JP3373800B2 - New optical resin - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a resin used for optical materials such as plastic lenses, prisms, optical fibers, information recording substrates, filters and light emitting diodes, and a polymerizable composition as a raw material of the resin. In particular, it relates to a polymerizable composition which is preferably used as a raw material for plastic lenses for spectacles.

[0002]

2. Description of the Related Art Plastic lenses are lighter in weight and harder to break than inorganic lenses and can be dyed, and thus have been rapidly popularized in optical materials such as spectacle lenses and camera lenses in recent years.

The optical properties that have been continuously required for these plastic lenses are high refractive index, high Abbe number,
The physical properties are high workability, high heat resistance, and low specific gravity.

Among these performances, high heat resistance and low specific gravity have been realized at a high level even with current high refractive index plastic lenses. Currently, as a resin widely used for these purposes, there is a resin obtained by radical polymerization of diethylene glycol bis (allyl carbonate) (hereinafter referred to as DAC). This resin has various characteristics such as excellent impact resistance, light weight, excellent dyeability, and good workability such as machinability and abrasiveness. . However, this resin has a low refractive index Nd of about 1.50, which increases the center thickness and edge thickness of the lens, and thus a resin for lenses having a higher refractive index has been desired.

D. A. Polythiourethane resin (Japanese Patent Publication No. 4-58489, etc.) or sulfur-containing O-, which has a higher refractive index than C resin, has a sulfur atom introduced into the resin.
(Meth) acrylate resin (JP-A-4-161410, etc.) and thio (meth) acrylate resin (JP-B-3-
No. 59060, etc.) is known. The polythiourethane resin is a well-balanced resin having a high refractive index and good impact resistance.

However, it is very difficult to improve both the refractive index and the Abbe number at the same time because they have contradictory physical properties that the higher the refractive index, the lower the Abbe number. Therefore, studies for increasing the refractive index while suppressing the decrease of the Abbe number are being actively conducted.

The most typical proposal among these examinations is
JP-A-9-110979 and JP-A-9-7158.
No. 0 and JP-A-9-255781 disclose a method of using an episulfide compound.

[0008]

According to these methods, a high refractive index can be realized while having a relatively high Abbe number. However, episulfide-based resins made from episulfide compounds have a strong tendency to be colored yellow during heat treatment in the secondary step and during long-term storage or use,
In a spectacle lens that requires fashionability, this yellowing causes a change in hue, which does not satisfy the demands of spectacle wearers. A method proposed to solve this problem is Japanese Patent Application Laid-Open No. 10-298287 and the like, and by adding a thiol compound to an episulfide compound,
Yellowing can be prevented. However, in these methods, although it is possible to prevent yellowing, by the addition of a thiol compound, particularly in monofunctional and difunctional thiol compounds, the heat resistance is greatly reduced, and satisfactory physical properties are obtained in the field requiring heat resistance. You may not get it.

[0009]

Means for Solving the Problems As a result of intensive studies for solving the above-mentioned problems, the present inventors have found that the following formula (1) is included in one molecule.

[0010]

[Chemical 3]

(In the formula, R ₁ is a divalent hydrocarbon group having 1 to 10 carbon atoms, R ₂ , R ₃ and R ₄ are each a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom. X is S or O, and the number of S is 50% or more on average with respect to the sum of S and O constituting the three-membered ring.) Compound (a) having one or more structures represented by ₂ groups per molecule 1
A compound having one or more compounds and / or one or more compounds (b) selected from compounds having one or more NH groups per molecule, wherein the episulfide group and the epoxy group in the compound (a) are included. The resin obtained by curing the polymerizable composition in which the ratio of the total number of moles of NH ₂ groups and NH groups in the compound (b) to the total number of moles of is 0.001 to 0.5 is high, The present invention was found to have the effect of suppressing the decrease in heat resistance and yellowing while maintaining the Abbe number.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION JP-A-9-110979 and JP-A-9-71580 relating to episulfide resins.
JP-A-9-255781 and JP-A-9-255781.
In JP-A 0-298287 and the like, primary and secondary amine compounds corresponding to the compound (b) of the present invention are mentioned as curing catalysts, but examples using them are hydrogenated in Examples and Comparative Examples. There is nothing other than 4,4'-diaminodiphenylmethane. According to the study of the present inventors, when hydrogenated 4,4′-diaminodiphenylmethane is used as a curing catalyst,
Simultaneously with the mixing of hydrogenated 4,4′-diaminodiphenylmethane with the compound (a), the polymerization locally progressed and became a cloudy liquid, and the transparency was lost. Further, the polymerization was not completed even by the heat treatment, and a good resin could not be obtained. Among the other exemplified amine compounds, the primary and secondary amine compounds, which are the compounds (b) of the present invention other than the tertiary amine compound, do not have sufficient effect as a curing catalyst and the polymerization is not completed, resulting in a viscosity It became a thick liquid or rubbery resin. That is, the present invention has found that the compound (b) can be used not as a curing catalyst for an episulfide-based resin but as a yellowing inhibitor with suppressed decrease in heat resistance.

In the present invention, the ratio of the total number of moles of NH ₂ groups and NH groups in the compound (b) to the total number of moles of episulfide groups and epoxy groups in the compound (a) is 0.001 to 0.5. And more preferably 0.01 or more and less than 0.3.

When the ratio of the total number of moles of NH ₂ groups and NH groups in compound (b) to the total number of episulfide groups and epoxy groups in compound (a) exceeds 0.5, a resin obtained by polymerization and curing is obtained. The heat resistance and refractive index of are decreased. If it is less than 0.001, the effect of preventing yellowing, which is the object of the present invention, cannot be obtained.

In order to realize a high refractive index which is another object of the present invention, R ₁ in the formula (1) is a methylene group or an ethylene group, more preferably a methylene group. Also,
R ₂ , R ₃ and R ₄ are preferably a methyl group, an ethyl group or a hydrogen atom, more preferably a hydrogen atom.

The polymerizable composition according to the present invention is a composition containing the compound (a) and the compound (b). These compositions include dimers, trimers, and Four
Polyether oligomers or polysulfide oligomers such as polymers, inorganic acids and organic acids added as a polymerization inhibitor, organic compounds such as solvents and by-products, and inorganic compounds may be contained in a range not causing a problem.

The polymerizable composition according to the present invention is mainly used for adjusting the optical properties such as the refractive index of the obtained resin, adjusting various physical properties such as impact resistance and specific gravity, and the like. viscosity,
A resin modifier may be added for the purpose of improving the resin such as adjusting other handling properties.

As the resin modifier, episulfide compounds and amine compounds other than those contained in the polymerizable composition of the present invention, thiol compounds, mercapto organic acids,
Examples thereof include organic acids and anhydrides, amino acids and mercaptoamines, and olefins including (meth) acrylates.

In the present invention, the compound (a) is preferably a compound represented by the following formula (2).

[0020]

[Chemical 4]

(In the formula, R _{5 to} R ₁₀ are each 1 to 1 carbon atoms.
10 hydrocarbon groups or hydrogen atoms are shown. X represents S or O, and the number of S is 50% or more on average with respect to the total of S and O constituting the three-membered ring. Y represents a substituted or unsubstituted linear, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms, a substituted or unsubstituted 1,4-dithiane group, an arylene group or an aralkylene group. m represents an integer of 0 to 2,
n represents an integer of 0 to 4. )

The substituent of the linear, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms represented by Y is represented by the following structural formula (3).

[0023]

[Chemical 5] (Wherein, R ₁₁ to R ₁₃ represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, o is an integer of 0 to 2, p is an .X is S or O represents an integer of 1 or 2 The number of S can be 50% or more on average with respect to the total of S and O constituting the three-membered ring.).

Preferred specific examples of the compound (a) having at least one structure represented by the formula (1) are bis (2,3)
-Epithiopropyl) sulfide, bis (2,3-epithiopropyl) disulfide, bis (2,3-epithiopropylthio) methane, 1,2-bis (2,3-epithiopropylthio) ethane, 1 , 2-bis (2,3-epithiopropylthio) propane, 1,3-bis (2,3-
Epithiopropylthio) propane, 1,3-bis (2,
3-epithiopropylthio) -2-methylpropane,
1,4-bis (2,3-epithiopropylthio) butane, 1,4-bis (2,3epithiopropylthio) -2
-Methylbutane, 1,3-bis (2,3-epithiopropylthio) butane, 1,5-bis (2,3-epithiopropylthio) pentane, 1,5-bis (2,3-epithiopropyl) Thio) -2-methylpentane, 1,5-bis (2,3-epithiopropylthio) -3-thiapentane, 1,6-bis (2,3-epithiopropylthio) hexane, 1,6-bis (2,3-Epithiopropylthio) -2-methylhexane, 3,8-bis (2,3-epithiopropylthio) -3,6-dithiaoctane, 1,
2,3-tris (2,3-epithiopropylthio) propane, 2,2-bis (2,3-epithiopropylthio)
-1,3-bis (2,3-epithiopropylthiomethyl) propane, 2,2-bis (2,3-epithiopropylthiomethyl) -1- (2,3-epithiopropylthio) butane, 1,5-bis (2,3-epithiopropylthio) -2- (2,3-epithiopropylthiomethyl)
-3-Thiapentane, 1,5-bis (2,3-epithiopropylthio) -2,4-bis (2,3-epithiopropylthiomethyl) -3-thiapentane, 1- (2,3-
Epithiopropylthio) -2,2-bis (2,3-epithiopropylthiomethyl) -4-thiahexane, 1,
5,6-Tris (2,3-epithiopropylthio) -4
-(2,3-Epithiopropylthiomethyl) -3-thiahexane, 1,8-bis (2,3-epithiopropylthio) -4- (2,3-epithiopropylthiomethyl)-
3,6-dithiaoctane, 1,8-bis (2,3-epithiopropylthio) -4,5-bis (2,3-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,
8-bis (2,3-epithiopropylthio) -4,4-
Bis (2,3-epithiopropylthiomethyl) -3,6
-Dithiaoctane, 1,8-bis (2,3-epithiopropylthio) -2,5-bis (2,3-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (2, 3-Epithiopropylthio) -2,4,5-tris (2,3-epithiopropylthiomethyl) -3,6
-Dithiaoctane, 1,1,1-tris {[2- (2,
3-Epithiopropylthio) ethyl] thiomethyl} -2
-(2,3-Epithiopropylthio) ethane, 1,1,
2,2-Tetrakis {[2- (2,3-epithiopropylthio) ethyl] thiomethyl} ethane, 1,11-bis (2,3-epithiopropylthio) -4,8-bis (2,3) -Epithiopropylthiomethyl) -3,6,9
-Trithiaundecane, 1,11-bis (2,3-epithiopropylthio) -4,7-bis (2,3-epithiopropylthiomethyl) -3,6,9-trithiaundecane, 1, 11-bis (2,3-epithiopropylthio)
A chain aliphatic 2,3-epithiopropylthio compound such as -5,7-bis (2,3-epithiopropylthiomethyl) -3,6,9-trithiaundecane, and

1,3-bis (2,3-epithiopropylthio) cyclohexane, 1,4-bis (2,3-epithiopropylthio) cyclohexane, 1,3-bis (2,
3-epithiopropylthiomethyl) cyclohexane,
1,4-bis (2,3-epithiopropylthiomethyl)
Cyclohexane, 2,5-bis (2,3-epithiopropylthiomethyl) -1,4-dithiane, 2,5-bis {[2- (2,3-epithiopropylthio) ethyl] thiomethyl} -1 , 4-dithiane, 2,5-bis (2,3
-Epithiopropylthiomethyl) -2,5-dimethyl-
Cycloaliphatic 2,3-epithiopropylthio compounds such as 1,4-dithiane, 1,2-bis (2,3-epithiopropylthio) benzene, 1,3-bis (2,3-
Epithiopropylthio) benzene, 1,4-bis (2,
3 epithiopropylthio) benzene, 1,2-bis (2,3-epithiopropylthiomethyl) benzene,
1,3-bis (2,3-epithiopropylthiomethyl)
Benzene, 1,4-bis (2,3-epithiopropylthiomethyl) benzene, bis [4- (2,3-epithiopropylthio) phenyl] methane, 2,2-bis [4-
(2,3-Epithiopropylthio) phenyl] propane, bis [4- (2,3-epithiopropylthio) phenyl] sulfide, bis [4- (2,3-epithiopropylthio) phenyl] sulfone, Aromatic 2,3-epithiopropylthio compounds such as 4,4′-bis (2,3-epithiopropylthio) biphenyl, etc., and mercapto group-containing epithio compounds such as 3-mercaptopropylene sulfide and 4-mercaptobutene sulfide However, the present invention is not limited to these exemplified compounds. These may be used alone or in combination of two or more. Among these exemplified compounds, more preferable compounds are bis (2,3-epithiopropyl) sulfide and bis (2,3-epithiopropyl) disulfide. The most preferred compound is bis (2,3-epithiopropyl) disulfide.

Preferred compounds (b) of the present invention include (1) ethylamine, n-propylamine, isopropylamine, n-butylamine, sec-butylamine,
tert-butylamine, pentylamine, hexylamine, heptylamine, octylamine, decylamine, laurylamine, myristylamine, 3-pentylamine, 2-ethylhexylamine, 1,2-dimethylhexylamine, allylamine, aminomethylbicycloheptane, cyclopentyl Amine, cyclohexylamine, 2,3-dimethylcyclohexylamine, aminomethylcyclohexane, aniline, benzylamine, phenethylamine, 2-, 3-, or 4-methylbenzylamine, o-, m-, or p-methylaniline,
o-, m-, or p-ethylaniline, aminomorpholine, naphthylamine, furfurylamine, α-aminodiphenylmethane, toluidine, aminopyridine, aminophenol, aminoethanol, 1-aminopropanol, 2-aminopropanol, aminobutanol,
Aminopentanol, aminohexanol, methoxyethylamine, 2- (2-aminoethoxy) ethanol,
Monofunctional primary amine compounds such as 3-ethoxypropylamine, 3-propoxypropylamine, 3-butoxypropylamine, 3-isopropoxypropylamine, 3-isobutoxypropylamine and 2,2-diethoxyethylamine, ethylenediamine, 1,2- or 1,3-diaminopropane, 1,2-, 1,3-, or 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diamino Heptane, 1,8-diaminooctane, 1,10-diaminodecane, 1,2-, 1,3-, or 1,4-diaminocyclohexane, o-, m- or p-diaminobenzene, 3,4- or 4,4'-diaminobenzophenone, 3,4- or 4,4'-diaminodiphenyl ether, 4,4'-di Mino diphenylmethane,
4,4'-diaminodiphenyl sulfide, 3,3 '
-, Or 4,4'-diaminodiphenyl sulfone, 2,7-diaminofluorene, 1,5-, 1,8
-, Or 2,3-diaminonaphthalene, 2,3-,
2,6- or 3,4-diaminopyridine, 2,4
-, Or 2,6-diaminotoluene, m-, or p-xylylenediamine, isophoronediamine, diaminomethylbicycloheptane, 1,3-, or 1,
4-diaminomethylcyclohexane, 2-, or 4
-A primary piperamine compound such as aminopiperidine, 2-, or 4-aminomethylpiperidine, 2- or 4-aminoethylpiperidine, N-aminoethylmorpholine, N-aminopropylmorpholine,

(2) Diethylamine, dipropylamine, di-n-butylamine, di-sec-butylamine, diisobutylamine, di-n-pentylamine, di-3-pentylamine, dihexylamine, dioctylamine, di (2 -Ethylhexyl) amine, methylhexylamine, diallylamine, N-methylallylamine, piperidine, pyrrolidine, diphenylamine, N-
Methylamine, N-ethylamine, dibenzylamine,
N-methylbenzylamine, N-ethylbenzylamine, dicyclohexylamine, N-methylaniline, N
-Monofunctional secondary amine compounds such as ethylaniline, dinaphthylamine, 1-methylpiperazine, morpholine, N,
N'-dimethylethylenediamine, N, N'-dimethyl-1,2-diaminopropane, N, N'-dimethyl-
1,3-diaminopropane, N, N'-dimethyl-1,
2-diaminobutane, N, N'-dimethyl-1,3-diaminobutane, N, N'-dimethyl-1,4-diaminobutane, N, N'-dimethyl-1,5-diaminopentane, N, N '-Dimethyl-1,6-diaminohexane,
N, N'-dimethyl-1,7-diaminoheptane, N,
N'-diethylethylenediamine, N, N'-diethyl-1,2-diaminopropane, N, N'-diethyl-
1,3-diaminopropane, N, N'-diethyl-1,
2-diaminobutane, N, N'-diethyl-1,3-diaminobutane, N, N'-diethyl-1,4-diaminobutane, N, N'-diethyl-1,5-diaminopentane, N, N '-Diethyl-1,6-diaminohexane,
N, N'-diethyl-1,7-diaminoheptane, piperazine, 2-methylpiperazine, 2,5-dimethylpiperazine, 2,6-dimethylpiperazine, homopiperazine, 1,1-di- (4-piperidyl) methane , 1,2-
Di- (4-piperidyl) ethane, 1,3-di- (4-piperidyl) propane, 1,4-di- (4-piperidyl)
Examples thereof include secondary polyamine compounds such as butane and tetramethylguanidine, but are not limited to these exemplified compounds. These may be used alone or in combination of two or more. Among these exemplified compounds, benzylamine and piperazines are more preferable.

Specific examples of preferable epoxy resins that can be added as resin modifiers include phenol-based epoxy compounds obtained by condensation reaction of polyhydric phenol compounds such as bisphenol A glycidyl ether and epihalohydrin compounds, Hydrogenated bisphenol A
Alcohol-based epoxy compounds obtained by condensation of polyhydric alcohol compounds such as glycidyl ether and epihalohydrin compounds, 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate and 1,2-hexahydrophthalic acid diester Glycidyl ester epoxy compounds obtained by condensation of polyvalent organic acid compounds such as glycidyl ester and epihalohydrin compounds, amine epoxy compounds obtained by condensation of primary and secondary diamine compounds with epihalohydrin compounds, and others, vinylcyclohexene diepoxide Examples thereof include homoaliphatic polyepoxy compounds, but are not limited to these exemplified compounds. These may be used alone or in combination of two or more.

Specific examples of preferable thiol compounds include methyl mercaptan, ethyl mercaptan,
1,2-ethanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 2,2-propanedithiol, 1,4-butanedithiol, 1,2,3-trimercaptopropane, tetrakis (mercaptomethyl) Methane, 1,2-dimercaptocyclohexane, bis (2-mercaptoethyl) sulfide, 2,3-dimercapto-1-propanol, ethylene glycol bis (3-mercaptopropionate), diethylene glycol bis (3-mercaptopropionate) ), Diethylene glycol bis (2-mercaptoglycolate), pentaerythritol tetrakis (2-mercaptothioglycolate), pentaerythritol tetrakis (3-)
Mercaptopropionate), trimethylolpropane tris (2-mercaptothioglycolate), trimethylolpropane tris 3-mercaptopropionate), 1,1,1-trimethylmercaptoethane, 1,
1,1-trimethylmercaptopropane, 2,5-dimercaptomethylthiophane, 4-mercaptomethyl-
1,8-dimercapto-3,6-dithiaoctane, 2,
5-dimercaptomethyl-1,4-dithiane, 2,5-
Bis [(2-mercaptoethyl) thiomethyl] -1,4
-Dithiane, 1,3-cyclohexanedithiol, 1,
4-cyclohexanedithiol, 4,8-dimercaptomethyl-1,11-mercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-
Mercapto-3,6,9-trithiaundecane, 5,7
-Dimercaptomethyl-1,11-mercapto-3,
Aliphatic thiols such as 6,9-trithiaundecane, and benzyl mercaptan, thiophenol, 1,2-
Dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,2-bis (mercaptomethyl) benzene, 1,3-bis (mercaptomethyl) benzene, 1,4-bis (mercaptomethyl) )
Benzene, 2,2'-dimercaptobiphenyl, 4,
4'-dimercaptobiphenyl, bis (4-mercaptophenyl) methane, bis (4-mercaptophenyl) sulfide, bis (4-mercaptophenyl) sulfone, 2,2-bis (4-mercaptophenyl) propane, 1,2 , 3-Trimercaptobenzene, 1,2,4
Examples thereof include aromatic thiols such as trimercaptobenzene and 1,2,5-trimercaptobenzene, but the present invention is not limited to these exemplified compounds. These may be used alone or in combination of two or more.

Specific examples of preferable mercapto organic acid compounds include thioglycolic acid, 3-mercaptopropionic acid, thioacetic acid, thiolactic acid, thiomalic acid, and thiosalicylic acid, but the compounds are not limited to these exemplified compounds. Not a thing. Also, these can be used alone or 2
You may mix and use more than one kind.

Specific examples of preferable organic acids and their anhydrides include thiodiglycolic acid, thiodipropionic acid, dithiodipropionic acid, phthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride and methyltetrahydro. Examples thereof include phthalic anhydride, methylnorbornene anhydride, methylnalbornane anhydride, maleic anhydride, trimellitic anhydride, and pyromellitic anhydride, but are not limited to these exemplified compounds. These may be used alone or in combination of two or more.

Specific examples of preferable olefins include benzyl acrylate, benzyl methacrylate, butoxyethyl acrylate, butoxymethyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxymethyl methacrylate, glycidyl acrylate, Glycidyl methacrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, phenyl methacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate,
Tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, ethylene glycol bisglycidyl acrylate, ethylene glycol bisglycidyl methacrylate, bisphenol A diacrylate , Bisphenol A dimethacrylate,
2,2-bis (4-acryloxyethoxyphenyl) propane, 2,2-bis (4-methacryloxyethoxyphenyl) propane, 2,2-bis (4-acryloxydiethoxyphenyl) propane, 2,2- Bis (4-methacryloxydiethoxyphenyl) propane, bisphenol F diacrylate, bisphenol F dimethacrylate,
1,1-bis (4-acryloxyethoxyphenyl) methane, 1,1-bis (4-metacryloxyethoxyphenyl) methane, 1,1-bis (4-acryloxydiethoxyphenyl) methane, 1,1- Bis (4-methacryloxydiethoxyphenyl) methane, dimethylol tricyclodecane diacrylate, trimethylol propane triacrylate, trimethylol propane trimethacrylate, glycerol diacrylate, glycerol dimethacrylate, pentaerythritol triacrylate,
Pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, methylthioacrylate, methylthiomethacrylate, phenylthioacrylate, benzylthiomethacrylate, xylylenedithiol diacrylate, xylylenedithiol dimethacrylate, mercaptoethyl sulfide diacrylate, mercaptoethyl sulfide dimethacrylate, etc. (Meth) acrylate compounds, allyl glycidyl ether, diallyl phthalate, diallyl terephthalate, diallyl isophthalate, diallyl carbonate, allyl compounds such as diethylene glycol bis allyl carbonate, styrene, chlorostyrene, methylstyrene, bromostyrene, dibromostyrene, divinylbenzene,
Examples thereof include vinyl compounds such as 3,9-divinylspirobi (m-dioxane), diisopropenylbenzene, and the like, but are not limited to these exemplified compounds. These may be used alone or in combination of two or more.

These several types of resin modifiers may be used alone or in combination of two or more.

The polymerizable composition of the present invention can be polymerized by heating or standing at room temperature in the presence or absence of a curing catalyst to produce a resin. However, in the absence of a curing catalyst, the polymerization may not proceed satisfactorily, resulting in poor polymerization or no polymerization in some cases, and therefore it is preferable to use a curing catalyst. As the curing catalyst used in the present invention, amines other than the compound (b) of the present invention, phosphines, Lewis acids, radical polymerization catalysts, cationic polymerization catalysts and the like are usually used.

Specific examples of preferable curing catalysts include triethylamine, tri-n-butylamine and tri-n-amine.
-Hexylamine, N, N-diisopropylethylamine, triethylenediamine, triphenylamine, N,
N-dimethylethanolamine, N, N-diethylethanolamine, N, N-dibutylethanolamine, triethanolamine, N-ethyldiethanolamine,
N, N-dimethylbenzylamine, N, N-diethylbenzylamine, tribenzylamine, N-methyldibenzylamine, N, N-dimethylcyclohexylamine,
N, N-diethylcyclohexylamine, N, N-dimethylbutylamine, N-methyldicyclohexylamine, N-methylmorpholine, N-isopropylmorpholine, pyridine, quinoline, N, N-dimethylaniline,
N, N-diethylaniline, α-, β-, or γ-
Picoline, 2,2'-bipyridyl, 1,4-dimethylpiperazine, dicyandiamide, tetramethylethylenediamine, hexamethylenetetramine, 1,8-diazabicyclo (5,4,0) -7-undecene, 2,4,6-
Aliphatic and aromatic tertiary amines such as tris (N, N-dimethylaminomethyl) phenol, trimethylphosphine, triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine , Tribenzylphosphine, 1,2-bis (diphenylphosphino)
Phosphines such as ethane and 1,2-bis (dimethylphosphino) ethane, dimethyltin dichloride, dibutyltin dichloride, dibutyltin dilaurate, tetrachlorotin, dibutyltin oxide, zinc chloride, zinc acetylacetone, aluminum chloride, aluminum fluoride Lewis acids such as triphenylaluminum, tetrachlorotitanium and calcium acetate, 2,2′-azobis (2-cyclopropylpropionitrile), 2,2′-azobis (4-methoxy-2,
4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), t-butylperoxy-2-ethylhexanoate, n-butyl-4,
4'-bis (t-butylperoxy) valerate, t-
Radical polymerization catalyst such as butyl peroxybenzoate,
Examples include cationic polymerization catalysts such as diphenyliodonium hexafluorophosphoric acid, diphenyliodonium hexafluoroarsenic acid, diphenyliodonium hexafluoroantimony, triphenylsulfonium tetrafluoroboric acid, triphenylsulfonium hexafluorophosphoric acid, and triphenylsulfonium hexafluoroarsenic acid. However, the present invention is not limited to these exemplified compounds.

These curing catalysts may be used alone or in combination of two or more.

The amount of the curing catalyst added is preferably in the range of 0.001 to 10 wt%, more preferably 0, based on the total weight of the composition containing the epoxy or episulfide compound represented by the formula (1). It is used in the range of 0.01 to 1 wt%. The addition amount of the curing catalyst is 0.001wt
If it is less than%, the effect is so small that it may cause poor polymerization. On the other hand, it is possible to exceed 10 wt%, but the pot life is shortened, transparency, optical properties,
Alternatively, inconvenience such as deterioration of weather resistance may occur.

A typical polymerization method for obtaining the resin (for example, plastic lens) of the present invention is cast polymerization. That is, the polymerizable composition of the present invention is mixed with a curing catalyst and a resin modifier, if necessary, and then injected between molding molds held by a gasket or a tape. At this time, if necessary, treatment such as defoaming may be performed before or after the injection.

Next, the resin can be taken out by curing by heating in an oven or in a heatable device such as water.

The polymerization method, polymerization conditions and the like for obtaining the resin of the present invention cannot be unconditionally limited depending on the kind and amount of the curing catalyst and the like, and the kind and ratio of the monomers.

The thermal polymerization conditions of the polymerizable composition of the present invention injected into the molding mold are as follows: (a) and compound (b) of the present invention, kind of resin modifier, kind of curing catalyst, shape of molding mold. It cannot be limited because the conditions vary greatly depending on the conditions, but 0.1 to 10 at a temperature of about -50 to 200 ° C.
It will take 0 hours.

In some cases, it may be preferable to maintain the temperature in the range of 10 ° C. to 150 ° C. or gradually raise the temperature and polymerize in 1 to 80 hours.

Further, the polymerizable composition of the present invention can be shortened in polymerization time by irradiation with ultraviolet rays or the like. At this time, a curing catalyst such as a radical polymerization catalyst may be added.

Upon molding the resin of the present invention, a chain extender, a crosslinking agent,
Light stabilizers, ultraviolet absorbers, antioxidants, anti-coloring agents other than the present invention, dyes, fillers, internal and / or external release agents,
Various substances such as a compound having a hydroxyl group may be added as an internal and / or external adhesion improver and a dyeability improver.

Regarding the resin molded body taken out,
If necessary, a treatment such as annealing may be performed. Further, the resin of the present invention can be obtained as molded products of various forms by changing the molding mold at the time of cast polymerization, and it can be used for eyeglass lenses, camera lenses, light emitting diodes (LE).
It can be used for various purposes such as an optical material such as D) and a transparent resin. In particular, it is suitable as an optical material for eyeglass lenses, camera lenses, and the like.

Further, in the lens using the optical material of the present invention, improvement in antireflection, high hardness, abrasion resistance, chemical resistance, antifogging property, fashionability, etc. may be added if necessary. Therefore, a physical or chemical treatment such as surface polishing, antistatic treatment, hard coating treatment, anti-reflection coating treatment, dyeing treatment and the like can be performed.

[0047]

EXAMPLES Hereinafter, the present invention will be specifically described with reference to Examples.
It Of the performance tests of the resin obtained, the refractive index and
The basis number, specific gravity, heat resistance, and hue change are determined by the following test methods.
evaluated. ・ Refractive index (nd), Abbe number (νd): Pulfrich bending
It measured at 20 degreeC using the folding meter. ・ Heat resistance: TMA penetration method (load 50g,
Tg is measured with a pin tip of 0.5 mmφ and a temperature rise of 10 ° C / min)
It was ・ Hue change rate: Heat treatment at 120 ° C for 3 hours in air
B before heat treatment ^*Value and b after heat treatment^*Determined by the difference in value
I refused. Each compound (a) is used as the reference value for hue change.
Polymerized with only the curing catalyst without mixing the compound (b) with
Heat treatment in air at 120 ° C for 3 hours
B before doing^*Value and b after heat treatment^*The difference in value was used.

[0048]

[Equation 1]

Compound (a) used in Examples and Comparative Examples is bis (2,3-epithiopropyl) disulfide; hereinafter abbreviated as Compound (A), and bis (2,3-epithiopropyl) sulfide; Abbreviated as compound (B), further 4,
8 (or5,7or4,7) -bis (4,5-epithio-2-thiapentyl) -1,11-bis (3,4-epithio-1-thiabutyl) -3,6,9-trithiaundecane; Compound (C), each composition.

Example 1 100 g of the compound (A) as the compound (a), 5 g of n-propylamine as the compound (b), and N, N-dimethylcyclohexylamine (hereinafter referred to as DC) as a curing catalyst.
A) 0.2 g was added, and the mixture was stirred, degassed under reduced pressure for 0.4 hours, filtered through a 3 μm Teflon filter, and then poured into a molding mold composed of a glass mold and a gasket. The mold was gradually heated from 30 ° C. to 100 ° C. and polymerized in 10 hours. After completion of the polymerization, the resin was taken out from the mold by gradually cooling. The resin obtained is 1
Annealed at 00 ° C. for 2 hours. The obtained resin (lens) was further heat-treated at 120 ° C. for 3 hours and the physical properties were measured. The physical properties and hue changes are shown in Table 1.

Example 2 The same operation as in Example 1 was carried out except that 5 g of isopropylamine was used instead of n-propylamine as the compound (b). The physical properties and hue changes are shown in Table 1.

Example 3 As compound (b), n-propylamine was used instead of n-propylamine.
The same operation as in Example 1 was carried out except that 5 g of -butylamine was used. The physical properties and hue changes are shown in Table 1.

Example 4 As compound (b), s was used instead of n-propylamine.
Example 1 except that 5 g of ec-butylamine was used
The same operation was performed. The physical properties and hue changes are shown in Table 1.

Example 5 As compound (b), t was used in place of n-propylamine.
The same operation as in Example 1 was carried out except that 5 g of ert-butylamine was used. The physical properties and hue changes are shown in Table 1.

Example 6 As compound (b), n instead of n-propylamine was used.
The same operation as in Example 1 was carried out except that 5 g of hexylamine was used. The physical properties and hue changes are shown in Table 1.

Example 7 As compound (b), n instead of n-propylamine was used.
The same operation as in Example 1 was carried out except that 5 g of octylamine was used. The physical properties and hue changes are shown in Table 1.

Example 8 As compound (b), n instead of n-propylamine was used.
-The same operation as in Example 1 was carried out except that 5 g of laurylamine was used. The physical properties and hue changes are shown in Table 1.

Example 9 Example 1 was repeated except that 5 g of methoxyethylamine was used instead of n-propylamine as the compound (b).
The same operation was performed. The physical properties and hue changes are shown in Table 1.

Example 10 Example 1 was repeated except that 5 g of cyclohexylamine was used instead of n-propylamine as the compound (b).
The same operation was performed. The physical properties and hue changes are shown in Table 1.

Example 11 As compound (b), 2 instead of n-propylamine was used.
Example 1 except that 3 g of aminoethanol was used
The same operation was performed. The physical properties and hue changes are shown in Table 1.

Example 12 The same operation as in Example 1 was carried out except that 5 g of benzylamine was used instead of n-propylamine as the compound (b). The physical properties and hue changes are shown in Table 1.

Example 13 As compound (b), β was used in place of n-propylamine.
Example 1 except that 5 g of phenethylamine was used
The same operation was performed. The physical properties and hue changes are shown in Table 1.

Example 14 The same operation as in Example 1 was carried out except that 5 g of aniline was used instead of n-propylamine as the compound (b). The physical properties and hue changes are shown in Table 1.

Example 15 As compound (b), o was used in place of n-propylamine.
-The same operation as in Example 1 was carried out except that 5 g of toluidine was used. The physical properties and hue changes are shown in Table 1.

Example 16 As compound (b), 2 instead of n-propylamine was used.
The same operation as in Example 1 was carried out except that 5 g of methylbenzylamine was used. The physical properties and hue changes are shown in Table 1.
It was shown to.

Example 17 As compound (b), α was used in place of n-propylamine.
-The same operation as in Example 1 was carried out except that 5 g of naphthylamine was used. The physical properties and hue changes are shown in Table 1.

Example 18 The same operation as in Example 1 was carried out except that 3 g of ethylenediamine was used instead of n-propylamine as the compound (b). The physical properties and hue changes are shown in Table 1.

Example 19 The same operation as in Example 1 was carried out except that 3 g of diaminopropane was used instead of n-propylamine as the compound (b). The physical properties and hue changes are shown in Table 1.

Example 20 The same procedure as in Example 1 was carried out except that 3 g of diaminobutane was used as the compound (b) instead of n-propylamine. The physical properties and hue changes are shown in Table 1.

Example 21 The same operation as in Example 1 was carried out except that 3 g of diaminomethylbicycloheptane was used instead of n-propylamine as the compound (b). The physical properties and hue changes are shown in Table 1.

Example 22 As compound (b), m was used in place of n-propylamine.
-The same operation as in Example 1 was performed except that 3 g of xylylenediamine was used. The physical properties and hue changes are shown in Table 1.

Example 23 The same procedure as in Example 1 was carried out except that 3 g of 1,3-diaminomethylcyclohexan was used as the compound (b) instead of n-propylamine. The physical properties and hue changes are shown in Table 1.

Example 24 The same operation as in Example 1 was carried out except that 3 g of naphthalenediamine was used instead of n-propylamine as the compound (b). The physical properties and hue changes are shown in Table 1.

Example 25 The same operation as in Example 1 was carried out except that 3 g of N, N'-dimethylethylenediamine was used instead of n-propylamine as the compound (b). The physical properties and hue changes are shown in Table 1.

Example 26 The same operation as in Example 1 was carried out except that 3 g of piperazine was used instead of n-propylamine as the compound (b). The physical properties and hue changes are shown in Table 1.

Comparative Example 1 100 g of the compound (A) as the compound (a) was not mixed with the compound (b), 0.2 g of DCA was added as a curing catalyst, and the mixture was stirred and defoamed under reduced pressure for 0.4 hours. After filtering with a 3 μm Teflon filter, the mixture was poured into a molding mold composed of a glass mold and a gasket. The mold was gradually heated from 30 ° C. to 100 ° C. and polymerized in 10 hours. After completion of the polymerization, the resin was taken out from the mold by gradually cooling. The obtained resin was annealed at 100 ° C. for 2 hours. The resin (lens) obtained is further heated at 120 ° C.
And heat-treated for 3 hours to measure the physical properties. The physical properties and hue changes are shown in Table 2.

Comparative Example 2 The same operation as in Comparative Example 1 was carried out except that 100 g of the compound (B) was used as the compound (a) instead of the compound (A). The physical properties and hue changes are shown in Table 2.

Comparative Example 3 The same operation as in Comparative Example 1 was carried out except that 100 g of the compound (C) was used as the compound (a) instead of the compound (A). The physical properties and hue changes are shown in Table 2.

Comparative Example 4 100 g of the compound (A) as the compound (a) and 5 g of thiophenol as the addition compound were mixed, DCA was added as a curing catalyst and stirred, and the subsequent resin production flow was the same as that of Comparative Example 1. I went. The physical properties and hue changes are shown in Table 2.
It was shown to.

Comparative Example 5 100 g of the compound (A) as the compound (a) and 5 g of bis (mercaptoethyl) sulfide as the addition compound were mixed, and DCA was added as a curing catalyst and stirred. The same operation was performed. The physical properties and hue changes are shown in Table 2.

Comparative Example 6 100 g of the compound (B) as the compound (a) and 5 g of thiophenol as the addition compound were mixed, DCA was added as a curing catalyst and stirred, and the lens molding flow thereafter was the same as that of Comparative Example 1. I went. The physical properties and hue changes are shown in Table 2.

Comparative Example 7 100 g of the compound (A) as the compound (a) and 5 g of bis (mercaptoethyl) sulfide as the addition compound were mixed, and DCA was added as a curing catalyst and stirred. The same operation was performed. The physical properties and hue changes are shown in Table 2.

Comparative Example 8 100 g of the compound (C) as the compound (a) and 5 g of thiophenol as the addition compound were mixed, DCA was added as a curing catalyst and stirred, and the lens molding flow thereafter was the same as that of Comparative Example 1. I went. The physical properties and hue changes are shown in Table 2.

Comparative Example 9 100 g of the compound (C) as the compound (a) and 5 g of bis (mercaptoethyl) sulfide as the addition compound were mixed, DCA was added as a curing catalyst and stirred, and the lens forming flow thereafter was Comparative Example 1. The same operation was performed. The physical properties and hue changes are shown in Table 2.

Comparative Example 10 100 g of the compound (A) as the compound (a) and 5 g of n-hexylamine as the addition compound were mixed, and the mixture was stirred without adding a curing catalyst. The same operation was performed. The results are shown in Table 2.

Comparative Example 11 100 g of the compound (A) as the compound (a) and 5 g of benzylamine as the addition compound were mixed and added and stirred without adding a curing catalyst. The subsequent lens forming flow was the same as that of Comparative Example 1. The operation was performed. The results are shown in Table 2.

Comparative Example 12 100 g of the compound (A) as the compound (a) and 5 g of aniline as the addition compound were mixed and added and stirred without adding a curing catalyst. The subsequent lens forming flow was the same as in Comparative Example 1. The operation was performed. The results are shown in Table 2.

Comparative Example 13 100 g of the compound (B) as the compound (a) and 5 g of n-hexylamine as the additive compound were mixed, and the mixture was stirred without adding a curing catalyst. The same operation was performed. The results are shown in Table 2.

Comparative Example 14 100 g of the compound (B) as the compound (a) and 5 g of benzylamine as the additive compound were mixed, and the mixture was stirred without adding a curing catalyst. The subsequent lens molding flow was the same as in Comparative Example 1. The operation was performed. The results are shown in Table 2.

Comparative Example 15 100 g of the compound (B) as the compound (a) and 5 g of aniline as the additive compound were mixed and added and stirred without adding a curing catalyst. The subsequent lens molding flow was the same as that of Comparative Example 1. The operation was performed. The results are shown in Table 2.

Comparative Example 16 100 g of the compound (A) as the compound (a) and 4,4′-diaminodicyclohexylmethane 3 as the additive compound
g was mixed and added and stirred without adding the curing catalyst, and the subsequent lens molding flow was the same as in Comparative Example 1.
The results are shown in Table 2.

[0092]

[Table 1]

[0093]

[Table 2]

[0094]

[Table 3]

[0095]

[Table 4]

[0096]

[Table 5]

[0097]

According to the present invention, it is possible to obtain a transparent resin in which yellowing is prevented and heat resistance is prevented from being lowered while maintaining a high refractive index, and particularly contributes to thinning and fashionability of the lens in the field of spectacle lenses. To do.

Front page continuation (72) Seiichi Kobayashi Seiichi Kobayashi, Mitsui Chemicals Co., Ltd. 30 Asamu-cho, Omuta-shi, Fukuoka (72) Inventor Mitsuki Okazaki 30 Asamu-cho, Omuta-shi, Fukuoka Mitsui Kagaku Co., Ltd. (72) ) inventor Yoshinobu Kanamura Fukuoka Prefecture Omuta Asamuta-cho, 30 address Mitsui chemical Co., Ltd. in the (56) reference Patent flat 9-110979 (JP, a) (58 ) investigated the field (Int.Cl. ^7, DB Name) C08G 75/06 CA (STN) REGISTRY (STN)

Claims (15)

(57) [Claims] 1. A compound represented by the following formula (1) in one molecule: (In the formula, R ₁ is a divalent hydrocarbon group having 1 to 10 carbon atoms,
R ₂ , R ₃ and R ₄ each represent a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom. X represents S or O, and this S
Is 50% or more on average with respect to the total of S and O constituting the three-membered ring. ) One or two compounds selected from the compound (a) having one or more structures represented by the formula (1) and a compound having one or more NH ₂ groups per molecule and / or a compound having one or more NH groups per molecule. The compound (b) and a curing catalyst for an episulfide compound other than the compound (b)
A compound (c) , which may be an NH ₂ group and an N ₂ group in the compound (b) with respect to the total number of moles of the episulfide group and the epoxy group in the compound (a).
Total number of moles of H group Ri der 0.001, or
The total amount of the compound (c) added except the compound (c)
A polymerizable composition in the range of 0.01 to 1 wt% based on the total weight of the composition. 2. The polymerizable composition according to claim 1, wherein the compound (a) is a compound represented by the following formula (2). [Chemical 2] (In the formula, R _{5 to} R ₁₀ each represent a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom. X represents S or O, and the number of S is the sum of S and O constituting a three-membered ring. Is 50% or more on average, Y is a substituted or unsubstituted linear, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms, a substituted or unsubstituted 1,4-dithiane group, an arylene group, Represents an aralkylene group, m represents an integer of 0 to 2, and n represents an integer of 0 to 4.) 3. The polymerizable composition according to claim 1, wherein the compound (b) is a compound having one NH ₂ group per molecule and / or a compound having one or more NH groups per molecule. 4. The polymerizable composition according to claim 1, wherein the compound (b) is a compound having one NH ₂ group per molecule and / or a compound having one or two NH groups per molecule. 5. The compound (b) is a compound having one NH ₂ group per molecule and / or a compound having one or two NH groups per molecule and having a cyclic structure. Polymerizable composition. 6. A compound (c) which can be a curing catalyst for an episulfide compound other than the compound (b) is a tertiary amine,
The polymerizable composition according to claim 1, which is one or more compounds selected from phosphines, Lewis acids, radical polymerization catalysts, and cationic polymerization catalysts. 7. A resin obtained by polymerizing the composition according to any one of claims 1 to 6 . 8. An optical material comprising the resin according to claim 7. 9. A method for producing a resin, characterized in that the polymerizable composition according to any one of claims 1 to 6 is cast -polymerized. 10. A compound represented by the following formula (1) in one molecule: (In the formula, R ₁ is a divalent hydrocarbon group having 1 to 10 carbon atoms,
R ₂ , R ₃ and R ₄ each represent a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom. X represents S or O, and this S
Is 50% or more on average with respect to the total of S and O constituting the three-membered ring. In curing the compound (a) having one or more structures represented by the formula (1), one selected from a compound having one or more NH ₂ groups per molecule and / or a compound having one or more NH groups per molecule. Alternatively, two or more kinds of the compound (b), a compound (c) which can be a curing catalyst for an episulfide compound other than the compound (b) and the compound (a) are mixed and cured. And a NH ₂ group and N in the compound (b) with respect to the total number of moles of the episulfide group and the epoxy group in the compound (a).
The ratio of the total number of moles of H groups is 0.001 to 0.5, and the addition amount of the compound (c) is the whole set excluding the compound (c).
The above method, wherein the mixing is performed so as to be in the range of 0.01 to 1 wt % with respect to the total weight of the product. 11. The method for preventing yellowing of an episulfide-based cured resin according to claim 10, wherein the compound (a) is a compound represented by the following formula (2). [Chemical 102] (In the formula, R _{5 to} R ₁₀ each represent a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom. X represents S or O, and the number of S is the sum of S and O constituting a three-membered ring. Is 50% or more on average, Y is a substituted or unsubstituted linear, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms, a substituted or unsubstituted 1,4-dithiane group, an arylene group, Represents an aralkylene group, m represents an integer of 0 to 2, and n represents an integer of 0 to 4.) 12. The yellowing of the episulfide-based cured resin according to claim 10, wherein the compound (b) is a compound having one NH ₂ group per molecule and / or a compound having one or more NH groups per molecule. Prevention method. 13. The episulfide-based cured resin according to claim 10, wherein the compound (b) is a compound having one NH ₂ group per molecule and / or a compound having one or two NH groups per molecule. How to prevent yellowing. 14. The compound (b) is a compound having one NH ₂ group per molecule and / or a compound having one or two NH groups per molecule and having a cyclic structure. Method for preventing yellowing of episulfide-based cured resin of. 15. A compound (c) which can be a curing catalyst for an episulfide compound other than the compound (b) is a tertiary amine, a phosphine, a Lewis acid, a radical polymerization catalyst,
The method for preventing yellowing of a cured episulfide resin according to any one of claims 10 to 14, which is one or more compounds selected from cationic polymerization catalysts.