JPH02251533A - Resin composition for optical material - Google Patents

Abstract

PURPOSE:To obtain the subject novel composition having light weight, excellent heat resistance, surface hardness, processability, etc., and easy moldability by bulk-polymerizing a mixture containing one or more kinds of a specific monomer and one or more kinds of another kind of monomer and three-dimensionally cross-linking the polymer. CONSTITUTION:The objective composition is produced by mixing (A) one or more kinds of the 1st monomer having >=2 SH groups in one molecule and expressed preferably by formula (Y is O=C-O or O-C=O; R is methyl or ethyl; (k) is 1 or 2; (p) is 3 or 4) and (B) one or more kinds of the 2nd monomer containing >=2 radically polymerizable functional groups containing carbon- carbon double bond irrespective of the kind of the functional group (e.g. divinylbenzene), adding a polymerization initiator, an ultraviolet absorber, etc., to the mixture, polymerizing by bulk-polymerization and three-dimensioally cross-linking the polymer. The total number of the SH groups in the component A is selected to be 0.1 to 1.2 times the total number of the functional groups in the component B.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention provides a novel resin for optical materials that is lightweight, has excellent transparency, heat resistance, surface hardness, impact resistance, and processability, and is easy to mold. It is something that will take place.

[Conventional technology]

Conventionally, various synthetic resins to replace inorganic glass have been researched, proposed, and put into practical use. For example, diethylene glycol bisallyl carbonate can be mentioned.Recently, various allyl carbonates have been radically polymerized, various (meth)acrylic monomers have been radically polymerized, and isocyanate compounds and polyols and polythiols have been radically polymerized. Examples include urethane or thiourethane resins obtained by reaction, and resins obtained by combining them.

Furthermore, conventionally, compounds with SH groups have not been used as chain transfer agents in radical polymerization, as intermediate raw materials for radically polymerizable compounds such as acrylic monomers, or as raw materials for thiourethane resins. ing. It has also been reported that a compound having an SH group is directly subjected to radical addition polymerization to obtain mainly linear polymers. (For example, JP-A-62-2706
[Problem to be solved by the invention] However, conventional resins do not necessarily satisfy all required physical properties.In other words, allyl carbonate resin and (meth)acrylic resin are easy to mold, but have poor impact resistance. There are also disadvantages such as poor properties and a large number of synthesis processes to obtain the monomer. Furthermore, some urethane resins have good impact resistance, but their disadvantage is poor moldability during cast polymerization.

(Means for Solving the Problem!!) The present inventors have completed the present invention as a result of intensive research to improve the drawbacks of conventional resins. At least one type of first monomer having at least two SH groups in the molecule, and its Il, which is a radically polymerizable functional group containing a carbon-carbon double bond in the molecule.
A thermosetting resin composition for optical materials obtained by bulk-polymerizing and three-dimensionally crosslinking a liquid mixture containing at least one kind of second monomer having at least two of them immediately after g, by a radical polyaddition reaction. be.

In the present invention, the 21st L-mer may undergo radical polymerization in parallel with this radical polyaddition reaction.
As the first monomer of the present invention, monomers selected from Group A shown below are preferable. Monomers selected from Group I of the present invention are represented by general formulas (1) to (■). Among these, a diamer represented by the general formula (I) having at least three SH groups in the molecule is particularly preferred.

(In the formula, Y is -o=c-o- or ・oc=o-1t
(R represents a methyl group or an ethyl group, k represents 1 or 2, and p represents 3 or 4) General formula (■) HS - (CHz) m-Z - < (CI2). -(X)
-) Q--(CHz)e-Z-(CI2)h-9H(
In the formula, 2 represents 10=C-0- or -0-C=O-.

X represents an oxygen atom or an S atom, a represents 0 or 1, k-n-p each independently represents 1 or 2, q
represents an integer from 1 to 9) General formula (m) Group A general formula (1) % formula %)) (In the formula, X represents an oxygen atom or an S atom, a represents 0 or l, k% 0% p each independently represents 1 or 2, q represents an integer from θ to 9) General formula (■) In the formula, X and Y each independently represent a chlorine atom, a bromine atom,
Represents an alkyl group or a phenyl group, a.

(b each independently represents an integer of 0 to 5, n represents an integer of 0 to 2, and k represents an integer of 2 to 4) The compound represented by the general formula (1) of the present invention is specifically Trimethylolpropane tris (thioglycolate), trimethylolpropane tris (β-thiopropionate), trimethylolethane tris (thioglycolate), trimethylolethane tris (β-thiopropionate),
Examples include compounds such as pentaerythritol tetrakis (thioglycolate) and pentaerythritol tetrakis (β-thiopropionate).

Specifically, the compound represented by the general formula (II) of the present invention includes ethylene glycol dithioglycolate, ethylene glycol dithioprobionate, diethylene glycol dithioglycolate, diethylene glycol ditheopropionate, triethylene glycol ditheoglycolate, Triethylene glycol dithioprobionate,
1,4-butanedioldithioglycolate, 1.4-
Butanedioldithiopropionate, 1,6-hexanethioldithioglycolate,! , 6-hexanethioldithiobrobionate, 1,9-nonanedioldithioglycolate, 1,9-nonanedioldithioprobionate, ethylene bissulfur (2-ethanol)
Examples include compounds such as bis(β-thiopropionate), ethylenebissulfur(2-ethanol)bis(thioglycolate), and the like.

Specifically, the compound represented by the general formula (III) of the present invention is: , 2-ethanedithiol, 1.3-propanedithiol, 1.4-butanedithiol, 1.5-pentanedithiol, 1.6-hexanedithiol, ! , 7-
Hebutanedithiol, 1,8-octanedithiol, 1
゜9-nonanedithiol, 1. Compounds such as lO-decanedithiol, 2-mercaptoethyl ether, 2-mercaptoethyl sulfide, methylenebisoxyethanethiol, and ethylenebisoxyethanethiol are mentioned.

Specifically, the monomer represented by the general formula (TV) used in the present invention includes 1,2-dimercaptobenzene, 1.3
- Dimercaptobenzene! , 4-dimercaptobenzene,! , 2.3-) dimercaptobenzene, 1,2.
4-trimercaptobenzene, 1,3.5-trimercaptobenzene, 1, 2,3.4-tetramercaptobenzene, 1.2,3.5-tetramercaptobenzene, 1
．． 2,4.5-tetramercaptobenzene, 1.2-bis(mercaptomethyl)benzene, 1.3-bis(mercaptomethyl)benzene, 1.4-bis(mercaptomethyl)benzene, 1,2.3-) Lis(mercaptomethyl)benzene, 1.2.4-Tris(mercaptomethyl)benzene, L3.5-) Lis(mercaptomethyl)benzene, 1.2゜3.4-Tetrakis(mercaptomethyl)benzene, J, 2 .3.5-tetrakis(mercaptomethyl)benzene, 1,2,4.5-tetrakis(mercaptomethyl)benzene, l,2-bis(mercaptoethyl)benzene, 1.3-bis(mercaptoethyl)benzene, 1 .4-bis(mercaptoethyl)benzene, 1,2.3-)lis(mercaptoethyl)benzene, 1,2.4-)lis(mercaptoethyl)benzene, 1,3.5-tris(mercaptoethyl)benzene , 1,2,3.4-tetrakis (mercaptoethyl)
Benzene, 1,2,3.5-tetrakis(mercaptoethyl)benzene, 1,2,4.5-tetrakis(mercaptoethyl)benzene, 3-bromo-1,2-
Dimercaptobenzene, 5-bromo-1,3-dimercaptobenzene, 3-bromo-1,4-dimercaptobenzene, 5-bromo-1,2,3-)dimercaptobenzene, 5-bromo-1,2, 4-trimercaptobenzene, 2-bromo-1,3,5-trimercaptobenzene,
5-bromo-1,2,3,4-tetramercaptobenzene, 3,5-dibromo-1,2-dimercaptobenzene, 2,4-dibromo-1,3-dimercaptobenzene,
2,4,6-dibromo-1,3-dimercaptobenzene, 2,4,6-)dibromo-1,3,5-)dimercaptobenzene, 3-dibromo-1,3-dimercaptobenzene, 5- Chloro-1°3-dimercaptobenzene,
3-chloro-1,4-dimercaptobenzene, 5-chloro-1,2,3-trimercaptobenzene, 5-chloro-1,2,4-)dimercaptobenzene, 2-chloro-
1,3,5-)dimercaptobenzene, 5-chloro-1
, 2,3,4-tetramercaptobenzene, 3,5-dichloro-1,2-dimercaptobenzene, 2.4-dichloro-1,3-dimercaptobenzene, 2.4°6-dolichloro1.3- Dimercaptobenzene, 2.4゜6
-Dolichloro1.3.5-) Dimercaptobenzene, 3-methyl-1,2-dimercaptobenzene, 5-methyl-1,3-dimercaptobenzene, 3-methyl-1
, 4-dimercaptobenzene, 5-methyl-1,2,3
-) dimercaptobenzene, 5-methyl-1,2,4-
Tris-mercaptobenzene, 2-methyl-1,3,5-
) dimercaptobenzene, 5-methyl-J, 2,324
-tetramercaptobenzene, 3,5-dimethyl-1,
2-dimercaptobenzene, 2,4-dimethyl-1,3
-dimercaptobenzene, 2.4.6-)dimethyl-
1,3-dimercaptobenzene, 2.4.6-)dimethyl-1,3,5-)dimercaptobenzene, 3-ethyl-1,2-dimercaptobenzene, 5-ethyl-1,
3-dimercaptobenzene, 5.ethyl-1゜2.4-
) dimercaptobenzene, 2-ethyl-1,3,5-
trimercaptobenzene, 5-ethyl-j, 2,3.4
-tetramercaptobenzene, 3,5-diethyl-1,
2-dimercaptobenzene, 2,4-diethyl-1,3
-dimercaptobenzene, 2,4.6-) liethyl-1,3-dimercaptobenzene, 2,4.6-) liethyl-1,3.5-trimercaptobenzene, 3-propyl-dimer, 2-dimercaptobenzene , 2-propyl-
1,3,5-) dimercaptobenzene, 5-propyl-
1,2,3,4-tetramercaptobenzene, 3.5-
Dipropyl-1,2-dimercaptobenzene, 2.4-
Dipropyl-1,3-dimercaptobenzene, 2,4.
6-) ribrovir-1,3-dimercaptobenzene,
5-phenyl-1,2-dimercaptobenzene, 2-phenyl-! , 3.5-) mercaptobenzene derivatives in which a mercapto group is directly bonded to the benzene ring, such as rimercaptobenzene, 3-bromo-1,2-bis(mercaptomethyl)benzene, 5-bromo-1,3-bis( mercaptomethyl)benzene, 3-bromo-1,4-bis(mercaptomethyl)benzene, 5-bromo-1,2,3-)
Lis(mercaptomethyl)benzene, 5-bromo-1,
2,4-tris(mercaptomethyl)benzene, 5-bromo-1,2,3,4-tetrakis(mercaptomethyl)benzene, 2,4-dibromo-1,3-bis(mercaptomethyl)benzene, 2,4 .6-) dibromo-1,
3,5-)lis(mercaptomethyl)benzene, 3-chloro-1,2-bis(mercaptomethyl)benzene, 5
-chloro-1,3-bis(mercaptomethyl)benzene, 5-chloro-1,2,4-tris(mercaptomethyl)benzene, 5-chloro-1,2,3,4-tetrakis(mercaptomethyl)benzene, 3,5-dichloro-1
,2-bis(mercaptomethyl)benzene, 2,4.6
-Dolichloro1.3.5-) Lis(mercaptomethyl)benzene, 3-methyl-1,2-bis(mercaptomethyl)benzene, 5-methyl-1,3-bis(mercaptomethyl)benzene, 5-methyl- 1,2,3-tris(mercaptomethyl)benzene, 5-methyl-1,2,
3,4-tetrakis(mercaptomethyl)benzene,
3.5-dimethyl-1,2-bis(mercaptomethyl)
Benzene, 2,4.6-trimethyl-1,3-bis(mercaptomethyl)benzene, 2,4.6-)dimethyl-1,3,5-tris(mercaptomethyl)benzene,
3-ethyl-1゜2-bis(mercaptomethyl)benzene, 5-ethyl-1,3-bis(mercaptomethyl)benzene, 5-ethyl-1,2,4-)lis(mercaptomethyl)benzene, 2- Ethyl-1,3,5-)lis(
Mercaptomethyl)benzene, 3-a and 1,2-
Bis(mercaptomethyl)benzene, 2-propyl-1
, 3,5-tris(mercaptomethyl)benzene, 5-
Phenyl-1,2-bis(mercaptomethyl)benzene, 2-phenyl-1,3,5-tris(mercaptomethyl)benzene, 5-bromo-1,3-bis(mercaptoethyl)benzene, 3-bromo-1 , 4-bis(mercaptoethyl)benzene, 5-bromo-1,2,3-tris(mercaptoethyl)benzene, 5-bromo-1,2
,4-)lis(mercaptoethyl)benzene, 5-bromo1.2,3.4-tetrakis(mercaptoethyl)
Benzene, 2,4-dibromo-monitor, 3-bis(mercaptoethyl)benzene, 2,4゜6-dibromo-1,3
．． 5-) Lis(mercaptoethyl)benzene, 3-chloro-1,2-bis(mercaptoethyl)benzene, 5
-Chloro-1,3-bis(mercaptoethyl)benzene, 5-chloro-1,2,4-)lis(mercaptoethyl)benzene, 5-chloro-1,2,3,4-tetrakis(mercaptoethyl) Benzene, 3,5-dichloro-1
,2-bis(mercaptomer)benzene, 2,4.6
-Dolichloro1.3.5-tris(mercaptoethyl)benzene, 3-methyl-! , 2-2-mercaptoethyl)benzene, 5-methyl-1,3-bis(mercaptoethyl)benzene, 5-methyl-1,2,3-tris(mercaptoethyl)benzene, 5-methyl-1,2 ，
3,4-tetrakis(mercaptomethyl)benzene, 3
,5-dimethyl-1,2-bis(mercaptoethyl)benzene, 2,4.6-)dimethyl-1,3-bis(mercaptoethyl)benzene, 2,4.6-)dimethyl-1,3,5 −) lis(mercaptoethyl)benzene,
3-ethyl-1,2-bis(mercaptoethyl)benzene, 5-ethyl-1,3-bis(mercaptoethyl)benzene, 5-ethyl-1,2,4-tris(mercaptoethyl)benzene, 2-ethyl -1,3,5-tris(
Mercaptoethyl)benzene, 3-propyl-1,2-
Bis(mercaptoethyl)benzene, 2-propyl-1
,3,5-)lis(mercaptoethyl)benzene,5.
Mercaptoalkylbenzenes with an alkyl group between the mercapto group and the benzene ring, such as phenyl-1,2-bis(mercaptoethyl)benzene, 2-phenyl-1,3,5-tris(mercaptoethyl)benzene, etc. Examples include compounds.

In the present invention, the mixing ratio of the first monomer and the second monomer is such that the total number of SH groups in the first monomer is 0.1-1 of the total number of functional groups in the second monomer. It is preferable to double the amount, and 0. 5-1. It is more preferable to set it to 0 times. The SH group of the first monomer undergoes an addition reaction with the functional group of the second monomer in the presence of a radical polymerization initiator. moreover,
Polymerization continues by addition of the remaining SH groups to functional groups of another molecule. However, the number of SH groups in the first monomer is 1 or 2 relative to the total number of functional groups in the second monomer.
If the number is more than twice as large, the radical polyaddition reaction will not proceed efficiently and only products with low molecular weight will be obtained.On the other hand, if the total number of SH groups in the first monomer is 0.
If it is less than 1 time, the content of the first monomer will be too small, which will deviate from the gist of the present invention.

When the first monomer has two SH groups and the second monomer has two radically polymerizable functional groups, the molar ratio of the first monomer to the second monomer is The first monomer is preferably used in a ratio of 0.1-0.8. When an amount exceeding 8 is used, the radical polyaddition reaction does not proceed efficiently and only a low molecular weight product is obtained, making it difficult to obtain a resin having a three-dimensional crosslinked structure.

In addition, the functional groups of the second monomer used in the present invention include:
Examples include, but are not limited to, vinyl group, (meth)acrylic group, allyl group, and allyl carbonate group.When using a first monomer having two SH groups, at least three It is preferable to use a second monomer having a functional group, and when a second monomer having two SH groups is used, a first monomer having at least three functional groups is used. is preferred.

The molecule of the present invention contains at least 2 fj radically polymerizable functional groups containing carbon-carbon double bonds, regardless of the type thereof.
Specifically, the second monomer having A is a polyvalent vinyl compound such as divinylbenzene or divinylnaphthalene as a monomer having a vinyl group; - diacryloxybenzene, 1.4
- benzene derivatives such as dimethacryloxybenzene, 1,4-diacryloxyethoxybenzene, lid, 4-dimethacryloxyethoxybenzene, 1,5-diacryloxynaphthalene, l,5-dimethacryloxinaphthalene, Naphthalene derivatives such as 1, 5-bis(β-acryloxyethoxy)naphthalene, 1,5-bis(β-dimethacryloxyethoxy)naphthalene, 2,2'-bisacryloxybiphenyl, 2,2'- biphenyl derivatives such as bismethacryloxybiphenyl, 2.2'-bis(β-acryloxyethoxy)biphenyl, 2.2'-
Bis(β-dimethacrylokijetoxy)biphenyl, 2
．． 2'-bis(thoacryloxyphenyl)propane, 2
．． 2'-bis(4-methacryloxyphenyl)propane, 2,2'-bis(4-acryloxyethoxyphenyl)propane, 2,2'-bis(4-methacryloxyethoxyphenyl)propane, 2,2'- Bis(4-acryloxypolyethoxyphenyl)propane, 2,2'-bis(4-methacryloxypolyethoxyphenyl)propane, 2,2'-bis(4-7cryloxy3,5-dibromophenyl)propane, 2,2'-bis(tometacryloxy-3,5-dibromophenyl)propane, 2.2
'-Bis(4-acryloxyethoxy-3,5-dibromophenyl)propane, 2,2'-bis(4-methacryloxyethoxy-3,5-dibromophenyl)propane, 2,2'-bis(toacryloxyethoxy-3,5-dibromophenyl)propane, Roxyboethoxy-3,
5-dibromophenyl)propane, 2,2'-bis(4
-methacryloxypolyethoxy-3,5-dibromophenyl)propane, 2,2'-bis(4-acryloxy-
3,5-dichlorophenyl)propane, 2,2'-bis(4-methacryloxy-3,5-dichlorophenyl)
Propane, 2,2''-bis(4-acryloxyethoxy-3,5-dichlorophenyl)propane, 2,2'-bis(4-methacryloxyethoxy-3,5-dichlorophenyl)propane, 2,2'-bis (Toacryloxyboriethoxy-3,5-dichlorophenyl)propane, 2
．． Bisphenol A derivatives such as 2'-bis(4-methacryloxypolyethoxy-3゜5-dichlorophenyl)propane, 2.2'-bis(4-7cryloxyphenyl)sulfone, 2.2'-bis( tomethacryloxyphenyl) sulfone, 2,2'-bis(toacryloxyethoxyphenyl) sulfone, 2,2'-bis(4-methacryloxyethoxyphenyl) sulfone, 2,2'-bis(4-acryloxypoly) ethoxyphenyl) sulfone,
2.2'-bis(4-methacryloxypolyethoxyphenyl)sulfone, 2.2'-bis(4-acryloxy-
3,5-dibromophenyl) sulfone, 2,2'-bis(4-methacryloxy-3,5-dibromophenyl) sulfone, 2,2'-bis(4-acryloxyethoxy-
3,5-dibromophenyl) sulfone, 2゜2'-bis(4-methacryloxyethoxy-3,5-dibromophenyl) sulfone, 2,2'-bis(4-acryloxypolyethoxy-3,5-dibromo phenyl) sulfone, 2
．． 2'-bis(4-methacryloxypolyethoxy-3,
5-dibromophenyl)sulfone, 2,2'-bis(
4-acryloxy-3,5-dichlorophenyl) sulfone, 2,2'-bis(4-methacryloxy-3,5-dichlorophenyl) sulfone, 2,2'-bis(4-acryloxyethoxy-3,5-dichlorophenyl) Sulfone, 2,21-bis(4-methacryloxyethoxy-3
, 5-dichlorophenyl) sulfone, 2,2'-bis(
4-acryloxypolyethoxy-3,5-dichlorophenyl)sulfone, 2,2'-bis(4-methacryloxypolyethoxy-3,5-dichlorophenyl)sulfone,
Bisphenol S derivatives such as bis(4-acryloxyphenyl) sulfide, bis(4-methacryloxyphenyl) sulfide, bis(toacryloxyethoxyphenyl) sulfide, bis(4-methacryloxyethoxyphenyl) sulfide, bis(4-methacryloxyphenyl) sulfide, -Acryloxypolyethoxyphenyl) sulfide, bis(tometacryloxyboriethoxyphenyl) sulfide, bis(4-acryloxy-3,5-dibromophenyl) sulfide, bis(tometacryloxy-3,5-dibromophenyl) sulfide, (4-acryloxyethoxy-3,5-
dibromophenyl) sulfide, bis(4-methacryloxyethoxy-3,5-dibromophenyl) sulfide, bis(4-acryloxypolyethoxy-3,5-dibromophenyl) sulfide, bis(4-methacryloxypolyethoxy-3,5-dibromophenyl) sulfide ,5-dibromophenyl) sulfide, bis(4-acryloxy-3,5-dichlorophenyl) sulfide, bis(4-methacryloxy-3°5-dichlorophenyl) sulfide, bis(4-acryloxyethoxy-3,5-dichlorophenyl) Sulfide, bis(4-methacryloxyethoxy-3,5-dichlorophenyl) sulfide, bis(4-acryloxypolyethoxy-3,5-dichlorophenyl) sulfide, bis(
Thiodiphenol derivatives such as tomethacryloxypolyethoxy-3,5-dichlorophenyl) sulfide, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, nano ethylene glycol diacrylate, ethylene glycol Dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, nanoethylene glycol dimethacrylate, 1,4-butanediol diacrylate, 1゜4-butanediol dimethacrylate, 1,3-butanediol dimethacrylate acrylate, I,
3-butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, 1,9-nonanediol dimethacrylate, 1.1
Aliphatic alcohol derivatives such as 0-decanediol diacrylate, l,10-decanediol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate; The monomers include bisallyl terephthalate, bisallyl isophthalate, triallyl trimellitate, bisallyl diphenate, bis(allyloxycarbonylmethyl) terephthalate, 5,5'-dimethylbiphenyl. -3,3'-dicarboxylic acid allyl ester,
Polyvalent allyl esters such as 1,9-dimethoxynaphthalene-3,7-dicarboxylic acid allyl ester, 1,1'-dimethyldiphenylmethane-3,3'-dicarboxylic acid allyl ester; as a monomer having an allyl carbonate group is 1.3 benzene allyl carbonate, 1.
4-naphthalene bisallyl carbonate, 1,5-naphthalene bisallyl carbonate, 1,6-naphthalene bisallyl carbonate, 1. ? - Naphthalene bisallyl carbonate, 2,6-naphthalene bisallyl carbonate, 2,7-naphthalene bisallyl carbonate, 4
．． 41-diphenylbroban bisallyl carbonate,
Examples include compounds such as polyvalent allyl carbonates such as 4.4'-diphenylsulfone bisallyl carbonate and diethylene glycol bisallyl carbonate.

Moreover, the mixture for a resin composition for optical materials of the present invention has a first
In addition to the monomer and the second monomer, at least one third monomer having one radically polymerizable functional group containing a carbon-carbon double bond in the molecule regardless of its type. 0
The third monomer, which may be contained in an amount of up to 30% by weight, is suitably used, for example, when it is desired to adjust the refractive index of the resin or to improve the impact resistance and heat resistance of the resin. If the content of the third monomer exceeds 30% by weight, the crosslinking density of the resin obtained by polymerization becomes small and the object of the present invention cannot be achieved. Specific examples of such compounds include:
Styrene, 4-chlorostyrene, dichlorostyrene, bromostyrene, dipromostyrene, tophenylmaleimide, N-(2-chlorophenylmaleimide), N-cyclohexylmaleimide, triethylphenylmaleimide, trimethylphenylmaleimide, maleic anhydride, phenyl Acrylate, phenyl methacrylate, chlorophenyl acrylate, chlorophenyl methacrylate, dichlorophenyl acrylate, dichlorophenyl methacrylate, trichlorophenyl acrylate, trichlorophenyl methacrylate, bromophenyl acrylate, bromophenyl methacrylate, dibromophenyl acrylate, dibromophenyl methacrylate,
Tribromophenyl acrylate, tribromophenyl methacrylate, chlorophenoxyethyl acrylate, dichlorophenoxyethyl acrylate, trichlorophenoxyethyl acrylate, chlorophenoxyethyl methacrylate, dichlorophenoxyethyl methacrylate, trichlorophenoxyethyl methacrylate,
Bromophenoxyethyl acrylate, dibromophenoxyethyl acrylate, tribromophenoxyethyl acrylate, bromophenoxyethyl methacrylate, dibromophenoxyethyl methacrylate, tribromophenoxyethyl methacrylate, benzyl acrylate, benzyl methacrylate, bromobenzyl acrylate, dibromobenzyl acrylate, bromobenzyl methacrylate, dibromobenzyl methacrylate,
Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate,
Butyl methacrylate, pentyl acrylate, bench methacrylate, octyl acrylate, octyl methacrylate, dodecyl acrylate, dodecyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 2-ethylhexyl acrylate,
Examples include 2-ethylhexyl methacrylate, bornyl acrylate, bornyl methacrylate, dicyclopentenyl acrylate, dicyclopentenyl methacrylate, allyl benzoate, allyl naphthalenecarboxylate, phenyl acrylic carbonate, benzyl allyl carbonate, and the like.

In the present invention, a monomer mixture consisting of a first monomer and a second monomer mixed in a specific ratio is subjected to bulk polymerization in the presence of a polymerization initiator.

The method of polymerizing the resin composition of the present invention is not particularly limited, and any known polymerization method can be employed. For example, resin molded articles can be produced by heating the mixed solution in the presence of a polymerization initiator between molds held by gaskets or spacers, but also by photopolymerization or radiation polymerization. The polymerization initiator used here is not particularly limited, and known ones can be used. The polymerization initiator used for thermosetting is, for example, 2°2
'-Azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2-cyclopropylprobionitrile), 2.2'-azobis(2,4-dimethylvaleronitrile), 2, 2'-azobis(2-methylpropionitrile), 2,2'-azobis(2-methylbutyronitrile), t,t'-azobis(cyclohexane-1-carbonetrile), 2-phenyrazo 4-
methoxy-2,4-dimethylvaleronitrile), 2,2
'-azobis(2,4,4-trimethylpentane), 2
．． 2'-azobis(2-methylpropane), dimethyl 2
．． Azo compounds such as 21-azobis(2-methylpropionate), or t-butylperoxyisopropyl carbonate, cumylperoxyoctoate, t-
- Peroxy esters such as butyl peroxy isobutyrate, t-butyl peroxy bivalate, t-butyl peroxy (2-ethylhexanoate), diisopropyl peroxy dicarbonate, similystyl peroxy dicarbonate, etc. Peroxydicarbonates, benzoyl peroxide, diacyl peroxides such as 3,3.5-)ethylhexanoyl peroxide, isobutyryl peroxide, dialkyl such as dicumyl peroxide, di-t-butyl peroxide, etc. Peroxides, hydroperoxides such as dipropylbenzene hydroperoxide, t-butyl hydroperoxide,! , 1. Examples include peroxyketals such as -bis(t-butylperoxy)cyclohexane, ketone peroxides such as cyclohexanone peroxide, methyl ethyl ketone peroxide, and other peroxides. Further, initiators for curing with ultraviolet rays include benzoin isopropyl ether, benzophenone, benzoin isobutyl ether, acetophenone, etc., but are not limited to these.

The amount of the initiator is usually 0°001 relative to the monomer.
-10% by weight, preferably 0.01-5% by weight.

The type and concentration of the polymerization initiator used are determined in consideration of the composition of the monomer mixture, reactivity, reaction rate control, etc.

In addition, the resin composition of the present invention may contain an ultraviolet absorber of 0.03 to improve its light resistance and weather resistance, if necessary.
It is desirable to contain ~3.0% by weight, but if the concentration of the ultraviolet absorber is 0.01% by weight, the light resistance will be extremely low.
It has almost no effect on improving weather resistance, and if it exceeds 3.0% by weight, the coloring of yellow capsules becomes noticeable and the commercial value tends to decrease.

As the ultraviolet absorber used in the present invention, a wide range of UV absorbers can be used, such as benzotriazole type, benzophenone type, salicylic acid type, cyanoacrylate type, hindered amine type as ultraviolet stabilizer, Nlfl type, benzoate type, etc.

Furthermore, during polymerization, additives such as 1llJl agents, antioxidants, antistatic agents, various stabilizers, and bluing agents may be contained as necessary. In order to improve mechanical stability, a coating can also be applied to the surface of the molded body.

[Effect]

The resin composition of the present invention has excellent transparency, surface properties, surface hardness, heat resistance, impact resistance, and processability, and also has a higher refractive index than diethylene glycol bisallyl carbonate resin (CR-39), and is suitable for optical materials. It is an extremely excellent material. Furthermore, the polymerization method is simple and moldability is good.

The resin composition of the present invention is suitably used for optical materials such as eyeglass materials, so-called lenses such as camera lenses, prisms, disks such as video disks, mirrors such as concave mirrors and polygons, and optical fibers.

(Example) Next, the present invention will be described in detail, but the present invention is not limited thereto. The test method for each characteristic was performed as follows.

Transparency: Those with high transparency were rated as good (0), those with high transparency were rated as good (Δ), those with good transparency were rated as slightly good (Δ), and those with poor transparency were rated as poor (×).

Refractive index and Atsube number: Measured using an Atsube refractometer.

Processability: Those with a good polished surface after being ground with a beading machine for eyeglass lens processing were rated as good (0), those that were somewhat good were rated as somewhat good (Δ), and those that were poor were rated as poor (X).

Impact resistance: A concave lens with a center thickness of 2■■ was subjected to a steel ball drop test according to FDA standards, and those with no cracks were rated Good (○), those with slight cracks were rated Fair (Δ), and those with cracks were rated Poor ( x).

hardness: Measured by pencil hardness.

Example 1 40 parts by weight of pentaerythritol tetrakis (β-thiopropionate), 60 parts by weight of diphenic acid bisallyl ester
A mold was assembled using a glass mold and a gasket made of ethylene-vinegar and copolymer. The mixture was poured into a container and heated from 40°C to 90°C over 20 hours. As shown in Table 1, the lenses thus obtained were colorless and transparent, had excellent processability, impact resistance, surface hardness, refractive index, and Atsube's number, and had good dyeability.

Examples 2 to 15 Polymerization was carried out in exactly the same manner as in Example 1 to obtain colorless and transparent lenses of various compositions. The results are shown in Table 1, and all showed excellent dyeing properties.

Claims (1)

[Scope of Claims] (1) At least one type of first monomer having at least two SH groups in the molecule, and the type of functional group capable of radical polymerization containing a carbon-carbon double bond in the molecule. A thermosetting resin composition for optical materials, which is obtained by bulk polymerizing and three-dimensionally crosslinking a liquid mixture containing at least one kind of second monomers having at least two of them, regardless of the composition. (2) The thermosetting resin composition for optical materials according to claim 1, wherein the first monomer has at least three SH groups in its molecule. (3) The heat for optical materials according to claim 1 or 2, wherein the second monomer has at least three radically polymerizable functional groups in the molecule regardless of the type thereof. Curable resin composition. (4) Claim 2 or 3, wherein the total number of SH groups in the first monomer is 0.1 to 1.2 with respect to the total number of functional groups in the second monomer. The resin composition for optical materials described above. (5) The first monomer has two SH groups in the molecule, and the second monomer has two radically polymerizable functional groups in the molecule regardless of the type thereof. It is a thing,
The resin composition for optical materials according to claim 1, wherein the total number of SH groups in the first monomer is 0.1 to 0.8 with respect to the total number of functional groups in the second monomer. thing. (6) The resin composition for optical materials according to claim 1, wherein the first monomer is at least one monomer selected from Group A shown below. Group A general formula (I) {HS-(CH_2)_k-(Y)_■-CH_2}_
p-C-(R)_4_-_p (in the formula, Y represents O=C-O or O-C=O group, R represents a methyl group or ethyl group, k represents 1 or 2, p represents 3 or 4) General formula (II) HS-(CH_2)_k-Z-{(CH_2)_n-(
X)_a}_q^--(CH_2)_p-Z-(CH_
2)_k-SH (in the formula, Z is O=C-O or O-C=
represents an O group, X represents an O or S atom, a represents 0 or 1, k, n, p each independently represents 1 or 2, q represents an integer from 1 to 9) General formula ( III) HS-(CH_2)_n{(X)_a-(CH_2)_
p}_q^--(X)_a-(CH_2)_k-SH (wherein, X represents an oxygen atom or an S atom, a represents 0 or 1, and k, n, and p each independently represent 1 or 2, and q represents an integer from 0 to 9) General formula (IV) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, X and Y each independently represent a chlorine atom, a bromine atom,
(7) the above-mentioned second 2. The resin composition for optical materials according to claim 1, wherein the functional group of the monomer is a vinyl group, (meth)acrylic group, allyl group, or allyl carbonate group. (8) A claim in which the mixture further contains at least one type of third monomer having one radically polymerizable functional group containing a carbon-carbon double bond in the molecule regardless of its type. 2. The resin composition for optical materials according to item 1. (9) The functional group of the third monomer is a vinyl group, (meth)
9. The resin composition for optical materials according to claim 8, which is an acrylic group, an allyl group, and an allyl carbonate group, and the mixture contains 0 to 30% by weight of a third monomer.