable resin composition becomes high in viscosity, and the handleability is deteriorated, and the obtained cured product is easily colored. In other words, in general, the production of a linear thiophene type epoxy compound or a bisphenol oxime type epoxy compound in an epoxy compound is sufficient. (4) However, the refractive index of the 'parts has not been extensively improved for such an epoxy compound, for example, the patent document... However, in these documents, the safety of the compound in the resin composition has problems in terms of the preservation property of crystal precipitation and the coloring property of the obtained cured product. 148 938 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 A curable resin composition excellent in stability and storage stability, and a high refractive index cured product excellent in low coloring property. The inventors of the present invention have repeatedly conducted intensive studies and found that a curable resin combination comprising an epoxy compound having a benzo or naphthocyclic ring structure and an energy ray-sensitive cationic polymerization initiator is found. The hardened material can achieve the above purpose. Specifically, the present invention provides a curable resin composition containing an epoxy compound represented by the following formula (I) and an energy ray-sensitive cationic polymerization initiator, and the like, based on the above knowledge and findings. The curable resin composition is irradiated with a cured product obtained by an energy ray. [Chemical 1]

(wherein, XY and Z are each independently a carbon substituted by a γ atom, an alkyl group having a number of 1 to 10, and a carbon atom number 6 to 20 which may be substituted by a octyl atom: 148938.doc 201113305 An aryloxy group having 6 to 2 ring carbon atoms substituted by an atom, an arylthio group having 6 to 20 carbon atoms which may be substituted by a fang atom, and an aryl group having 8 to 20 amino groups substituted by a south atom. An arylalkyl group having 7 to 20 carbon atoms which may be substituted by a halogen atom, a heterocyclic group having 2 carbon atoms or a halogen atom which may be substituted by a dentate atom; a methylene group in the phenotype and the aryl ray group, and the aryl group The direct bond of the base t can be composed of an unsaturated bond, 〇 _ or s_ 胄, 乂 can be formed by adjacent X, k table 0~4, p 〇~8, ^ 〇~4, n is 〇~, X is 〇~4, y is 〇~4, the total of the number is 2~4, and the optical isomer present when η is not 可 can be any Effect of the isomerized product The curable resin composition of the present invention can provide a cured product having low viscosity and excellent storage stability, high refractive index, and low coloring property. In the following, the curable resin composition of the present invention and the cured product thereof are described in detail based on preferred embodiments. The epoxy compound used in the present invention has benzene in the structure represented by the above formula (1). And a naphthoquinone ring structure. The alkyl group having 1 to 10 carbon atoms substituted by a ruthenium, osmium and 2 represented by the above formula (I) may be, for example, methyl or ethyl. Base, propyl, isopropyl, butyl, secondary butyl, tert-butyl, isobutyl, pentyl, isopentyl, decylpentyl, hexyl, heptyl, isoheptyl, third g Base, n-octyl, isooctyl, trioctyl, 2-ethylhexyl, n-decyl, n-decyl, 148938.doc 201113305 difluoromethyl, monomethyl, monofluoromethyl, pentafluoro Ethyl, tetradecylethyl, difluoroethyl, difluoroethyl, heptafluoropropyl, hexafluoropropyl, pentafluoropropyl, tetrafluoropropyl, trifluoropropyl, perfluorobutyl, trigas Sulfhydryl, di-gas methyl, mono-halogen, di-haloethyl, di-haloethyl, tetra-propylpropyl, tri-propylpropyl, tribromoindolyl, dibromoindolyl, monobromoindolyl, tribromoethane base, Dibromoethyl, bis- odoryl, mono-anthracene, monomethyl, decyloxy, decyloxymethyl, methoxyethyl, decyloxyethoxy, decyloxyethoxy Ethoxy thiolthio, ethoxy, ethoxylated, ethoxyethyl, ethylthio, vinyloxy, propoxy, isopropoxy, butoxy, butylthio, iso Butoxy, second butoxy, pentyloxy, pentylthio, isopentyloxy, third pentyloxy, neopentyloxy, hexyloxy, hexylthio, cyclohexyloxy, isohexyloxy , heptyloxy, octyloxy, 2-ethylhexyloxy, decyloxy, decyloxy, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclopentane a linear, branched, and cyclic group of a base or a cyclic fluorenyl group. The aryl group having 6 to 20 carbon atoms which may be substituted by a halogen atom, represented by X, γ and z in the above formula (I), For example, phenyl, naphthyl, 2-naphthyl, 1-indenyl, 1-phenanthryl, ortho-tolyl, m-tolyl, p-tolyl, 3-indenyl, 9-anthracene , 1-tetrahydronaphthyl, 2-tetrahydronaphthyl, anthracene-fluorenyl, 1-indanyl, 2-indanyl, 4-vinyl , 3-isopropylphenyl, 4-isopropylphenyl, 4-butylphenyl, 4-isobutylphenyl, 4-tert-butylphenyl, 4-hexylphenyl, 4- Cyclohexylphenyl, 4-octylphenyl, 4-(2-ethylhexyl)phenyl, 2,3-diphenylphenyl, 2,4-diphenylphenyl, 2,5-dimethyl Phenyl, 2,6-dimethylphenyl, 3,4-didecylphenyl, 3,5-fluorenyl basic, 2,4-di-t-butylphenyl, 2,5-di- Tert-butylbenzene H8938.doc * 6 - 201113305 keto-2,6 second butylphenyl '2,4_di-t-pentylphenyl, 2,5-di-t-pentylphenyl, Cyclohexylphenyl, biphenyl, decyltrimethylphenyl, 4-carbene, 34-dichlorophenyl, 4-trisylphenyl, 4-trifluorophenyl, perfluorophenyl, and the like. An aryloxy group having 6 to 20 carbon atoms which may be substituted by a (tetra) atom represented by x or uz in the above formula (1), and examples thereof include a phenoxy group, a 2-methylphenoxy group, and 3 -Methylphenoxy, 4-methylphenoxy, 2,3-dimethylphenoxy, 2,4-dimethylphenoxy, 2,5-dimethylphenoxy, 2, Butyl dimethyl benzoate, 3,4-dimethylphenoxy, 3,5-dimethylphenoxy, 2,3,4-trimethylphenoxy, 2,3,5-tri Methylphenoxy, 2,3,6-trimethylphenoxy, 2,4,5-trimethylphenyloxy, 2,4,6-trimethylphenyloxy, 3,4,5 Trimethylphenoxy, 2,3,4,5-tetramethylphenoxy, 2,3,4,6·tetramethylphenoxy, 2,3,5,6-tetramethyl oxy , pentamethylphenoxy, ethylphenoxy, n-propylphenoxy, isopropylphenoxy, n-butylphenoxy, diethyl butyl phenoxy, tert-butyl phenoxy , n-hexylphenoxy, n-octylphenoxy, n-decylphenoxy, n-tetradecylphenoxy, fluorenyl-naphthyloxy, 2-naphthyloxy, 1-decyloxy, 1-phenanthrene Oxyl, o-tolyloxy, m-nonylphenoxy, p-nonylphenoxy, 9-decyloxy, 1-tetrahydronaphthyloxy, 2_ Hydrogen naphthoxy, Shu _ acenaphthylene group of 1 - indan group, a 2-indanyl group and the like. The arylthio group having 6 to 20 carbon atoms which may be substituted by a halogen atom represented by X, Y and z in the above formula (I) may, for example, be a phenylthio group or a 2-mercaptophenylthio group. 3-methylphenylthio, 4-methylphenylthio, 2,3-dimercaptothio, 2,4-dimethylphenylthio, 2,5-dimercaptophenylthio, 2 ,6-dimethylphenylthio, 3,4-dimercaptophenylthio, 3,5-dimercaptophenylthio, 2,3,4-triazole 148938.doc 201113305 phenylthio, 2 ,3,5-trimethylphenylthio, 2,3,6-trimercaptophenylthio, 2,4,5-trimethylphenylthio, 2,4,6-trimethylphenylthio , 3,4,5-trimethylphenylthio, 2,3,4,5-tetradecylphenylthio, 2,3,4,6-tetramethylphenylthio, 2,3,5, 6-tetradecylphenylthio, pentamethylphenylthio, ethylphenylthio, n-propylphenylthio, isopropylphenylthio, n-butylphenylthio, secondary butyl phenylthio , tert-butylphenylthio, n-hexylphenylthio, n-octylphenylthio, n-decylphenylthio, n-tetradecylphenylthio, 1-naphthylthio, 2-naphthyl, 1- , 'Sulfuryl, 1-phenanthylthio, o-nonylphenylthio, m-tolylthio, p-nonylphenylthio, 9-fluorenylthio 1- thio four nitrogen Chennai, 2 - four mice Nai sulfur group of 1 - thio risk of 1 - thio full section, 2 - full section group and the like. The arylalkenyl group having 8 to 20 carbon atoms which may be substituted with a halogen atom represented by X, Y and Z represented by the above formula (I), and examples thereof include a styryl group and a 4-fluorobenzene. Vinyl and the like. The arylalkyl group having 7 to 20 carbon atoms which may be substituted by a X atom in the above formula (I), and may be, for example, a benzyl group, a phenethyl group or a 2-benzene group. Propyl, diphenylmethyl, triphenylindenyl, 4-phenylphenylindenyl, T-oxy, 1-naphthylmethoxy, 2-naphthylmethoxyl, 1-indenyl Alkoxy groups, etc. The heterocyclic group having 2 to 20 carbon atoms which may be substituted by a halogen atom, which is represented by the above formula (I), X, Y and Z, may, for example, be a pyrrolyl group, a pyridyl group, a pyrimidinyl group or a fluorenyl group. The base of the tour, the bottom of the D, the base, the ratio of the base. ratio. Sitting base, three bases, D than σ each yard base, 噎琳基, 啥啥琳, 11 meters β sit, benzo and meter. Sitting on the base, three. Sitting group, D-fumanyl, benzofuranyl, fluorenyl, thiophenyl, benzothiophenyl. The plug II is sitting on the base. Plug. Sitting on the base, benzene and ° plug. Sitting on the base, ah D sitting on the base, benzene and evil 148938.doc 201113305 Junji, different. Ββ坐基, 异°αα坐基,叫丨朵基,久久ini bite, morphine, thiomorpholinyl, 2-pyrrolidinone-1-yl, 2-piperidone丨 _ base, 2, 4 _ dioxo σ m 嗤 -3- -3- yl, 2, 4- dioxo oxime _ 3- base. The above formula (1) may be constituted by a ring formed by adjacent ones, and may be, for example, a cyclopentane ring, a cyclohexane ring, a cyclopentene ring, a benzene ring, a η bottom bite ring, a linpo ring, and an inner vinegar ring. And (4) a condensed ring of 5 to 7 member rings such as an amine ring and a ring of Cai ring, f ring, nucleus ring, anthracene ring, anthracene ring, and a naphthalene ring. The dentate atom of X, oxime and 2* in the above formula (1), the X atom of the above formula (1), the alkyl group, the aryl group, the aryl group and the heterocyclic group which are substituted by the above formula (1) It can be compared with fluorine, chlorine, desert and broken. In the group represented by the above formula (1), the methylene group in the aryl group and the aryl group and the direct bond in the aryl group may be interrupted by an unsaturated bond, -〇- or -S- , Halogen-based H-straight and -〇- or -S· interrupt bit ° 壬思' contains -Q. or _S_ directly linked to each ring. The epoxy compound towel of the above formula (1), in the case of a structure, the yoke y / ding has a singularity, and the singularity is not limited to specific opticals. Isomer. [, the epoxy compound of the formula (I), the substance No. 1 to No. 42, #丁心 7疋, for example, the following compound _+ + the limitation of these compounds. Also, T, t, # @ in the formula, 〗 1 table 0 to 10 number. Also released chemistry 148938.doc 201113305 [Chemical 2]

Compound No. 1

Compound No. 2

Compound No. 3 Compound No. 4

Compound No.! Compound No. 6 148938.doc -10- 201113305 [Chemical 3]

Compound No. 12 148938.doc -11 - 201113305 [Chemical 4]

Compound No. 13 Compound No. 14 Compound No. 15

Compound No. 16

148938.doc -12- 201113305 [Chemical 5]

148938.doc -13- 20111^305 61

148938.doc -14- 201113305 [Chemistry 7]

148938.doc -15- 201113305 [Chem. 8]

OH

148938.doc - 16- 201113305 [Chem. 9]

Among these compounds, the following compounds are satisfactory in terms of availability of raw materials, good productivity, and excellent storage stability. In the above formula (1), or 3, y is 〇, χ is a carbon atom (7). An alkyl group, an aryl group having 6 to 2 Å or a ring formed by X is an aromatic ring group, and Y and Z are an alkyl group having a carbon number of 丨~丨〇 or a carbon number of 6 to 148938. .doc •17- 201113305 aryl, a compound having k, p, r of 0 to 2, particularly a compound having η of 0 to 5; a compound represented by the following formula (II): [Chem. 9-1]

(wherein X, Υ, z, k, r and η are the same as in the above formula (I)). In the above formula (I) or (II), η is a compound of ruthenium, and γ is a compound of phenyl group. 'k is 0 or 1; when k is 1, X is a compound having an alkyl group having 1 to 1 ring of carbon atoms or an aryl group having 6 to 20 carbon atoms; in the above formula (I), X is 2, y For 〇, γ is phenyl, let 〇, and r is a compound in which Ο 'η is 0. The method for producing the epoxy compound represented by the above formula (I) is not particularly limited, and for example, it is a slave of the international patent publication No. 2,8,8,399,24 [0032] to [0042] ( The manufacturing method described in [0025] to [0034] of US2010/00 15551Α1. Next, an energy ray-sensitive cationic polymerization initiator which is used together with the epoxy compound represented by the above formula (1) will be described. The energy ray-sensitive cationic polymerization initiator used in the present month is a compound which can be subjected to f-line sensitization irradiation, more specifically, a substance which initiates cationic polymerization by irradiation of an energy ray described later. As the above-mentioned energy ray sensitizing ^α λα e ^ , θ submerging initiator, a particularly good enthalpy by energy ray sensitization (IV) 出 路 酸 148 148 148 148 148 938 a compound such as a derivative thereof. Representative of such a compound, a salt of a cation and an anion represented by the formula [A]y+[B]y• can be mentioned. Here, the cation [Α] is preferably ruthenium, and its structure can be shown, for example. In the above structural formula, the R group has a carbon number of 丨~(9), an organic group containing a plurality of atoms other than a carbon atom, and an integer of the parent 丨~5. Each of R may independently be the same or different, and at least one of them may be an aromatic group. The q table is selected from atoms or groups of atoms comprising S, N, Se, Te, P, As, Sb, Bi, hydrazine, hydrazine, hydrazine, C1 F, and N=N. Further, when the valence of Q in the cation [A]y+ is z, it is necessary that y = xz is established. Further, the anion [B]y- is preferably a complex of a compound, and its structure is, for example, [LXs]y. Hungarian "Metalloid" in the central structure of the L-form halide complex, and may be, for example, B, p, & ' ^, ^,

Sn, A, Ca, In, Ti, Zn, Sc, v, . , —, c〇, etc. An integer of the table halogen atom '~7. Further, when the atom 仏 of the anion [B]y• is 1, it is necessary that y=s-t is established. The specific example of the anion [LXs]y· which constitutes the sulfonium salt of the above formula can be used for the tetrafluorinated egg F4), the hexafluorinated scale (PF6), and the hexafluoride (SbF6)_ / , fluorinated Kun (AsF6) _, hexachlorinated recording (like similar, better sputum (SbF6) ·. Rat structure as an anion [B] y •, can be used to [[10] which. L, X, and S are the same as above. Further, other available anions include peroxy acid ions (C1q4). Trifluoromethanesulfite (CF3s〇3)·148938.doc -19·201113305

Fluoric acid ion (FS〇3)·, toluenesulfonic acid anion, trinitrobenzenesulfonic acid anion, etc. W is also used as the anion [B]y·, and tetrakis(pentafluorophenyl)borate can also be used. According to the present invention, it is particularly effective to use an aromatic rust salt in such a phosphonium salt. Among them, 'extra good is the aromatic halogen oxime contained in 5 Japanese Patent Publication No. 50-丨5丨997 (GB 15 16511(A)) and JP-A-50_158680 (US4394403(A)). Salt, 曰本特开昭50-1 5 1997 (GB1516511(A)), JP-A-52-30899 (US4256828(A)), JP-A-56-55420, JP-A-55_1 251 芳香族 〇 ( ( US US US US US US US US US US US US US US VI VI VI VI VI VI VI VI VI VI VI VI VI VI VI VI 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 Gazette 56-8428, special opening

(III), (IV) or (V): VA aromatic rust salt, pp. 56-149402 [Chem. 10]

201113305 R11Q, 3,

(v) R14 (wherein R1 to R14 are the same or different hydrogen atoms, a halogen atom or a hydrocarbon group which may contain an oxygen atom or a halogen atom, or an alkoxy group which may have a substituent; a compound having a phosphonium cation represented by one or more hydrogen atoms substituted with a phenyl group; a compound having a (tricumyl) iodonium cation; a compound having a bis(t-butylphenyl) iodine rust cation; having a triphenyl group a compound of a phosphonium cation or the like. For example, 4-(4-benzoyl-phenylthio)phenyl-di-(4-fluorophenyl)phosphonium hexafluorophosphate; 4,4,-bis[bis((β-hydroxy) Ethoxy)phenyl)monovalent phenyl thioether-bis-hexafluorophosphate, 4,4,_bis[dihydroxyethoxy)phenyl)monovalent fluorenyl]phenyl thioether- Bis-hexafluoroantimonate; 4,4,_bis[bis(fluorophenyl)monovalent fluorenyl]phenyl sulfide-bis-hexafluorophosphate, 4,4,_bis[bis(fluorophenyl) Monovalent mercapto]phenylthioether•bis-hexafluoroantimonate; 4,4,_bis(diphenylmonovalent fluorenyl)phenyl sulfide-bis-hexafluorophosphate, 4,4, · bis(diphenyl monovalent fluorenyl) phenyl sulfide-bis-hexafluoroate; 4-(4-phenylmercaptophenylthio)phenyl-di-(4-(β-hydroxyethoxy) Phenyl) nickel hexafluorophosphate, 4-(4-benzoylphenylthio)phenyl-di-(4-(β-hydroxyethoxy)phenyl)phosphonium hexafluoroantimonate; 4_ ( 4- azathiophenylthio)phenyl-bis-(4-fluorophenyl)phosphonium hexafluorophosphate, phenylmercaptophenylthio)phenyl-di-(4-fluorophenyl)phosphonium hexafluoroantimony Acid salt; 4-(4-phenylmercaptophenylthio)phenyl-diphenyl sulphate, 4-(4-phenylmercaptobenzene Thio)phenyl-diphenylphosphonium hexafluoroantimonate; 4-(phenylthio)phenyl-di-(4-(β- •2b 148938.doc 201113305 hydroxyethoxy)phenyl) hexafluorocyclohexane Phosphate, 4-(phenylthio)phenyl-bis-(4-(β-hydroxyethoxy)phenyl) hexafluoroantimonate; 4-(phenylthio)phenyl-di-(4) -fluorophenyl)phosphonium hexafluorophosphate, 4-(phenylthio)phenyl-di-(4-fluorophenyl) hexahydrocarbonate, 4-(phenylthio)benyl-diyl Saponin, 4 _(phenylthio)phenyl-diphenylphosphonium hexafluoroantimonate; 4-(2- gas-4-phenylmercaptophenylthio)phenyl bis(4-fluoro Phenyl)phosphonium hexafluorophosphate, 4-(2- gas-4-phenylmercaptophenylthio)phenylbis(4-fluorophenyl)phosphonium hexafluoroantimonate; 4-(2-chloro-4) -phenylphenylsulfonyl)phenyldiphenylphosphonium hexafluorophosphate, 4-(2- gas-4-phenylmercaptophenylthio)phenyldiphenylphosphonium hexafluoroantimonate; 4-( 2-ox-4-phenylmercaptophenylthio)phenylbis(4-hydroxyphenyl)phosphonium hexafluorophosphate, 4-(2- gas-4-phenylmercaptophenylthio)phenyl bis (4 -hydroxyphenyl) hexafluoroantimonate; triphenylsulfonium hexafluorophosphate, triphenyl sulphate; Phenyl cumyl) iodine hexafluorophosphate, (nonylphenyl cumyl) iodine hexafluoroantimonate, (nonylphenyl cumyl) iodonium tetrakis(pentafluorophenyl) borate; double (third Butylphenyl) iodine hexafluorophosphate, bis(t-butylphenyl) iodine hexafluoroantimonate, bis(t-butylphenyl) iodine ruthenium tetrakis(pentafluorophenyl)borate; Nucleo-4-hydroxyphenylindenyl hexafluorophosphate, benzyl-4-hydroxyphenylmethyl hexafluoroantimonate; benzyl difluorenyl hexafluorophosphate, benzyl diindenyl hydrazine Hexafluoroantimonate; p-benzylbenzyl-4-hydroxyphenylindenyl hexafluorophosphate, p-oxybenzyl-4-hydroxyphenylsulfonyl hexafluoroantimonate; 4-ethoxime Phenyl phenyl fluorenyl hexafluorophosphate, 4-ethenyloxy phenyl dimethyl hexafluoroantimonate; 4-decyloxycarbonyloxy phenyl dimethyl hexafluorophosphate, 4 - anthranoxycarbonyloxyphenyldifluorenyl hexafluoroantimonate; 4-ethoxycarbonyloxyphenyldimethylphosphonium hexafluorophosphate, 4-ethoxycarbonyloxyphenyldifluorene Hexafluoroantimonate; α-naphthylmethyldifluorenyl hexafluorene 148938.doc -22- 201113305 M acid salt, α_Caiji Yinji dimethyl town hexa(tetra) acid salt '·α_ 基 yl methyl four gas benzene hexaploate disc acid, α-Cai-methyl methyl four gas benzene hexahydro acid salt; : Gui-methyl hexafluoride - acid salt, cinnamyl dimethyl nickel hexafluoro acid, cinnamyl tetrahydro benzoic acid, salt, cinnamyl tetrahydrogen, benzene, six gas, salt, salt, ': (α-本基基基) cyanoguanidine Bite rust hexa-acid salt, Ν_(α_phenyl phenyl): 2-cyanopyridine hexafluoroantimonate; ν_cinnamyl_2_cyanoacridinium fluoride 14U Ν-cinnamyl_2_ Cyano group 比 hexafluoroate salt; ν, methyl group)-2-cyanopyridine rust hexafluorophosphate, ν ♦ naphthyl ketone 2 cyano quinone hexafluoroate salt; Nm cyano (4) Hexafluoroantimonate, N-subsyl-2-cyano. Than the wrong six gas recording acid salt, · (4 · phenyl phenyl phenylthio) phenyl bis ( 4- fluoro smear tetra (3, 5 _: fluorine _ 4 _ oxy benzoate salt, etc. Other preferred examples include xylene, cyclopentadienyl iron (II) hexahydrate, olefin-cyclopentadienyl iron (π) hexahydrocyanate, and xylene ring. An iron/propadiene complex such as pentane dilute iron („)·tris(trifluoromethyl fluorenyl) fluorenyl anion, etc., a complex/photodegradation compound, an initiator, etc. The linear cation cationic polymerization initiator may be used in combination of two or more kinds. The energy ray-sensitive cationic polymerization initiator is preferably used in an amount of 1 part by mass based on the epoxy compound represented by the above formula (1). 0.05 to 20 parts by mass. When the amount used is less than 5 parts by mass, the curing of the curable resin composition is insufficient, deformation or unevenness may occur, or cracks may occur during heating. When the amount is more than 5 parts by mass, the content of the ionic substance in the adhesive layer formed by hardening the curable resin composition is increased, and there is hardening. The hygroscopicity is increased, or the long-term performance of 148938.doc -23·201113305 is not fully obtained. The better use amount of the energy ray-sensitive cationic polymerization initiator is 0.05 parts by mass relative to 100 parts by mass of the epoxy resin. Further, in the curable resin composition of the present invention, a hard catalyst reactive and/or non-reactive diluent (plasticizer), a filler, a pigment, a residual coupling agent, and a surfactant may be contained as necessary. , lubricants, tackifiers, thixotropic agents, antioxidants, photosensitizers, light stabilizers, UV absorbers, flame retardants, defoamers, anti-recording agents, preservation stabilizers, knee dioxide: In the case of the curable resin composition of the present invention, any of the additives may be used in combination with the epoxy compound 1 represented by the above formula (1). 〇〇 mass part

500 parts by mass or less. θ ° °T In the curable resin composition of the present invention, a material can also be used. At this time, 〉the amount of the use of the grain medium, should be extended, and the epoxy compound and the energy line sensitive cationic polymerization initiator shown in the clock A countless county + ^

The amount of Ji, , yv A, . 3 is 5 to 90% by mass in the sclerosing tree sassafras composition of the present invention, more preferably 〇 〇 5 5% by mass, and specific examples of the solvent, for example The ketones such as methyl ethyl sulfenyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, ketone, cyclohexanone, etc.; , U-diethoxy B; 'four. Fufang, two% ^ u · 7 ^ Earthen one-propanol-alcohol monoether ether, such as ether, wide W, acetic acid U, acetic acid positive (tetra), isopropyl acetate, etc. , glycol-ethylene glycol, propylene glycol-methyl 7β ^ acetal oxime cellulose-based solvent; methanol, ethanol iso- or n-propanol, iso- or n-butanol pentanol and other alcohol-based solvents · benzene , toluene, two ^ (4) m, Xin Xuan ^ I48938.doc -24 - 201113305 Institute of aliphatic hydrocarbon solvent; turpentine, D_. citric acid, thin and other olefinic hydrocarbon oil; mineral oil, Swazilu #31〇 (aromatic mixed solvent, COSMO Matsuyama Oil Co., Ltd.), Sorube Shou #1〇〇 (aromatic solvent, EXXON Chemical Co., Ltd.) and other stone butterfly solvent; An aliphatic hydrocarbon-based solvent such as carbon chloride, chloroform, trichloroethane or di-methane; a toluene-aromatic solvent such as chlorobenzene; a carbitol-based solvent, aniline, triethylamine, (iv), Acetic acid, acetonitrile, carbon disulfide, N,N-dimethylformamide, N-methylpyrrolidone, etc.; among them, ketones or fibers and excipients are preferred. Further, the solvent used in the synthesis of the above epoxy compound may be contained in the curable resin composition of the present invention without being removed. The curing resin composition of the present invention is usually irradiated by an energy line such as ultraviolet rays (it can be hardened into a dry state or a solvent insoluble state after U seconds to several minutes. As an appropriate energy line, as long as it can be induced The decomposer of the cationic polymerization initiator may be used, preferably by ultra high, high, medium and low pressure mercury lamps, xenon lamps, carbon arc lamps, metal toothed lamps 'fluorescent lamps, tungsten lamps' excimer lamps, killing g Lamps, excimer lasers, nitrogen lasers, nitrogen ion lasers, cadmium cadmium lasers, helium lasing lasers, gas ion lasers, various semiconductor lasers, YAG lasers, light-emitting diodes, CRT light sources, etc. It has 2 kinds of electromagnetic wave energy or electron beam, X-ray, and radiation of the south energy line of 7000A wavelength. The date: the curable resin composition can be hardened by heat treatment, but it is a cured product of good quality. 'The energy ray irradiation treatment and the heat treatment are preferably performed in a heat treatment before and after the energy ray irradiation. The curable resin composition of the present invention is other than the optical parts 148938.doc -25·201113305 described below. , It can be used as an oil/ink, a protective film, a paint, a coating, an adhesive, an insulating material, a structural material, a disc, a sealant, or a photo-forming agent. The cured product of the present invention is irradiated with the curable resin composition of the present invention. The energy line to be used is as described above. The shape of the cured product of the present invention is not particularly limited, and examples thereof include a shape of a lens, a film, a braid, and a plate. Further, the material may be coated or sealed by hardening it on another material. The cured product of the present invention is an optical lens, an optical film, a light guide plate, a waveguide, an optical element, an optical connector, or the like. The present invention will be described in more detail by way of examples and comparative examples, but the present invention is not limited by the examples and the like. In the examples and the comparative examples, "parts" means " In the examples, the preparations of the curable resin composition of the present invention are shown in the examples, and the comparative examples of the composition of the curable resin composition are shown in the comparative example. 2·4 to Comparative Examples 2_1 and 2_ 2 ' show the production examples of the cured product and the comparative cured product of the present invention, and Examples 3-1 to 3-4 and Comparative Examples 3-1 and 3-2 show the cured product and the comparative cured product of the present invention. [Examples 1-1 to 1-4 and Comparative Examples 1 to 1 to 1-3] Curable resin composition No. 1 to Νο. 4 and comparative curable resin composition No. 1 to Νο· Production of 3 The following (1-1) to (1-3) epoxy compound and (2) diluent were heated at 80 ° C according to [Table 1], and then cooled to 6 ° C, and then added (3). -1) and (3-2) an energy ray-sensitive cationic polymerization initiator to completely dissolve them, respectively forming a hardening tree 148938.doc • 26· 201113305 fat composition No. 1 to No. 4 and a comparative hardening resin combination Νο·卜 No.3. [Complex] (1-1) 1,1-bis(4-(2,3-epoxypropoxy)phenyl)_3_phenylindole (corresponding to π=0 of the above compound No. 40) In the case of the following, it is the following epoxy compound No. 1. [化11]

(1-2) 1,1_bis(4_(2,3_epoxypropoxy)phenyl)_35_diphenyl moiety (corresponding to the case of n=〇 of the above compound No. 31), as The following epoxy compound N 〇. [化 12]

D-3) 9,9·bis(4-(2,3-epoxypropoxy)phenyl)anthracene, as the following epoxy compound No. 1. [Chem. 13]

I48938.d〇c •27· 201113305 (3-l)ADEKAOPTOMER SP-170 (Daily Salt Co., Ltd. made salty energy line sensory cationic polymerization initiator: 4,4'-double [double ((β_) (Ethyl ethoxy) phenyl) monovalent sulfhydryl] phenyl sulfide bis-hexafluoroantimonate) [Chem. 14]

(3_2)ADEKAOPTOMER SP-172 (a salt-based energy line-sensitive cationic polymerization initiator made by ADEKA Co., Ltd.: '(2_gas_4_phenylphenylthio)phenylbis(4-fluorophenyl) Hexafluoroantimonate) [Chem. 15]

With respect to the adhesion and storage properties of the obtained curable resin combinations _〇1 to N〇4 and the comparative curable resin composition NOH3, the following evaluation was carried out. These results are recorded in [Table]. <Preservation stability> People... 丨王树畑殂 The contents were cooled to room temperature, and evaluated for presence or absence. When the sediment is not confirmed, it is recorded as 0, and it is confirmed that there is a precipitate in the first week. However, it is set to △, and the right is △, #w... The main child does not confirm that "there is a precipitate when it is placed for 1 hour. 148938.doc -28- 201113305 <Viscosity> The viscosity of the obtained curable resin composition and the comparative curable resin composition at 40 ° C, manufactured by Toki Sangyo Co., Ltd. The viscosity meter TVE-20 was measured. Further, it was confirmed that the amount of the precipitated product was found to be large in comparison with the curable resin composition No. 1. However, it was not measured because of the preservation stability. [Table 1] Example 1-1 Example 1-2 Example 1-3 Example 1-4 Comparative Example 1-1 Comparative Example 1-2 Comparative Example 1-3 Curable resin composition comparative hardening resin composition compound No. 1 No. 2 Νο. 3 Νο.4 No.l No.2 Νο.3 谋(M) 4.0 2.5 2.5 Distribution (1-2) 2.5 Scene (1-3) 4.0 2.5 / (2) 6.0 7.5 7.5 7.5 6.0 7.5 10.0 Buying (3 -1) 0.2 0.2 0.1 0.2 0.2 0.2 parts (3-2) 0.1 Preservation stability 〇〇〇〇X Δ 〇 Viscosity/mPa.s 25000 6100 7100 Ποοο ---- 1100 0 1200 It can be confirmed from [Table 1] that (4) the curable resin composition having the q-oxygen compound (epoxidized character Ν〇.βΝο·2) of the present invention (the epoxy compound of the conventional compound mixed with the conventional product (Comparative) Epoxy compound H) Resin composition (Comparative Example 丨 丨 丨 and 丨 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Preservation of the composition> The epoxy b of the preparation, the composition (epoxy compound No. 1) was not confirmed to have precipitates, and the stability was excellent (Examples and ^), whereas the compound (Comparative epoxy compound Ν〇·丨) was confirmed to have poor precipitation stability (Comparative Example 1 _丨 and 丨_2). Treatment with epoxidized 'composition' and 'mixed with the same mass In the case of the epoxy compound, the curable resin composition of Loose No. 1 has a particularly low viscosity and is excellent in properties (Examples 1-2 and 1-3). [Examples 2-1 to 2-4 and Comparative Example 2 -1 and 2-2] Production of cured materials No. 1 to No. 4 and comparative cured materials No. 2 and No. 3, the above Examples 1-1 to 1-4 and ratio Shu _2 Example 1-3 and the obtained curable resin composition and comparative curable resin composition are heated at 6〇 < t, and applying it to a release treatment has been accepted on the glass substrate. The composition was sandwiched with another piece of glass together with a spacer of 1 mm, and the formed product was exposed to a glass sheet surface at 3000 mJ/cm 2 (6000 mJ/cm 2 ) with a high pressure mercury lamp at 150°. C was hardened by treatment for 2 hours. After cooling to room temperature, the cured product was peeled off from the glass to form cured products No. 1 to No. 4 and comparative hardened materials N 〇 · 2 and N 〇. [Examples 3-1 to 3-4 and Comparative Examples 3-1 and 3-2] Evaluation of cured product No. 1 to Νο·4 and comparative hardened materials n〇.2 and No. 3 for Example 2-1 "Reflection", "Discoloration" and "Transparency" of the cured materials No. 1 to No. 4 and Comparative cured materials No. 2 and No. 3 obtained in Comparative Examples 2-1 and 2-2 ''The following assessment was conducted. The results are shown in the following [Table 2]. <Refractive Index> 148938.doc -30-201113305 Using the Abbe refractometer DR-M2 manufactured by ATAGO Co., Ltd., the refractive index nd of the obtained d-line and e-line of the cured product at 25 ° C was performed. Determination of ne. <Discoloration> The spectrophotometer SE6000 manufactured by Sakamoto Electric Co., Ltd. was measured for the yellowness of the obtained cured product: YI (ASTM E313). <Transparency> The total light transmittance of the obtained cured product was measured by a turbidity meter NDH5000 manufactured by Sakamoto Denshoku Industries Co., Ltd. [Table 2] Composition hardened material nd ne YI Total light transmittance % Example 3-1 Curable resin composition No. 1 Hardened material No. 1. 1.604 1.609 15 86.6 Example 3-1 Curable resin composition No. 2 Hardened material No. 2 1.597 1.602 21 83.6 Example 3-1 Curable resin composition No. 3 Hardened material No. 3 1.596 1.601 13 89.8 Example 3-1 Curable resin composition No. 4 Hardened material No. 4 1.599 1.604 10 87.5 Comparative Example 3-1 Comparative Curable Resin Composition No. 2 Comparative Cured Product No. 2 1.600 1.606 40 70.0 Comparative Example 3-2 Comparative Curable Resin Composition No. 3 Comparative Hardened No. 3 1.582 1.587 82 42.9 It can be seen from [Table 2] that the cured compounds No. 1 to No. 4 of the epoxy compound (epoxy compound No. 1 or Νο. 2) of the present invention are incorporated in refractive index, coloring property and 148938. Doc -31 - 201113305 Excellent in any aspect of the rate, etc. (Examples. It is confirmed that, especially by the compounding ratio of epoxy compounds, higher refractive index, less coloration, and high transmittance can be obtained. (Examples 3-1 and 3-2). In contrast, the hardenable component is only harder than the diluent. The refractive index of the material 3 is not sufficient, and there is a large coloring phenomenon, and the transmittance is also insufficient (Comparative Example 3-2). Further, 'the epoxy compound (comparative ring, material No.) of the conventional product is mixed) Comparing the hardened material N〇2, although it can impart high refractive index, the color of the kernel and the transmittance are insufficient (Comparative Example 3 _ 1). The epoxy compound is a cured product which is excellent in characteristic preservation stability, and is suitable for light. As is apparent from the above, it is useful to use a curable resin composition of the present invention to provide a material having a high refractive index which is excellent in handleability, coloration, and color transmission. 148938.doc -32·

Claims (1)

201113305 VII. Patent Application Range: 1. A curable resin composition containing an epoxy compound represented by the following formula (I) and an energy ray-sensitive cationic polymerization initiator: [Chemical Formula 1] (wherein X, γ and z are each independently, an alkyl group having 1 to 10 carbon atoms which may be substituted by a halogen atom, a carbon atom which may be substituted by a halogen atom, 6 to an aryl group, and a number of carbon atoms which may be substituted by a halogen atom An aryloxy group of 6 to 20, an arylthio group having 6 to 2 carbon atoms which may be substituted by a dentate atom, an arylalkenyl group having 8 to 20 carbon atoms which may be substituted by a south atom, may be substituted by a fang atom An arylalkyl group having 7 to 20 carbon atoms, a heterocyclic group or a hydroxyl atom having 2 to 20 carbon atoms which may be substituted by a south atom; a methylene group in the aryl group and the aryl group, and the aryl group The direct bond in the 'can be unsaturated key, · 〇 _ or -μ break, X is the ring that can be formed by the adjacent x, • Table 0~4 number, η table 〇~1〇, χ k table 〇~4, p table 〇8 number table 〇~4 number '#〇~4 number, the total of the number is 2+η non-Χ The optical isomer present when 〇 can be any different Structure). 2. ^Requests! The curable resin composition, wherein the above is 2 or 3, ^, an aryl group having a carbon number of 148938.doc 201113305 6 to 20 or a group which may form a ring by an adjacent X. γ and z are an alkyl group having 1 to 1 ring of carbon atoms or an aryl group having 6 to 20 carbon atoms, and k, p and r are each independently 〇 2 . 3. The curable resin composition of claim 1, wherein the epoxy compound is a compound represented by the following formula (〗): [Chemical 2] (wherein, X, Y, Z, k, r and η are the same as defined in the above formula (1)). 4. The curable resin composition of claim 1, wherein in the above formula (1), η is 0. The curable resin composition according to claim 1 or 3, wherein in the above formula (I) or in the above formula (II), hydrazine is a phenyl group. 6. The curable resin composition according to claim 1 or 3, wherein in the above formula (1) or the above formula (II), 'k is 0 or 1; when k is 1, X is a carbon atom 丨~1〇 An alkyl group or an aryl group having 6 to 20 carbon atoms. A cured product obtained by irradiating a curable resin composition as claimed in claim 1 with an energy ray. 148938.doc 201113305 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 best indication of the characteristics of the invention. Chemical formula: 148938.doc