JP2002097217A - Photocurable resin composition and its cured product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition with an excellent storage stability which has a good curable property by the irradiation of an active energy ray such as an ultraviolet light or the like and an excellent handling property on a process from the viewpoint of balance such as a refractive index, mobility or the like, and to provide an optical material whereby the physical properties of a molded product after curing have a high refractive index and a high transparency. SOLUTION: The photocurable resin composition is characterized by containing (A) a sulfur-containing (meth)acrylate compound represented by the formula (I) or a radical reactive composition containing the compound, (B) a polymerization inhibitor of 0.001-0.5 pts.wt. with respect to the component (A) of 100 pts.wt. and (C) a polymerization initiator.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photocurable composition having excellent storage stability and exhibiting good curability upon irradiation with active energy rays such as ultraviolet rays. This composition has a refractive index and transparency. Suitable for manufacturing high optical lenses, optical components, anti-reflection coatings, adhesives, etc.

[0002]

2. Description of the Related Art Conventionally, polyfunctional (meth) acrylates having a high refractive index have been disclosed in JP-A-4-337307, JP-A-5-164903, JP-A-6-220131, and JP-A-10-67970. JP-A-10-67
No. 977, acrylates having a fluorene ring, JP-A-2-160762, JP-A-5-142.
No. 501, JP-A-6-3628, etc., sulfur-containing (meth) acrylates such as bis (4-methacryloylthiophenyl) sulfide are disclosed in JP-A-58-52601.
JP, JP-A-1-135853, JP-A-3-3
No. 6582, etc., halogen-containing (meth) acrylates such as 2,2′-bis (3,5-dibromo-4- (2-methacryloyloxyethoxy) phenyl) propane have been used, but most of them have been used. It is a solid with a melting point of 50 ° C or higher. If these (meth) acrylates are molecularly designed to have a high refractive index, it is necessary to introduce halogen atoms such as bromine and iodine, and atomic groups such as benzene rings and sulfur, and as a result, they must be liquefied at room temperature. Becomes difficult.

In addition, when these atomic groups are introduced, fluidity is required at the time of casting into a mold or at the time of coating, so that a large amount of diluting monomer is required, and as a result, physical properties such as lowering the refractive index are reduced. In addition, when used as a main component, it is necessary to heat to a temperature exceeding 60 ° C. and cast it, and it is necessary to continue heating during curing molding as well, and its handling properties and storage stability (especially during heating) In many cases).

[0004]

DISCLOSURE OF THE INVENTION The present invention solves the above problems, has excellent storage stability, shows good curability upon irradiation with active energy rays such as ultraviolet rays, and has a high refractive index and a high fluidity. It is an object of the present invention to provide a composition excellent in handling properties in terms of a manufacturing method from the viewpoint of balance and an optical material having high refractive index and high transparency in physical properties of a molded product after curing.

[0005]

Means for Solving the Problems In view of the above problems, as a result of intensive studies, the present inventors have added a specific amount of a polymerization inhibitor to a sulfur-containing (meth) acrylate compound represented by the general formula (I) as a polymerization initiator. By containing together, it shows good curability, composition with excellent handling properties from the viewpoint of balance between refractive index, fluidity, etc., and physical properties of molded products after curing have high refractive index and transparency They have found that a high optical material can be provided, and have completed the present invention. That is, the gist of the present invention is that (A) a radical-reactive composition containing a sulfur-containing (meth) acrylate compound represented by the general formula (I), (B) 0.001 part by weight based on 100 parts by weight of (A).
The present invention relates to a photocurable composition comprising -0.5 parts by weight of a polymerization inhibitor and (C) a polymerization initiator, and a cured product obtained by curing the composition.

[0006]

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[Wherein, R ¹ represents a hydrogen atom or a methyl group, R ² represents a divalent hydrocarbon group having 1 to 12 carbon atoms, and Ar may be substituted with a halogen atom other than a fluorine atom. A good C 6-30 arylene group or a C 7-30 aralkylene group which may be substituted with a halogen atom other than a fluorine atom, and X represents —O— or —.
Y represents -S- or-when X represents -O-;
SO ₂ - indicates if shows the X is -S- Y is -S -, -
SO ₂ —, —CO—, an alkylene group having 1 to 12 carbon atoms, an aralkylene group having 7 to 30 carbon atoms, or —Ar— (Y—Ar) p—

[0008]

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(Wherein, R ³ represents an alkylene group having 1 to 12 carbon atoms which may have an ether bond, and k is a number of 1 to 5 representing an average degree of oligomerization). Oligomer or

[0010]

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(Wherein 1 represents an average degree of oligomerization.
-5. )), And Z represents -O- or -S-. m and n each represent an integer of 1 to 5, and p represents an integer of 0 to 10. ]

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The (A) sulfur-containing (meth) acrylate compound used in the present invention or a radical reactive composition containing the same comprises the sulfur-containing (meth) acrylate represented by the general formula (I). In the present invention, (meth) acrylate refers to both methacrylate and acrylate.
The radical-reactive composition containing a sulfur-containing (meth) acrylate compound usually refers to a mixture of the compound of the general formula (I) and a reactive monomer, a reactive oligomer or a polymer. The compound of the general formula (I) exhibits a high refractive index,
Since it has a well-balanced structure, it can be compatible with various solvents, reactive monomers, reactive oligomers, polymers, and the like. When the radical-reactive composition contains a reactive monomer, a reactive oligomer, a polymer, or the like other than the general formula (I), the content of the compound of the general formula (I) in the radical-reactive composition is determined by the radical-reactive composition For the whole thing,
It is usually at least 50% by weight, preferably at least 70% by weight.

In the general formula (I), R ¹ represents a hydrogen atom or a methyl group. R ² represents a divalent hydrocarbon group having 1 to 12 carbon atoms, such a group having 1 to 12 carbon atoms, being composed of a carbon atom and a hydrogen atom,
It is not particularly limited as long as it has one, but specific examples include an alkylene group such as a methylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a hexamethylene group, an octamethylene group, and a decamethylene group. Preferably, an alkylene group having 1 to 6 carbon atoms, more preferably, an alkylene group having 2 to 4 carbon atoms is used. A
r represents an arylene group having 6 to 30 carbon atoms which may be substituted with a halogen atom except fluorine, or an aralkylene group having 7 to 30 carbon atoms which may be substituted with a halogen atom except fluorine. C6-30, preferably 6
Specific examples of the arylene groups (1) to (12) include a phenylene group and a naphthylene group. Carbon number 7-30,
Preferably, the aralkylene group of 7 to 14 is-(C
_{H 2) x-Ar '-} , - Ar' - (CH 2) x -, - (CH
_{2) x-Ar '- (} CH 2) y- , and the like. Ar ′ represents an arylene group having 6 to 29 carbon atoms such as a phenylene group or a naphthylene group, x and y each represent an integer of 1 to 24, and the sum of the carbon numbers of the arylene groups represented by x, y and Ar ′ Is 7 to 30. These arylene groups and aralkylene groups may be usually substituted with 1 to 12, preferably 2 to 8 halogen atoms excluding a fluorine atom.

X represents -O- or -S-. Y is X
If but a -O-, -S- or -SO ₂ - shows a. Further, Y is when X is -S- _{are, -S -, - SO 2 -} ,
-CO-, an alkylene group having 1 to 12 carbon atoms, 7 to 7 carbon atoms
30 aralkylene groups, or -Ar- (Y-Ar) p
− Is

[0015]

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(R ³ represents an alkylene group having 1 to 12 carbon atoms which may have an ether bond in the chain, and k is a number of 1 to 5 representing an average degree of oligomerization.) Oligomer or

[0017]

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(1 is an integer of 1 to 5 representing the average degree of oligomerization). X is -S-
For, Y is preferably, -S -, - SO ₂ - and the like.

As the alkylene group having 1 to 12 carbon atoms,
Specifically, a methylene group, an ethylene group, a propylene group,
Examples include a trimethylene group, a tetramethylene group, a hexamethylene group, an octamethylene group, a decamethylene group, and a dodecamethylene group. Preferably, an alkylene group having 1 to 6 carbon atoms is used. 7-30 carbon atoms, preferably 7 carbon atoms
The ~ 14 aralkylene _{group, - (CH 2) x-} A
r '-, - Ar' - (CH 2) x -, - (CH 2) x-A
r '- represented by (CH ₂₎ y-. Ar ′ represents an arylene group having 6 to 29 carbon atoms such as a phenylene group or a naphthylene group; x and y each represent an integer of 1 to 24;
the sum of the carbon number of the arylene group represented by y and Ar ′ is 7
-30, preferably 7-14. As the alkylene group which may have an ether bond in the chain having 1 to 12 carbon atoms represented by R ³ , any alkylene group having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms The group which may have 1 to 5 -O- groups at the position of may be mentioned. Z represents -O- or -S-. m and n each represent an integer of 1 to 5, preferably 1 to 3, and p represents a number of 0 to 10, preferably 0 to 5.

Specific examples of the sulfur-containing (meth) acrylate represented by the general formula (I) include p-bis (β
-(Meth) acryloyloxyethylthio) xylene,
p-bis (β- (meth) acryloylthioethylthio)
Xylene, m-bis (β- (meth) acryloyloxyethylthio) xylene, m-bis (β- (meth) acryloylthioethylthio) xylene, α, α′-bis (β
-(Meth) acryloyloxyethylthio) -2,3
5,6-tetrachloro-p-xylene, α, α′-bis (β- (meth) acryloylthioethylthio) -2,
3,5,6-tetrachloro-p-xylene, 4,4′-
Di (β- (meth) acryloyloxyethoxy) diphenyl sulfide, 4,4′-di (β- (meth) acryloylthioethoxy) diphenyl sulfide, 4,4′-
Di (β- (meth) acryloyloxyethoxyethoxy) diphenylsulfone, 4,4′-di (β- (meth)
Acryloylthioethoxyethoxy) diphenylsulfone, 4,4′-di (β- (meth) acryloyloxyethylthio) diphenylsulfide, 4,4′-di (β-
(Meth) acryloylthioethylthio) diphenyl sulfide, 4,4′-di (β- (meth) acryloyloxyethylthio) diphenyl sulfone, 4,4′-di (β
-(Meth) acryloylthioethylthio) diphenylsulfone, 4,4′-di (β- (meth) acryloyloxyethylthio) diphenylketone, 4,4′-di (β-
(Meth) acryloylthioethylthio) diphenyl ketone, 2,4′-di (β- (meth) acryloyloxyethylthio) diphenyl ketone, 2,4′-di (β- (meth) acryloylthioethylthio) diphenyl ketone ,
4,4′-di (β- (meth) acryloyloxyethylthio) -3,3 ′, 5,5′-tetrabromodiphenylketone, 4,4′-di (β- (meth) acryloylthioethylthio) -3,3 ', 5,5'-tetrabromodiphenyl ketone, β, β'-bis (p- (meth) acryloyloxyphenylthio) diethyl ether, β, β'
-Bis (p- (meth) acryloylthiophenylthio)
Diethyl ether, β, β′-bis (p- (meth) acryloyloxyphenylthio) diethylthioether,
β, β′-bis (p- (meth) acryloylthiophenylthio) diethylthioether and the like.

Among the compounds represented by the general formula (I),
The compound represented by the following general formula (II) is preferably used from the viewpoint of balance of optical properties such as refractive index and chromatic aberration.

[0022]

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Where R¹¹Represents a hydrogen atom or a methyl group
Then R¹²Represents a divalent hydrocarbon residue having 1 to 12 carbon atoms.
Hal represents a chlorine atom or a bromine atom, and Y is -S
-, -SO _Two-Or -CO-, wherein Z is -O- or-
Represents S-. p ′ and q ′ are each independently 0 to 4
Represents an integer. In the general formula (II), R¹²Carbon indicated by
The divalent hydrocarbon residue of the formulas 1 to 12 has 1 carbon atom.
~ 12, consisting of carbon and hydrogen atoms,
There is no particular limitation as long as it has two joints,
Specifically, methylene, ethylene, propylene,
Limethylene group, tetramethylene group, hexamethylene group,
Alkylene groups such as octamethylene group and decamethylene group
No.

Specific examples of the sulfur-containing (meth) acrylate compound represented by the general formula (II) are:
4′-di (β- (meth) acryloyloxyethylthio) diphenyl sulfone, 4,4′-di (β- (meth)
Acryloylthioethylthio) diphenylsulfone,
4,4′-di (β- (meth) acryloyloxyethylthio) diphenyl sulfide, 4,4′-di (β- (meth) acryloylthioethylthio) diphenyl sulfide, 4,4′-di (β- ( (Meth) acryloyloxyethylthio) diphenyl ketone, 4,4′-di (β- (meth) acryloylthioethylthio) diphenyl ketone,
2,4′-di (β- (meth) acryloyloxyethylthio) diphenyl ketone, 2,4′-di (β- (meth)
Acryloylthioethylthio) diphenyl ketone, 4,
4′-di (β- (meth) acryloyloxyethylthio) -3,3 ′, 5,5′-tetrabromodiphenylketone 4,4′-di (β- (meth) acryloylthioethylthio) -3, 3 ', 5,5'-tetrabromodiphenyl ketone and the like.

Reactive monomers usable as a mixture with the compound represented by formula (I) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate and i-butyl (meth) acrylate. Acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, sterial (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, phenoxyethyl ( (Meth) acrylate, phenoxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2
-Hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycidyl (meth)
Acrylate, tetrahydrofurfuryl (meth) acrylate, phenylglycidyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, phenylcellosolob (meth) acrylate, dicyclopentenyl (meth) acrylate, biphenyl (meth) acrylate, Mono (meth) acrylate compounds such as 2-hydroxyethyl (meth) acryloyl phosphate; ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) Acrylate, nonaethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, trimethylo Tri (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexamethylene di (meth) acrylate,
Hydroxypivalic acid ester neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tris (meth) acryloxyethyl isocyanurate, etc. Functional (meth) acrylate compound; styrene, vinyl toluene, chlorostyrene,
Monovinyl compounds such as 1-vinylnaphthalene, 2-vinylnaphthalene and N-vinyl-2-pyrrolidone; and polyfunctional vinyl compounds such as divinylbenzene and divinylnaphthalene.

Reactive oligomers which can be used by mixing with a sulfur-containing (meth) acrylate include: (1) a hydroxyl, glycidyl or amino group-containing (meth) acrylate and two or more isocyanate groups in the molecule; (2) Epoxy ring-opening reaction product of (meth) acrylic acid and an epoxy compound having at least one epoxy group in a molecule; (3) Polyhydric alcohol and polybasic acid (4) a polyester (meth) acrylate which is a reaction product of a polyester obtained from and (meth) acrylic acid; (4) an esterification reaction product of (meth) acrylic acid with a polyfunctional hydroxyl compound, containing a hydroxyl group or a glycidyl group ( (5) an esterification reaction product of a meth) acrylate and a polyvalent carboxyl compound; It can be mentioned transesterification reaction with various (meth) acrylate and a polyhydric hydroxyl compound.

A urethanization product of a hydroxyl group, glycidyl group or amino group-containing (meth) acrylate and an isocyanate compound having two or more isocyanate groups in a molecule; specific examples of the hydroxyl group-containing (meth) acrylate include: 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-
Hydroxybutyl (meth) acrylate; addition reaction product of monoepoxy compound such as butyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, glycidyl methacrylate and (meth) acrylic acid; (meth) of polyethylene glycol and polypropylene glycol And acrylic acid monoesters.

Specific examples of the isocyanate compound having at least two isocyanate groups in the molecule include aliphatic, aromatic or alicyclic isocyanates such as tetramethylene diisocyanate, hexamethyldiisocyanate, trimethylhexamethylene diisocyanate, and dimer. Acid diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenyl methane diisocyanate, m-phenylene diisocyanate, dicyclohexyl methane diisocyanate, naphthalene diisocyanate, biphenyl diisocyanate, and the like. At least one active hydrogen atom such as a hydroxyl group, a carboxyl group, or water Compounds having at least one isocyanate group in the resulting molecules by reaction with a compound which, or the like trimeric 5 dimer of the diisocyanate compounds may also be used. The urethanization reaction between the hydroxyl group-containing (meth) acrylate and the isocyanate compound having at least two isocyanate groups in the molecule can be performed by a known method, for example, a method in which a hydroxyl group-containing (meth) acrylate and a catalyst are used in the presence of an isocyanate compound. For example, it can be produced by dropping a mixture with dibutyltin dilaurate under the condition of 50 ° C to 90 ° C.

An epoxy ring-opening reaction product of (meth) acrylic acid and an epoxy compound having at least one epoxy group in the molecule; specific examples of the epoxy compound having at least one epoxy group in the molecule include bis Aromatic and alicyclic epoxy compounds such as phenol A diglycidyl ether, bisphenol F diglycidyl ether, phenol novolak glycidyl ether, and cresol novolac glycidyl ether; glycidyl esters of aliphatic polycarboxylic acids; dimer of these epoxy compounds A pentamer to a pentamer can be used.

As the polyvalent carboxyl compound, dicarboxylic anhydride such as phthalic anhydride can be used. The reaction of these epoxy compounds with (meth) acrylic acid or an adduct of a hydroxyl group-containing (meth) acrylate and a polyvalent carboxyl compound with a dicarboxylic anhydride such as phthalic anhydride can be carried out by a known method, for example, an epoxy compound and (meth) A mixture of acrylic acid and a catalyst, for example, a tertiary amino compound such as dimethylaminoethyl methacrylate, a quaternary amine salt, and a mixture of a quaternary amine salt at 60 ° C. to 110 ° C.
It can be manufactured by heating to. Polyester (meth) acrylate which is a reaction product of a polyester obtained from a polyhydric alcohol and a polybasic acid with (meth) acrylic acid; specific examples of polyester acrylate include ethylene glycol, 1,4-butanediol, 1 Polyhydric alcohols such as 1,6-hexanediol, diethylene glycol, trimethylolpropane, dipropylene glycol, polyethylene glycol, and polypropylene glycol, and phthalic acid, adipic acid, maleic acid, trimellitic acid, itaconic acid, succinic acid, terephthalic acid, etc. A condensation reaction product of a polyester obtained from a polybasic acid and (meth) acrylic acid is exemplified. The reaction between a polyhydric alcohol and a polybasic acid is performed by heating to 200 ° C in the presence of a catalyst such as dibutyltin oxide to obtain a polyester, which is then subjected to a condensation reaction with (meth) acrylic acid at 100 ° C. Can be.

As the reactive oligomer, in addition to the above-mentioned oligomers, bisphenol A, bisphenol F or bisphenol S obtained by adding ethylene oxide or propylene oxide in an amount of n mol to an esterification reaction with (meth) acrylic acid. The resulting oligo (meth) acrylate is exemplified. As the reactive monomer and the reactive oligomer used in combination with the sulfur-containing (meth) acrylate compound, when the cured product of the photocurable resin is used for an application requiring a high refractive index, a halogen atom excluding fluorine, an aromatic atom, Monomers and oligomers containing a ring and / or a sulfur atom are preferred.

Other than the above-described monomers and oligomers containing an aromatic ring and a halogen atom, bis (4-methacryloylthiophenyl) sulfide, 2,4,6-tribromophenyl (meth) acrylate, 2,4,6 -Tribromophenylethyl (meth) acrylate, 2,2
-Bis [3,5-dibromo-4- (2-methacryloyloxyethoxy) phenyl] propane can be added in a range that does not impair the effects of the present invention.

The radical-reactive composition may be mixed with a polymer for adjusting viscosity, preventing polymerization shrinkage, imparting flexibility, and the like. Specific examples include polyethylene glycol,
Polypropylene glycol, polyethylene glycol,
Non-reactive polymers such as monoalkyl ether, polypropylene glycol monoalkyl ether, ethylene oxide or propylene oxide adduct of bisphenol A, ethylene oxide or propylene oxide adduct of tetrabromobisphenol A, and various poly (meth) acrylates; A polymer having a reactive group such as poly (meth) acrylate having a reactive group such as a hydroxyl group, an epoxy group, a vinyl group, an isocyanate group, a carboxyl group, or a mercapto group at a terminal or a side chain may be added. The molecular weight is preferably about 1,000 to 500,000 in terms of weight average molecular weight, and is preferably about several thousand to 200,000 for compatibility and development of physical properties.

The polymerization inhibitor (B) used in the present invention includes hydroquinone, p-methoxyphenol, 2-t
-Butylhydroquinone, 2,5-bis (1,1,3,
Phenols such as 3-tetramethylbutyl) hydroquinone and 2,5-bis (1,1-dimethylbutyl) hydroquinone; aromatic amines such as phenothiazine; and 2,2-diphenylpicrylhydrazyl (DPP)
H), tri-p-nitrophenylmethyl, di-p-fluorophenylamine, N- (3N-oxyanilino-
1,3-dimethylbutylidene) -aniline oxide,
Quaternary ammonium chlorides such as 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) and benzyltrimethylammonium chloride; diethylhydroxylamine, cyclic amides, nitrile compounds,
Substituted urea, benzothiazole, 4-amino-2,2,
6,6-tetramethylpiperidine, bis- (1,2,
Organic acids such as (2,6,6 pentamethyl-4-pipedinyl) separate, lactic acid, oxalic acid, citric acid, tartaric acid, and benzoic acid; and t-butyl pyrocatechol, organic phosphine, and phosphite. The amount of the polymerization inhibitor (B) to be added is 0.0 to 100 parts by weight of the component (A).
The amount is from 0.01 to 0.5 part by weight, preferably from 0.005 to 0.3 part by weight. If the amount of the polymerization inhibitor is too small, there is a problem in storage stability, and if the amount is too large, poor curing occurs or excessive addition of the polymerization initiator is required.

As the polymerization initiator (C) used in the present invention, for example, radical polymerization initiators and cationic polymerization initiators known as photopolymerization initiators are used, and 2,6-dimethylbenzoyldiphenylphosphine oxide, 2,
4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylphosphinic acid methyl ester, 2,6-dichlorobenzoylphenylphosphine oxide, 2,6-dimethyloxybenzoyldiphenylphosphine oxide, bis (2
6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, bis (2,4,6-
(Bis) acylphosphine oxides and (bis) acylphosphinic esters such as trimethylbenzoyl) -phenylphosphine oxide; 1-phenyl-2
-Hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 4-diphenoxydichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1- Acetophenone compounds such as benzophenone, 4-phenylbenzophenone, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, benzophenone compounds such as 3,3'-dimethyl-4-methoxybenzophenone, diphenoxybenzophenone; aromatics Diazonium salts; aromatic sulfonium salts; aromatic iodonium salts; metallocene compounds and the like.

The photopolymerization initiators may be used alone or in combination of two or more.
It is preferable to use a compound having an absorption wavelength even at 0 nm or more. This is because the light resistance and weather resistance of the sulfur-containing (meth) acrylate compound represented by the general formula (I) are not so good, so that the short-wavelength side light is cut off during molding and irradiated, or a UV absorber is added. This is because the composition is required to be cured with light of a long wavelength side so that the reaction is not inhibited by the molding methods and additives. As the compound having an absorption wavelength of 400 nm or more, (bis) acyl phosphine oxides are preferably used. Another one of photopolymerization initiator
As the species, it is preferable to use benzophenones and acetophenones having excellent surface curability and having absorption on the short wavelength side, and (bis) acyl phosphine oxide having excellent internal curability.

In order to quickly complete the curing of the photocurable composition of the present invention, photocuring and heat curing may be used in combination. When heat curing is used in combination, it is preferable to use a photopolymerization initiator and a heat polymerization initiator in combination as the polymerization initiator (C). As the thermal polymerization initiator, benzoyl peroxide, diisopropyl peroxycarbonate, lauroyl peroxide, t-butylperoxy (2-ethylhexanoate), azobisisobutyronitrile, and the like may be used. In the case of heating at 45 to 60 ° C. at the time of casting or the like, it is desired that the curing does not progress even in such an environment, and that the initiator has a 10-hour half-life temperature of 90 ° C. or more. For example, 1,1
-Bis (t-butylperoxy) cyclohexane, 2,
2-bis (4,4-di-t-butylperoxycyclohexyl) propane, 1,1-bis (t-butylperoxy) cyclododecane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid , T-butylperoxy 3,5, -trimethylhexanate, t-butylperoxylaurate, 2,5-
Dimethyl-2,5-di (m-toluoxyperoxy) hexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy 2-ethylhexyl monocarbonate, t-hexylperoxybenzoate,
2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxyacetate,
2-bis (t-butylperoxy) butane, n-butyl-4,4-bis (t-butylperoxy) valerate,
Di-t-butylperoxyisophthalate, α, α′-
Bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,
5-di (t-butylperoxy) hexane, t-butylcumyl peroxide, di-t-butylperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3 and the like. No.

The amount of the polymerization initiator (C) to be added is as follows.
The amount is preferably 0.01 to 10 parts by weight, more preferably 0.02 to 5 parts by weight, based on 00 parts by weight. If the amount of the initiator is too large, not only the internal homogeneity of the cured resin is poor, but also the hue is deteriorated. If the amount is too small, poor curing occurs. As a result of intensive studies on the addition amounts of the polymerization inhibitor (B) and the polymerization initiator (C), the weight ratio of the polymerization initiator and the polymerization inhibitor to the component (A) (polymerization initiator (C) / polymerization inhibitor ( B)) was found to have a significant effect on stability and the like. The weight ratio of (C) / (B) is usually 0.05 to 50.
00, preferably 0.1 to 2000. When both are added in such a weight ratio, the long-term storage stability at room temperature is excellent, and the temperature applied during casting and molding is 45 to 60.
Shows good stability even at ℃. If the ratio is too large, the polymerization inhibitor is small, so that long-term storage stability and the effect of inhibiting curing during a heating process such as casting during heating cannot be obtained. On the other hand, if it is too small, the amount of the initiator is small relative to the amount of the polymerization inhibitor, so that poor curing occurs.

The photopolymerizable composition of the present invention may contain, if necessary, a compound having a thiol group, an ultraviolet ray inhibitor, a light stabilizer, an antioxidant, a photosensitizer, a solvent, a release agent, and a colorant. , Fillers and other additives can be appropriately compounded.
Known additives can be used as these additives.

Specific examples of the compound having a thiol group include ethyl mercaptan, hexyl mercaptan,
Octyl mercaptan, dodecyl mercaptan, stearyl mercaptan, mercaptoethanol, 1,2-ethanedithiol, 1,3-propanedithiol, 1,6-hexanedithiol, 1,12-dodecanedithiol, mercaptomethyl sulfide, 2-mercaptoethyl sulfide, 3-mercaptopropyl sulfide, 6-mercaptohexyl sulfide, 1,2-bis-2-mercaptoethylthioethane, 1,
2-bis-3-mercaptopropylthioethane, 1,3-bis-2
-Mercaptoethylthiopropane, 1,4-bis-2-mercaptoethylthiobutane, 1,6-bis-2-mercaptoethylthiohexane, bis-2- (2-mercaptoethylthio) ethylsulfide, 2-mercaptoethyl Ether, 3-mercaptopropyl ether, 6-mercaptohexyl ether, 1,4-cyclohexanedithiol, bis-2-mercaptoethoxymethane, 1,2-bis-2-mercaptoethoxyethane, bis-2- (2-mercaptoethoxy ) Ethyl ether, 1,4-benzenedithiol, 1,3-benzenedithiol, 1,2-benzenedithiol, 4-t-butyl-1,2-benzenedithiol, 1,2-bis (mercaptomethylene) benzene, 1 1,3-bis (mercaptomethylene) benzene, 1,4-bis (mercaptomethylene) benzene, 1,2-bis (mercaptoethylene) benzene, 1,3-bis (mercaptoethylene) Ren) benzene, 1,4-bis (mercaptomethyl ethylene) benzene, 1,2-bis (mercaptomethyl methylene thio) benzene, 1,
3-bis (mercaptomethylenethio) benzene, 1,4-bis (mercaptomethylenethio) benzene, 1,2-bis (2-mercaptoethylenethio) benzene, 1,3-bis (2-mercaptoethylenethio) benzene, 1,4-bis (2-mercaptoethylenethiomethylene) benzene, 1,2-bis (2-mercaptoethylenethiomethylene) benzene, 1,3-bis (2-mercaptoethylenethiomethylene) benzene, 1,4-bis ( 2-mercaptoethylenethiomethylene) benzene, 1,2-bis (mercaptomethyleneoxy) benzene, 1,3-bis (mercaptomethyleneoxy) benzene, 1,4-bis (mercaptomethyleneoxy) benzene, 1,2-bis (2-mercaptoethyleneoxy) benzene, 1,3-bis (2-mercaptoethyleneoxy) benzene, 1,4-bis (2-mercaptoethyleneoxy) benzene, 4,4'-thiodithiopheno , 4,4 '
-Biphenyldithiol, 1,3,5-trimercaptobenzene, trimercaptoethylisocyanurate, pentaerythritol tetrathioglycolate, pentaerythritol trithioglycolate, pentaerythritol dithioglycolate, pentaerythritol tetramercaptopropionate, pentaerythritol Trimercaptopropionate, pentaerythritol dimercaptopropionate, trimethylolpropanetrithioglycolate, trimethylolpropanedithioglycolate, trimethylolpropane trimercaptopropionate, trimethylolpropanedimercaptopropionate, mercaptopropyl isocyanate Nurate and the like.

Many of these compounds having a thiol group have a high refractive index because of containing a sulfur atom, and show various Abbe numbers. Therefore, usually, the refractive index and Abbe number of the composition are maintained and adjusted. Used for As the compound having a thiol group, a polyfunctional thiol is preferably used. Specific examples include pentaerythritol thiols and isocyanurate thiols.
The polyfunctional thiol has a reaction promoting effect due to its reactivity and a flexible skeleton, and can impart flexibility. Further, since the thiol group has a radical chaining ability and a radical scavenging ability, it can prevent yellowing during curing and improve weather resistance. The amount of the compound having a thiol group is usually 1 to 30 parts by weight based on 100 parts by weight of the radical reactive composition.
Parts by weight, preferably 2 to 15 parts by weight. If the amount of the thiol-containing compound is too small, the above-mentioned effects cannot be expected. If the amount is too large, poor curing, bleed-out and the like may occur.

Examples of the ultraviolet absorber include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole,
2- (2'-hydroxy-5'-t-butylphenyl)
Benzotriazole, 2- (2'-hydroxy-5'-
Octylphenyl) benzotriazole, 2- (2'-
(Hydroxy-4′-octoxyphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′,
5′-di-t-butylphenyl) benzotriazole,
2- (2'-hydroxy-3 ', 5'-di-t-amylphenyl) benzotriazole, 2- (2'-hydroxy-3'-dodecyl-5'-methylphenyl) benzotriazole, 2- (2 '-Hydroxy-3', 5'-bis (α, α-dimethylbenzyl) phenyl) benzotriazole, 2- (2'-hydroxy-3'-t-butyl-
5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole, 2-
(2′-hydroxy-5 ′-(meth) acryloxyethylphenyl) -2H-benzotriazole, 2- (2 ′
-Hydroxy-5 '-(meth) acryloxyethylphenyl) -2H-benzotriazole alone or as a copolymer with an ethylenically unsaturated compound, such as a benzotriazole ultraviolet absorber; 2,4-dihydroxybenzophenone, 2- Hydroxy-4-methoxybenzophenone,
2-hydroxy-4-n-octoxybenzophenone,
2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2- Hydroxy-4-methoxy-5
-Sulfoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2 ',
4,4′-tetrahydroxybenzophenone, 2,2 ′
-Dihydroxy-4,4'-dimethoxy-5-sodiumsulfoxybenzophenone, bis (5-benzoyl-4
-Hydroxy-2-methoxyphenyl) methane, 2-hydroxy-4- (meth) acryloxyethoxybenzophenone, 2-hydroxy-4- (meth) acryloxyethoxybenzophenone homopolymer or copolymer with ethylenically unsaturated compound Benzophenone ultraviolet absorbers such as polymers; phenyl salicylate, 2,5-di-t-butyl-4-hydroxybenzoic acid n-hexadecyl ester, 4-t-butylphenyl salicylate, 4-t-octylphenyl salicylate; Salicylate UV absorbers such as 2,4-di-t-butylphenyl-3 ′, 5′-di-t-butyl-4′-hydroxybenzoate;
Ethyl (β, β-diphenyl) cyanoacrylate, 2
A cyanoacrylate-based ultraviolet absorber such as -ethylhexyl (β, β-diphenyl) cyanoacrylate;
Oxalic acid derivative-based ultraviolet absorbers such as ethoxy-2′-ethyl oxalic acid bisanilide and 2-ethoxy-5-tert-butyl-2′-ethyl oxalic acid bisanilide; [(4-methoxyphenyl) -methylene] dimethylpropanediate; And benzylidene malonic esters.

As light stabilizers, phenyl-4-pipedinyl carbonate, 1,1- (1,2-ethanediyl)
Bis (3,3,5,5-tetramethylpiperazinone), bis (2,2,6,6-tetramethyl-4-pipedinyl) sebacate, bis (N-methyl-2,2,
6,6, -tetramethyl-4-pipedinyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4
-Pipedinyl) -1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-pipedinyl) -1,2,3,4-butanetetracarboxylate, 3-dodecyl-1- (2,
2,6,6-tetramethyl-4-pipedinyl) pyrrolidine-2,5-dione, N-acetyl-3-dodecyl-
Hindered amine (HALS) -based light stabilizers such as 1- (2,2,6,6-tetramethyl-4-pipedinyl) pyrrolidine-2,5-dione and the like can be mentioned.

Examples of the antioxidant include 2,6-di-t-butylphenol, 2,4-dimethyl-6-t-butylphenol, 2,6-di-t-butyl-4-methylphenol, and 2,6-di-t-butylphenol. Di-tert-butyl-4-ethylphenol, 2,4,6-tri-tert-butylphenol, 2,6
-Di-t-butyl-4-s-butylphenol, 2-t
-Butyl-4-methoxyphenol, vitamin E, 2,
6-di-t-butyl-4-hydroxymethylphenol, n-octadecyl-β- (4′-hydroxy-
3 ′, 5′-di-butylphenyl) propionate, 2
-T-butyl-6- (3'-t-butyl-5'-methyl-2'-hydroxybenzyl) -4-methylphenyl acrylate, propyl gallate, octyl gallate, lauryl gallate, 2,2'-methylene bis (4 -Methyl-6-t-butylphenol), 2,2′-methylenebis (4-ethyl-6-t-butylphenol), 4,
4'-methylenebis (2,6-di-t-butylphenol), 2,2'-methylenebis (4-methyl-6-cyclohexylphenol), 2,2'-dihydroxy-
3,3′-di (α-methylcyclohexyl) -5,5 ′
-Dimethyldiphenylmethane, 2,2'-ethylidene-
Bis (4,6-di-t-butylphenol), 2,2 ′
-Butylidenebis (4-methyl-6-t-butylphenol), 4,4'-butylidenebis (3-methyl-6-
t-butylphenol), triethylene glycol-N
-Bis [3- (3-t-butyl-4-hydroxy-5-
Methylphenyl) propionate], 1,6-hexanediol bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 4,4′-thiobis (6-t-butyl-m- Cresol), 4,4'-
Thiobis (3-methyl-6-t-butylphenol),
4,4'-thiobis (4-methyl-6-t-butylphenol), bis (3,5-di-t-butyl-4-hydroxybenzyl) sulfide, tetrakis [methylene-3
-(3 ', 5'-di-t-butyl-4-hydroxyphenyl) propionate)] a phenolic antioxidant such as methane; triphenyl phosphite, diphenyl nonyl phenyl phosphite, tris (2,4-di- -T-
Butylphenyl) phosphite, trisnonylphenyl phosphite, diphenylisooctyl phosphite,
2,2'-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, diphenylindesyl phosphite, diphenyl mono (tridecyl) phosphite, phenyl diisodensyl phosphite, phenyl di (tridecyl) phosphite , Tris (2-ethylhexyl) phosphite, tris (indyl) phosphite, tris (tridecyl) phosphite, dibutyl hydrogen phosphite, trilauryl trithiophosphite, 4,4'-butylidenebis (3-methyl-6-t
-Butylphenyl) di-tridecyl phosphite, 3,
Phosphorus antioxidants such as 5-di-t-butyl-4-hydroxybenzyl phosphite diethyl ester; dilauryl-3,3′-thiodipropionate, ditridecyl-3,3′-thiodipropionate; Dimyristyl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate,
Lauryl stearyl-3,3'-thiodipropionate, pentaerythritol tetra (β-lauryl thiopropionate) ester, stearyl thiopropionamide, dioctadecyl disulfide, 2-mercaptobenzimidazole, 2-mercapto- Sulfur-based antioxidants such as 6-methylbenzimidazole and 1,1′-thiobis (2-naphthol); alkylated diphenylamines such as 4,4′-dioctyldiphenylamine; alkylated N, N′-diallyl And aromatic amine antioxidants such as -p-phenylenediamine, N-phenyl-β-naphthylamine, and N, N'-di-2-naphthyl-p-phenylenediamine.

Examples of photosensitizers include triethanolamine, triisopropanolamine, 2-diethylaminobenzoic acid, ethyl diethylaminobenzoate, isoacyl diethylaminobenzoate, n-butylamine, di-n-
Amine derivatives such as butylamine; urea derivatives such as o-trithiourea; sulfur compounds such as sodium diethyldithiophosphate and s-benzylisothiuronium-p-toluenesulfinate; N, N-dimethyl-p
-Nitrile compounds such as -aminobenzonitrile and N, N-dimethyl-p-aminobenzonitrile; phosphorus compounds such as tri-n-butylphosphine; N-nitrosohydroxyamine derivatives, oxazolidine compounds, tetrahydro-1,3-oxazine compounds And Michler's ketone.

The photocurable composition of the present invention may be used after being diluted with a solvent or the like. The sulfur-containing (meth) acrylate represented by the general formula (I) is soluble in a solvent such as acetone, methyl ethyl ketone, tetrahydrofuran, ethyl acetate, butyl acetate, and toluene. Organic solvents can also be used.

When a (meth) acrylate compound synthesized from an isocyanate compound or an isothiocyanate compound and a polythiol or a polyol compound is used as the radical reactive composition, a metal compound such as dibutyltin dilaurate or aluminum triisopropoxide may be used. Lewis bases such as tertiary amines and tertiary phosphines may be added as a catalyst for the (thio) urethanation reaction.

The photocurable composition of the present invention is usually used at room temperature to
It is preferably liquid at a temperature of 60 ° C. The photocurable composition of the present invention can be easily copolymerized (also referred to as photopolymerization or photocuring) by being irradiated with an active energy ray in the presence of a polymerization initiator. The active energy ray is not particularly limited as long as it acts on a polymerization initiator to generate a radical, such as ultraviolet light, visible light, infrared light, and electron beam. Usually contains sulfur (meta)
The selection is made according to the characteristic wavelengths of the acrylate compound, the monomer used in combination, the photopolymerization initiator, and the sensitizer. The light source or heat source for light irradiation when performing photocuring is not particularly limited, but generally, a parallel light using an ultraviolet light source such as a high-pressure or low-pressure mercury lamp, a metal halide lamp, a short arc lamp, a chemical lamp, and a xenon lamp. Curing is performed by irradiating scattered light, but a visible or infrared light source such as a laser can be used in combination with a photosensitizer. With an electron beam or the like, polymerization curing can be performed without a photopolymerization initiator.

When using a mold when photocuring the photocurable composition, the shape of the mold is not particularly limited.
The method of obtaining a cured product using the photocurable composition of the present invention,
There is no particular limitation, and a known film forming method in the atmosphere or an inert gas, a known casting polymerization method, and the like can be employed. As an example of a typical polymerization method, the composition may be injected between a mold (quartz glass) held by an elastomer gasket or a spacer, and may be removed after irradiation with active energy rays. The irradiation light amount is appropriately selected depending on the type of the composition and the photopolymerization initiator, but is usually 0.01 to 300 J / cm ² , especially 20 to 10 J / cm ² .
0 J / cm ² is preferred.

The cured product obtained by curing the photocurable composition of the present invention is subjected to treatment such as annealing by heating after photocuring in order to promote curing and reduce stress distortion and optical distortion inside the resin. May go. Annealing is also effective in improving weather resistance, which is considered to be due to acceleration of curing. Further, the surface of the obtained cured product may be subjected to a hard coat, an antireflection coat, or dyeing, or the lens portion may be subjected to a selective surface treatment such as ion or low molecular diffusion.

[0051]

According to the present invention, excellent storage stability, good curability upon irradiation with active energy rays such as ultraviolet rays, and excellent handling properties in terms of the manufacturing method from the viewpoint of the balance between the refractive index and the fluidity. It is possible to provide an optical material having high refractive index and high transparency in physical properties of the composition and a molded article after curing.

[0052]

The present invention will be described below in detail with reference to examples, but is not limited to the following without departing from the gist thereof. In addition, the refractive index is Na (d) using an Abbe refractometer.
Line, measured at 25 ° C. The change in viscosity was measured using an E-type viscometer.
Measured in ° C. Hardness is measured by Barcol hardness tester SoftT
Using ype, it was expressed as an average of a total of 10 points for each of the front and back 5 points.

Example 1 0.1 part by weight of p-methoxyphenol was added to 100 parts by weight of 4,4'-di (β-methacryloyloxyethylthio) diphenylsulfone,
0.1 part by weight of 6-trimethylbenzoyldiphenylphosphine oxide (manufactured by BSF Japan Ltd., "Lucillin TPO") and 0.04 part by weight of benzophenone are added, and the mixture is uniformly stirred and mixed at 60 ° C. for 1 hour, followed by defoaming. Thus, a photocurable composition was obtained. Next, two pieces of 80 mm diameter quartz glass with mirror finish were faced to each other at an interval of 2 mm, and placed in a casting container surrounded by a gasket made of an ethylene-vinyl acetate copolymer. After the product was poured and left to return to room temperature, it was irradiated with 12 J / cm ^{2 using} a metal halide lamp at 30 mW / cm ² to obtain a uniform and transparent cured product. The refractive index of the obtained cured product was 1.
64 and hardness was 86. On the other hand, when the above-mentioned photocurable pre-composition was kept at 25 ° C, it remained uniform and transparent for about 3 weeks without crystallization. In addition, the initial physical properties were maintained for about one month when maintained at 45 ° C. and for about 2 weeks when maintained at 60 ° C. without any change in viscosity, coloration, etc.

<Example 2> The 2,4,6-trimethylbenzoyldiphenylphosphine oxide of Example 1 0.1
Example 1 was repeated except that 0.2 parts by weight of 1-hydroxycyclohexyl phenyl ketone was used instead of 1 part by weight. As a result, a uniform and transparent cured product was obtained. The refractive index of the obtained cured product was 1.64. On the other hand, when kept at 25 ° C., the photocurable composition kept uniform and transparent without crystallization for about 3 weeks. In addition, the initial physical properties were maintained for about one month when maintained at 45 ° C., and for about two weeks when maintained at 60 ° C., with no change in viscosity increase or coloring.

<Embodiment 3> The 4,4'-di (β
-50 parts by weight of 4,4'-di (β-methacryloyloxyethylthio) diphenylsulfone instead of 100 parts by weight of -methacryloyloxyethylthio) diphenylsulfone, p-bis (β-methacryloyloxyethylthio)
When the same procedure as in Example 1 was carried out except that 50 parts by weight of xylene and 0.05 part by weight of diethylhydroxyamine were further added, a homogeneous and transparent cured product was obtained. The refractive index of the obtained cured product was 1.62. On the other hand, when kept at 25 ° C., the photocurable composition maintained uniform transparency without crystallization for one month or more. In addition, the initial physical properties were maintained for about one month when maintained at 45 ° C., and for about two weeks when maintained at 60 ° C., with no change in viscosity increase or coloring.

Example 4 Instead of 50 parts by weight of p-bis (β-methacryloyloxyethylthio) xylene of Example 3, 50 parts by weight of diethylene glycol dimethacrylate was used, and the amount of p-methoxyphenol added was 0.1%.
The same operation as in Example 3 was performed except that the amount was changed from 0.06 parts by weight to 0.06 parts by weight, and diethylhydroxyamine was not added. As a result, a uniform transparent cured product was obtained. The refractive index of the obtained cured product was 1.57. On the other hand, when kept at 25 ° C., the photocurable composition maintained uniform transparency without crystallization for one month or more. When the temperature was maintained at 45 ° C., there was no change in viscosity or coloration for about one month, and the initial physical properties were maintained.

<Example 5> The procedure of Example 4 was repeated, except that 50 parts by weight of diethylene glycol dimethacrylate was used instead of 50 parts by weight of diethylene glycol dimethacrylate. Obtained. The refractive index of the obtained cured product was 1.57. On the other hand, when the photocurable composition is kept at 25 ° C., 1
Uniform and transparent without crystallization for more than a month. Also 4
When maintained at 5 ° C., there was no change in viscosity, coloration, etc. for about one month, and the initial physical properties were maintained.

<Embodiment 6> The 4,4'-di (β
Instead of 100 parts by weight of -methacryloyloxyethylthio) diphenylsulfone, 95 parts by weight of 4,4'-di (β-methacryloyloxyethylthio) diphenylsulfone and 5 parts by weight of glycidyl methacrylate were used. 0.1 parts by weight to 0.09
Except that the amount was changed to parts by weight, the same procedure as in Example 1 was carried out to obtain a uniformly transparent cured product. The refractive index of the obtained cured product was 1.62. On the other hand, when kept at 25 ° C., the photocurable composition maintained uniform transparency without crystallization for about one month. In addition, when maintained at 45 ° C., there was no change in viscosity, coloration, etc. for about one month, and the initial physical properties were maintained.

<Embodiment 7> The 4,4'-di (β
Instead of 100 parts by weight of -methacryloyloxyethylthio) diphenylsulfone, 90 parts by weight of 4,4'-di (β-methacryloyloxyethylthio) diphenylsulfone and 2,4,6-tribromophenyl methacrylate (Daiichi Kogyo Seiyaku Co., Ltd. Co., Ltd., "BR-30M") was used in the same manner as in Example 1 except that 10 parts by weight of p-methoxyphenol was used and the amount of p-methoxyphenol was changed from 0.1 part by weight to 0.09 part by weight. A uniformly transparent cured product was obtained. The refractive index of the obtained cured product was 1.64. On the other hand, when kept at 25 ° C., the photocurable composition maintained uniform transparency without crystallization for about one week. When the temperature was maintained at 45 ° C., there was no change in viscosity, coloration, etc. for about one month, and the initial physical properties were maintained.

Example 8 Instead of 10 parts by weight of 2,4,6-tribromophenyl methacrylate of Example 7,
Example 7 was repeated except that 10 parts by weight of 2-bis [3,5-dibromo-4- (2-methacryloyloxyethoxy) phenyl] propane (“BR-42M” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was used. When the same operation was performed, a uniformly transparent cured product was obtained. The refractive index of the obtained cured product was 1.63.
On the other hand, when kept at 25 ° C., the photocurable composition maintained uniform transparency without crystallization for about one week. 45 ° C
, There was no change in viscosity, coloration, etc. for about one month, and the initial physical properties were maintained.

Example 9 The amount of 2,4,6-trimethylbenzoyldiphenylphosphine oxide added in Example 1 was changed from 0.1 parts by weight to 0.2 parts by weight, and the irradiation light source was changed to a wavelength of 390 m or less. Except for cutting and irradiating, the same procedure as in Example 1 was carried out to obtain a uniformly transparent cured product. The refractive index of the obtained cured product was 1.64. On the other hand, when kept at 25 ° C., the photocurable composition maintained uniform transparency without crystallization for about 3 weeks. In addition, when maintained at 45 ° C., there was no change in viscosity, coloration, etc. for about one month, and the initial physical properties were maintained.

Example 10 0.04 parts by weight of benzophenone of Example 1 was added to 1-hydroxycyclohexyl phenyl ketone (Ciba Specialty Chemicals Co., Ltd.)
And "Irgacure 184") were carried out in the same manner as in Example 1 except that the amount was changed to 0.2 part by weight, whereby a uniformly transparent cured product was obtained. The refractive index of the obtained cured product was 1.64. On the other hand, when kept at 25 ° C., the photocurable composition maintained uniform transparency without crystallization for about 3 weeks. Also 45
When kept at ℃, there was no change in viscosity, coloration, etc. for about one month, and the initial physical properties were maintained.

<Example 11> In place of 100 parts by weight of 4,4'-di (β-methacryloyloxyethylthio) diphenylsulfone in Example 1, 4,4'-di (β-acryloyloxyethylthio) diphenylsulfone 100
When the same procedure as in Example 1 was carried out except for using parts by weight, a uniformly transparent cured product was obtained. The refractive index of the obtained cured product was 1.64. On the other hand, when the photocurable composition was kept at 25 ° C., it remained uniformly transparent without crystallization for one month or more. In addition, when maintained at 45 ° C., there was no change in viscosity, coloration, etc. for about one month, and the initial physical properties were maintained.

Example 12 The photocurable composition of Example 1 was diluted to 50 parts by weight with toluene, and the diluted solution was diluted with 50 μl.
m on a PET film with an applicator
After heating in a hot air oven for 2 hours to evaporate the toluene, put it in a quartz glass container with a nitrogen flow and place it in a non-oxygen atmosphere with a high-pressure mercury lamp at 30 mW / cm ² at 24 J / c.
Irradiation with m ² gave a transparent coating film.

Comparative Example 1 A photocurable composition was prepared in the same manner as in Example 1 except that the amount of p-methoxyphenol was changed from 0.1 part by weight to 0.0005 part by weight. Obtained. In the step of uniformly stirring at 60 ° C. for 1 hour to produce a photocurable composition, an increase in viscosity was observed, and when the obtained photocurable composition was kept at 45 ° C., it gelled in a few days. .

Comparative Example 2 A cured product was obtained in the same manner as in Example 1 except that the amount of p-methoxyphenol was changed from 0.1 part by weight to 1 part by weight. The obtained cured product had a refractive index of 1.63 and a hardness of 83, and was insufficiently cured.

Comparative Example 3 A cured product was prepared in the same manner as in Comparative Example 2, except that 1 part by weight of p-methoxyphenol was changed to 1 part by weight of diethylhydroxyamine. The obtained cured product was insufficiently cured, and when the cured product was removed from the mold, the cured product was deformed and was too soft to measure the hardness.

<Comparative Example 4> The 4,4'-di (β
2,2-bis [3,5-dibromo-4- (2-methacryloyloxyethoxy) phenyl] propane (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., "BR") instead of 100 parts by weight of -methacryloyloxyethylthio) diphenyl sulfone. −42
M ") Example 1 was repeated using 100 parts by weight and stirring at 60 ° C for 1 hour, but stirring at 80 ° C for 1 hour.
A photocurable composition was prepared and a cured product was prepared in the same manner as described above. However, the photocurable composition was poured into a casting glass container, and had already been solidified when left at room temperature.

<Comparative Example 5> The 4,4'-di (β
Bis (4-methacryloylthiophenyl) in place of -methacryloyloxyethylthio) diphenylsulfone
Using sulfide (manufactured by Sumitomo Seika Co., Ltd., “MPSMA”) and stirring at 60 ° C. for 1 hour, the temperature was reduced to 80 ° C.
A photocurable composition was prepared and a cured body was prepared in the same manner as in Example 1 except that the mixture was stirred for 1 hour, but the photocurable composition was poured into a casting glass container and left until the temperature reached room temperature. so,
It had already solidified. The compositions and evaluation results of Examples 1 to 11 are summarized in Table 1, and the compositions and evaluation results of Comparative Examples 1 to 5 are summarized in Table 2.

[0070]

[Table 1]

[0071]

[Table 2]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 4/06 C09D 4/06 5/00 5/00 Z 181/02 181/02 181/06 181/06 181/06 C09J 4/06 C09J 4/06 181/02 181/02 181/06 181/06 (72) Inventor Yutaka Tamura 8-3-1 Chuo, Ami-cho, Inashiki-gun, Ibaraki Pref. Mitsubishi Tsukuba Research Laboratories (72) Inventor Seiichiro Hayakawa 8-3-1 Chuo, Ami-cho, Inashiki-gun, Ibaraki Pref. F-term in Tsukuba Research Laboratory, Mitsubishi Chemical Corporation (reference) SA24 SA26 SA77 SA79 SA83 SA84 SA85 SA87 TA01 UA01 VA01 WA02 WA06 WA10 4J027 AC03 AC06 AE02 AE03 AE04 AG08 AG23 AG24 AG27 AH03 AJ02 BA05 BA07 BA08 BA09 BA10 BA11 BA12 BA20 BA26 CA29 CB10 CC05 CD04 CD08 CD1 4J038 FA 21 FA131 FA141 FA151 FA161 FA211 FA241 FA251 FA261 FA271 FA281 GA02 GA03 GA07 GA12 GA13 GA14 JA03 JA33 JA35 JA60 JA64 JA66 JB01 JB06 JB16 JB17 JB21 JB30 JC17 JC18 JC23 JC38 KA02 KA03 NA01 NA17 NA26 PA17 FAB11 FA141 FA141 FA0401 FA271 FA281 FA291 GA05 GA06 GA08 GA11 GA17 GA19 GA24 GA25 HB06 HB19 HB22 HB33 HB38 HB41 HC01 HC06 HC09 HC14 HC15 HC16 HC17 HC21 HD18 HD19 HD24 HD43 JB08 KA12 KA13 KA19 LA05 LA10 4J100 AB00Q AB02Q AB04Q03Q08 AL16Q08Q16 AL65Q AL66P AL67Q AQ08Q BA02P BA02Q BA03Q BA08Q BA12P BA51P BA53P BA58P BB01P BB03P BC04Q BC28Q BC43P BC44Q BC53Q BC54Q BC75Q CA01 CA04 CA23 DA62 DA63 JA01 JA03 JA33

Claims (9)

[Claims] (A) a sulfur-containing (meth) acrylate compound represented by the general formula (I) or a radical-reactive composition containing the same, and (B) 0.001 to 0 parts by weight per 100 parts by weight of the component (A). A photocurable composition comprising: 0.5 parts by weight of a polymerization inhibitor; and (C) a polymerization initiator. Embedded image [Wherein, R ¹ represents a hydrogen atom or a methyl group, R ² represents a monovalent hydrocarbon group having 1 to 12 carbon atoms, and Ar represents a carbon number which may be substituted with a halogen atom except a fluorine atom. An arylene group of 6 to 30 or an aralkylene group of 7 to 30 carbon atoms which may be substituted with a halogen atom except a fluorine atom, X represents -O- or -S-, and X represents -O- when Y is -S- or -SO ₂ - indicates,
If X represents -S- Y is _{-S -, - SO 2 -,} - CO
-Is an alkylene group having 1 to 12 carbon atoms, an aralkylene group having 7 to 30 carbon atoms, or -Ar- (Y-Ar) p-. Wherein R ³ represents an alkylene group having 1 to 12 carbon atoms which may have an ether bond, and k is a number of 1 to 5 representing an average degree of oligomerization. , (Wherein, l is a number from 1 to 5 representing the average degree of oligomerization) and represents a group selected from oligomers represented by
Represents -O- or -S-. m and n are each 1 to
5 represents an integer, and p represents an integer of 0 to 10. ] 2. (C) With respect to 100 parts by weight of the component (A),
The photocurable composition according to claim 1, wherein the component is 0.01 to 10 parts by weight. 3. The photocurable composition according to claim 2, wherein the weight ratio ((C) / (B)) of the component (C) to the component (B) is 0.05 to 5000. 4. The photocurable composition according to claim 1, wherein the polymerization initiator is a compound containing phosphorus. 5. A cured product obtained by curing the photocurable composition according to claim 1. 6. A resin composition for an optical lens, comprising the photocurable composition according to claim 1. 7. A resin composition for an optical component, comprising the photocurable composition according to claim 1. 8. A resin composition for antireflection coating, comprising the photocurable composition according to claim 1. 9. A resin composition for an adhesive, comprising the photocurable composition according to claim 1. Description: