JP5225797B2 - Composition, polymerizable composition containing the same, and method for producing the composition - Google Patents

Description

The present invention relates to a composition , a polymerizable composition containing the composition, and a method for producing the composition .

In recent years, a transparent organic polymer material has been used as a transparent material replacing inorganic glass. For example, when such a material is used for an optical resin, it is required to have a high refractive index and a high Abbe number.
For example, Patent Documents 1 and 2 disclose that a specific polythiol and sulfur are reacted to obtain a polythiol oligomer for a lens material.

Japanese Patent No. 3949498 International Publication 2008/026727 Pamphlet

  In recent years, a lens having an even higher refractive index has been demanded.

The present invention provides a composition capable of giving a high refractive index and a polymerizable composition containing the same.

The present invention is shown below.
[1] A composition obtained by reacting a compound represented by the formula (1), methanedithiol, and an oxidizing agent.

[2] A composition obtained by reacting a compound represented by the formula (1), a methanedithiol derivative represented by R ₁ —S—CH ₂ —SH (2), and an oxidizing agent, is subjected to alcoholysis or hydrolysis. A composition obtained by decomposition.
(In the above formula (2), R ₁ represents an alkyl group having 1 to 6 carbon atoms, or an acyl group having 2 to 6 carbon atoms.)

[3] A composition comprising at least one of the compound represented by the formula (1), the formula (3) and the compound represented by the formula (4), methanedithiol, and an oxidizing agent are reacted. The resulting composition.

[4] A composition comprising a compound represented by formula (1), at least one of formula (3) and a compound represented by formula (4), and R ₁ —S—CH ₂ —SH (2 A composition obtained by reacting a methanedithiol derivative represented by) with an oxidizing agent, followed by alcoholysis or hydrolysis.
(In the above formula (2), R ₁ represents an alkyl group having 1 to 6 carbon atoms, or an acyl group having 2 to 6 carbon atoms.)

［５］［１］または［２］に記載の組成物あるいは、［３］または［４］に記載の組成物と、イソシアナート化合物とを含む重合性組成物。
［６］［５］に記載の重合性組成物において、メルカプト基と、前記イソシアナート化合物のイソシアナト基のモル比（ＳＨ基／ＮＣＯ基）が１．０より大きく１．５以下である重合性組成物。
［７］［５］または［６］に記載の重合性組成物において、前記イソシアナート化合物が芳香環を有するイソシアナート化合物である重合性組成物。
［８］［７］に記載の重合性組成物において、前記芳香環を有するイソシアナート化合物が、トリレンジイソシアネート、フェニレンジイソシアネート、４，４′―ジフェニルメタンジイソシアネート、およびトリフェニルメタントリイソシアネート、ナフタレンジイソシアナートよりなる群から選択される１種以上である重合性組成物。
［９］［１］または［２］に記載の組成物あるいは、請求項３または４に記載の組成物と、エピチオ化合物とを含む重合性組成物。
［１０］［５］乃至［９］いずれかに記載の重合性組成物を注型重合して樹脂を得る工程を含む、樹脂の製造方法。
［１１］［５］乃至［９］いずれかに記載の重合性組成物を重合して得られる樹脂。
［１２］［１１］に記載の樹脂からなる光学部品。
［１３］式（１）で示される化合物と、メタンジチオールと、酸化剤とを反応させて組成物を得る組成物の製造方法。

[5] A polymerizable composition comprising the composition according to [1] or [2], or the composition according to [3] or [4] and an isocyanate compound.
[6] The polymerizable composition according to [5], wherein the molar ratio of the mercapto group to the isocyanate group of the isocyanate compound (SH group / NCO group) is greater than 1.0 and 1.5 or less. Composition.
[7] The polymerizable composition as set forth in [5] or [6], wherein the isocyanate compound is an isocyanate compound having an aromatic ring.
[8] The polymerizable composition according to [7], wherein the isocyanate compound having an aromatic ring is tolylene diisocyanate, phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, triphenylmethane triisocyanate, or naphthalene diisocyanate. A polymerizable composition that is at least one selected from the group consisting of nates.
[9] A polymerizable composition comprising the composition according to [1] or [2] or the composition according to claim 3 or 4 and an epithio compound.
[10] A method for producing a resin comprising a step of cast polymerization of the polymerizable composition according to any one of [5] to [9] to obtain a resin.
[11] A resin obtained by polymerizing the polymerizable composition according to any one of [5] to [9].
[12] An optical component made of the resin according to [11].
[13] A method for producing a composition , wherein a compound represented by the formula (1), methanedithiol, and an oxidizing agent are reacted to obtain a composition .

[14] A composition obtained by reacting a compound represented by the formula (1) with a methanedithiol derivative represented by R ₁ —S—CH ₂ —SH (2) and an oxidizing agent is subjected to alcoholysis or hydrolysis. A method for producing a composition, which is decomposed to obtain a composition .
(In the above formula (2), R ₁ represents an alkyl group having 1 to 6 carbon atoms, or an acyl group having 2 to 6 carbon atoms.)

According to this invention, the composition which can give a high refractive index, the polymeric composition containing this, etc. are provided.

First, the outline of the present invention will be described.
The thiol compound of the present invention is obtained by the following method (I) or (II).

(I) a compound represented by formula (1);
Methanedithiol,
React with oxidant.

(II) a compound represented by the above formula (1);
R ₁ —S—CH ₂ —SH (2)
A methanedithiol derivative represented by
A compound obtained by reacting with an oxidizing agent is subjected to alcoholysis or hydrolysis.
(In the above formula (2), R ₁ represents an alkyl group having 1 to 6 carbon atoms, or an acyl group having 2 to 6 carbon atoms.)

In the production method (I), examples of the oxidizing agent include bromine, iodine, oxygen, sulfur, sodium hypochlorite and the like. Here, the oxidizing agent is a reagent for synthesizing a disulfide bond from two mercapto groups. Among these oxidizing agents, it is preferable to use iodine from the viewpoints of reaction selectivity, handleability, availability, and the like.
In addition, when sulfur is used as the oxidizing agent, the resulting resin may cause problems such as non-uniformity, coloring, and turbidity. Therefore, it is preferable to use an oxidizing agent excluding sulfur.

If the manufacturing method of (I) is demonstrated in detail, the compound shown by Formula (1) and methanedithiol will be mixed in an organic solvent. An oxidizing agent is dropped into the mixed solution. At this time, reaction temperature is about 0 to 50 degreeC normally, Preferably it is the range of 5 to 20 degreeC.
In the production method of (I), one compound to four mercapto groups (SH groups) represented by the formula (1) are oxidatively added with methanedithiol or two compounds of the formula (1). It is thought that a body etc. produce | generate as a mixture. Among these, it is considered that the compound represented by the formula (5) is mainly produced.

The production method of (II) will be described in detail. A compound represented by formula (1) and a methanedithiol derivative represented by formula (2) are mixed in an organic solvent. An oxidizing agent is dropped into the mixed solution. At this time, reaction temperature is about 0 to 50 degreeC normally, Preferably it is the range of 5 to 20 degreeC.
In the production method of (II), a compound in which a methanedithiol derivative is oxidized and added to one to four SH groups of the compound represented by the formula (1), a dimer of the compound represented by the formula (1), and the like. It is thought to form as a mixture. Among these, it is considered that the compound represented by the formula (6) is mainly produced.

(R ₁ in formula (6) is the same as R _{1 in} formula (2).)
Here, in the compound represented by the formula (2), R ₁ may be an alkyl group having 1 to 6 carbon atoms, or an acyl group having 2 to 6 carbon atoms. Of these, handling property, easy availability, from the viewpoint of reactivity in the conversion reaction to the compound represented by the formula (5), R ₁ is preferably an acetyl group.
Moreover, as an oxidizing agent, what is used with the manufacturing method of (I) can be used.

Thereafter, the compound represented by the formula (6) is obtained by alcoholysis or hydrolysis of the compound represented by the formula (6). For example, when R ₁ is an acetyl group, for example, a compound represented by the formula (5) is obtained by an alcohol decomposition reaction with methanol under a temperature condition of 60 ° C. under acidic conditions.

  Here, the compound represented by the above formula (1) can be produced by the method described in JP-A No. 2004-2820. However, the compound represented by the formula (1) and the following formulas (3) and (4) ) And may be obtained as a mixture with at least one of the compounds shown below.

  In this case, without isolating the compound represented by the formula (1), a composition comprising the compound represented by the formula (1) and at least one of the compounds represented by the formula (3) and the formula (4) is prepared. It is also possible to use the production methods (I) and (II) described above.

In particular,
(III) a composition comprising a compound represented by formula (1) and at least one of compounds represented by formula (3) and formula (4);
Methanedithiol,
React with oxidant.

(IV) a composition comprising a compound represented by the general formula (1) and at least one of the compounds represented by the formula (3) and the formula (4);
R ₁ —S—CH ₂ —SH (2)
A methanedithiol derivative represented by
A composition obtained by reacting with an oxidizing agent is subjected to alcoholysis or hydrolysis.
(In the above formula (2), R ₁ represents an alkyl group having 1 to 6 carbon atoms, or an acyl group having 2 to 6 carbon atoms.)

In addition, it is preferable to use the composition which has each thiol compound of Formula (1), (3), (4) as a raw material from a viewpoint of omitting isolation operation of a compound.
The oxidizing agent and reaction temperature in the production methods of (III) and (IV) are the same as in the case of (I).
Moreover, the compound shown by (2) in the manufacturing method of (IV) is the same as that of (II).
In the production methods of (III) and (IV), it is considered that in addition to the above formula (5), a composition containing at least one thiol compound of the following formulas (7) and (8) can be obtained. .

In the present invention, in each of the above production methods (I) to (IV), it is considered that a compound having a disulfide bond represented by R ₂ — (S—S—CH ₂ SH) n can be obtained. R ₂ is aliphatic or alicyclic and is an organic group containing S.

  By using the compound obtained by the above production methods (I) and (II) or the composition obtained by the production methods (III) and (IV), an optical component having a high refractive index is obtained. Can do.

(Polymerizable composition)
Next, the polymerizable composition will be described. The polymerizable composition of the present embodiment includes a compound obtained by the production methods (I) and (II) or a composition obtained by the production methods (III) and (IV).
The content of the thiol compound in the total weight of the polymerizable compound contained in the polymerizable composition is not particularly limited, but from the viewpoint of refractive index and mechanical properties, it is 50% by weight or more and 70% by weight or less. It is preferable that

The polymerizable composition in the present invention may further contain, for example, an isocyanate compound as another component. By so doing, the mechanical properties and hue of the resin obtained by polymerizing the polymerizable composition can be further improved.
Moreover, the polymerizable composition may contain an epithio compound. By having an epithio compound, the refractive index and Abbe number of the resin obtained by polymerizing the polymerizable composition can be further improved.

Hereinafter, each component will be described with specific examples.
(Isocyanate compound)
The isocyanate compound used in the present invention is a compound containing one or more isocyanate groups (NCO groups) in the molecule. The mechanical properties and the like may be further improved by adding an isocyanate compound.

Specific examples of preferred isocyanate compounds used herein include methyl isocyanate, ethyl isocyanate, n-propyl isocyanate, isopropyl isocyanate, n-butyl isocyanate, sec-butyl isocyanate, tert-butyl isocyanate, pentyl isocyanate, hexyl isocyanate, Heptyl isocyanate, octyl isocyanate, decyl isocyanate, lauryl isocyanate, myristyl isocyanate, octadecyl isocyanate, 3-pentyl isocyanate, 2-ethylhexyl isocyanate, 2,3-dimethylcyclohexyl isocyanate, 2-methoxyphenyl isocyanate cyanate, 4-methoxyphenyl isocyanate, α -Methylbenzyl iso Monofunctional isocyanate compounds such as sulfonate, phenylethyl isocyanate, phenyl isocyanate, o-, m-, p-tolyl isocyanate, cyclohexyl isocyanate, benzyl isocyanate, isocyanatomethylbicycloheptane, and hexamethylene diisocyanate, 2,2-dimethylpentane Diisocyanate, 2,2,4-trimethylhexane diisocyanate, butene diisocyanate, 1,3-butadiene-1,4-diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,6,11-undecatriisocyanate, 1, 3,6-hexamethylene triisocyanate, 1,8-diisocyanato-4-isocyanatomethyloctane, o-xylylene diisocyanate, p-xylylene diisocyanate Aliphatic polyisocyanates such as cyanate, m-xylylene diisocyanate, bis (isocyanatomethyl) naphthalene, bis (isocyanatoethyl) carbonate, bis (isocyanatoethyl) ether, lysine diisocyanatomethyl ester, lysine triisocyanate Compound and isophorone diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, dicyclohexyldimethylmethane isocyanate, 2,2-dimethyl Dicyclohexylmethane isocyanate, 2,5-bis (isocyanatomethyl) bicyclo- [2,2,1] -heptane, 2 6-bis (isocyanatomethyl) bicyclo- [2,2,1] -heptane, 3,8-bis (isocyanatomethyl) tricyclodecane, 3,9-bis (isocyanatomethyl) tricyclodecane, 4, Alicyclic polyisocyanate compounds such as 8-bis (isocyanatomethyl) tricyclodecane and 4,9-bis (isocyanatomethyl) tricyclodecane,
And phenylene diisocyanate, tolylene diisocyanate, ethylphenylene diisocyanate, isopropylphenylene diisocyanate, dimethylphenylene diisocyanate, diethylphenylene diisocyanate, diisopropylphenylene diisocyanate, trimethylbenzene triisocyanate, benzene triisocyanate, biphenyl diisocyanate, toluidine diisocyanate, 4,4'-diphenylmethane diisocyanate 3,3-dimethyldiphenylmethane-4,4-diisocyanate, bibenzyl-4,4-diisocyanate, bis (isocyanatophenyl) ethylene, 3,3-dimethoxybiphenyl-4,4-diisocyanate, phenylisocyanatoethyl isocyanate, hexa Hydrobenzene Aromatic polyisocyanate compounds such as isocyanate, hexahydrodiphenylmethane-4,4-diisocyanate, triphenylmethane triisocyanate, naphthalene diisocyanate, and the like, and bis (isocyanatoethyl) sulfide, bis (isocyanatopropyl) sulfide, bis (isocyanato) Hexyl) sulfide, bis (isocyanatomethyl) sulfone, bis (isocyanatomethyl) disulfide, bis (isocyanatopropyl) disulfide, bis (isocyanatomethylthio) methane, bis (isocyanatoethylthio) methane, bis (isocyanatoethyl) Sulfur-containing aliphatic polyisocyanate compounds such as thio) ethane, bis (isocyanatomethylthio) ethane, 1,5-diisocyanato-2-isocyanatomethyl-3-thiapentane , And diphenyl sulfide-2,4-diisocyanate, diphenyl sulfide-4,4-diisocyanate, 3,3-dimethoxy-4,4-diisocyanatodibenzylthioether, bis (4-isocyanatomethylbenzene) sulfide, 4, 4-methoxybenzenethioethylene glycol-3,3-diisocyanate, diphenyl disulfide-4,4-diisocyanate, 2,2-dimethyldiphenyl disulfide-5,5-diisocyanate, 3,3-dimethyldiphenyl disulfide-5,5-diisocyanate 3,3-dimethyldiphenyl disulfide-6,6-diisocyanate, 4,4-dimethyldiphenyl disulfide-5,5-diisocyanate, 3,3-dimethoxydiphenyl disulfide-4,4-diisocyanate , Sulfur-containing aromatic polyisocyanate compounds such as 4,4-dimethoxydiphenyl disulfide-3,3-diisocyanate, and 2,5-diisocyanatothiophene, 2,5-bis (isocyanatomethyl) thiophene, 2, 5-diisocyanatotetrahydrothiophene, 2,5-bis (isocyanatomethyl) tetrahydrothiophene, 3,4-bis (isocyanatomethyl) tetrahydrothiophene, 2,5-diisocyanato-1,4-dithiane, 2,5- Bis (isocyanatomethyl) -1,4-dithiane, 4,5-diisocyanato-1,3-dithiolane, 4,5-bis (isocyanatomethyl) -1,3-dithiolane, 4,5-bis (isocyanato) A sulfur-containing heterocyclic polyisocyanate compound such as methyl) -2-methyl-1,3-dithiolane, etc. It can gel, but not limited to these exemplified compounds.

  Halogen-substituted products such as chlorine-substituted products and bromine-substituted products of these compounds, alkyl-substituted products, alkoxy-substituted products, nitro-substituted products, prepolymer-modified products with polyhydric alcohols, carbodiimide-modified products, urea-modified products, biurets Denatured products, dimerization or trimerization reaction products may be used. These isocyanate compounds may be used alone or in admixture of two or more.

Among these, from the viewpoint of increasing the refractive index, an isocyanate compound having an aromatic ring is preferable. Furthermore, it is more preferable that the isocyanate group is directly connected to the aromatic ring. Specifically, it is preferably at least one selected from the group consisting of tolylene diisocyanate, phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, triphenylmethane triisocyanate, and naphthalene diisocyanate.
In addition, from the viewpoint of increasing the refractive index of the resin, phenylene diisocyanate is more preferable. In order to further increase the transparency of the resin, the phenylene diisocyanate preferably includes m-phenylene diisocyanate.

Here, in the polymerizable composition, from the viewpoint of increasing the refractive index, it is preferable that the molar ratio of the mercapto group to the isocyanate group of the isocyanate compound (SH group / NCO group) is larger than 1.0. From the viewpoint of heat resistance, the molar ratio is preferably 1.5 or less.
Preferably, the molar ratio is 1.05 or more and 1.3 or less.
The molar ratio of mercapto group to isocyanato group (SH group / NCO group) means the total number of isocyanate groups contained in the isocyanate compound constituting the polymerizable composition of the present invention, and the polymerizable composition of the present invention. It is a ratio with the total number of moles of mercapto groups contained in the thiol compound to constitute.
In addition, when two or more kinds of isocyanate compounds are included, the number of moles of isocyanate groups possessed by two or more kinds of isocyanate compounds is added. In addition, in the case of including “other (poly) thiols” other than the thiol compound and the composition obtained by the above-described production methods (I) to (IV), the total mercapto group contained in the polymerizable composition Refers to the total number of moles.
When the polythiol compound is a mixture, it can be determined by the milliequivalent number (meq / g, hereinafter referred to as SHV value) of a mercapto group in 1 g of thiols determined by known titration.

(Epithio compound)
Specific examples of the epithio compound include bis (1,2-epithioethyl) sulfide, bis (1,2-epithioethyl) disulfide, bis (epithioethylthio) methane, bis (epithioethylthio) benzene, and bis [4. An epithioethylthio compound such as-(epithioethylthio) phenyl] sulfide, bis [4- (epithioethylthio) phenyl] methane;
Bis (2,3-epithiopropyl) sulfide, bis (2,3-epithiopropyl) disulfide, bis (2,3-epithiopropylthio) methane, 1,2-bis (2,3-epithiopropyl) Thio) ethane, 1,2-bis (2,3-epithiopropylthio) propane, 1,3-bis (2,3-epithiopropylthio) propane, 1,3-bis (2,3-epithio) Propylthio) -2-methylpropane, 1,4-bis (2,3-epithiopropylthio) butane, 1,4-bis (2,3-epithiopropylthio) -2-methylbutane, 1,3- Bis (2,3-epithiopropylthio) butane, 1,5-bis (2,3-epithiopropylthio) pentane, 1,5-bis (2,3-epithiopropylthio) -2-methylpentane 1,5-bis (2, -Epithiopropylthio) -3-thiapentane, 1,6-bis (2,3-epithiopropylthio) hexane, 1,6-bis (2,3-epithiopropylthio) -2-methylhexane, , 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-epithio Propylthio) butane, 1,5-bis (2,3-epithiopropylthio) -2- (2,3-epithiopropylthiomethyl) -3-thiapentane, 1,5-bis (2,3-epi Thiopropylthio) -2,4-bis ( , 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-epithiopropylthio) Methyl) -3,6-dithiaoctane, 1,8-bis (2,3-epithiopropylthio) -4,4-bis (2,3-epithiopropylthiomethyl) -3,6-dithiaoctane, 1, 8-bis (2,3-epithiop Lopyrthio) -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) -5,7-bis (2,3-epithiopropylthiomethyl) -3,6,9-tri Chain aliphatic 2,3-epithiopropylthio compounds such as thiaundecane;
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-1,4- Cycloaliphatic 2,3-epithiopropylthio compounds such as 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-epithiopropyl) Thiomethyl) 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, 4,4′-bis (2,3-epithiopropylthio) biphenyl, etc. Aromatic 2 , 3-epithiopropylthio compound;
Compounds having one epithio group such as ethylene sulfide, propylene sulfide, mercaptopropylene sulfide, mercaptobutene sulfide, epithiochlorohydrin;
Bis (2,3-epithiopropyl) ether, bis (2,3-epithiopropyloxy) methane, 1,2-bis (2,3-epithiopropyloxy) ethane, 1,2-bis (2, 3-epithiopropyloxy) propane, 1,3-bis (2,3-epithiopropyloxy) propane, 1,3-bis (2,3-epithiopropyloxy) -2-methylpropane, 1,4 -Bis (2,3-epithiopropyloxy) butane, 1,4-bis (2,3-epithiopropyloxy) -2-methylbutane, 1,3-bis (2,3-epithiopropyloxy) butane 1,5-bis (2,3-epithiopropyloxy) pentane, 1,5-bis (2,3-epithiopropyloxy) -2-methylpentane, 1,5-bis (2,3-epi Thiopropyloxy) 3-thiapentane, 1,6-bis (2,3-epithiopropyloxy) hexane, 1,6-bis (2,3-epithiopropyloxy) -2-methylhexane, 1,8-bis (2, 3-epithiopropyloxy) -3,6-dithiaoctane, 1,2,3-tris (2,3-epithiopropyloxy) propane, 2,2-bis (2,3-epithiopropyloxy) -1 , 3-bis (2,3-epithiopropyloxymethyl) propane, 2,2-bis (2,3-epithiopropyloxymethyl) -1- (2,3-epithiopropyloxy) butane, 1, 5-bis (2,3-epithiopropyloxy) -2- (2,3-epithiopropyloxymethyl) -3-thiapentane, 1,5-bis (2,3-epithiopropyloxy) -2, 4-bis (2, -Epithiopropyloxymethyl) -3-thiapentane, 1- (2,3-epithiopropyloxy) -2,2-bis (2,3-epithiopropyloxymethyl) -4-thiahexane, 1,5, 6-Tris (2,3-epithiopropyloxy) -4- (2,3-epithiopropyloxymethyl) -3-thiahexane, 1,8-bis (2,3-epithiopropyloxy) -4- (2,3-epithiopropyloxymethyl) -3,6-dithiaoctane, 1,8-bis (2,3-epithiopropyloxy) -4,5-bis (2,3-epithiopropyloxymethyl) 3,6-dithiaoctane, 1,8-bis (2,3-epithiopropyloxy) -4,4-bis (2,3-epithiopropyloxymethyl) -3,6-dithiaoctane, 1,8- Screw( 2,3-epithiopropyloxy) -2,5-bis (2,3-epithiopropyloxymethyl) -3,6-dithiaoctane, 1,8-bis (2,3-epithiopropyloxy) -2 , 4,5-tris (2,3-epithiopropyloxymethyl) -3,6-dithiaoctane, 1,1,1-tris [[2- (2,3-epithiopropyloxy) ethyl] thiomethyl]- 2- (2,3-epithiopropyloxy) ethane, 1,1,2,2-tetrakis [[2- (2,3-epithiopropyloxy) ethyl] thiomethyl] ethane, 1,11-bis (2 , 3-epithiopropyloxy) -4,8-bis (2,3-epithiopropyloxymethyl) -3,6,9-trithiaundecane, 1,11-bis (2,3-epithiopropyloxy) ) -4,7-Bis 2,3-epithiopropyloxymethyl) -3,6,9-trithiaundecane, 1,11-bis (2,3-epithiopropyloxy) -5,7-bis (2,3-epithiopropyl) Chain aliphatic 2,3-epithiopropyloxy compounds such as oxymethyl) -3,6,9-trithiaundecane;
1,3-bis (2,3-epithiopropyloxy) cyclohexane, 1,4-bis (2,3-epithiopropyloxy) cyclohexane, 1,3-bis (2,3-epithiopropyloxymethyl) Cyclohexane, 1,4-bis (2,3-epithiopropyloxymethyl) cyclohexane, 2,5-bis (2,3-epithiopropyloxymethyl) -1,4-dithiane, 2,5-bis [[ 2- (2,3-epithiopropyloxy) ethyl] thiomethyl] -1,4-dithiane, 2,5-bis (2,3-epithiopropyloxymethyl) -2,5-dimethyl-1,4- A cycloaliphatic 2,3-epithiopropyloxy compound such as dithiane; and
1,2-bis (2,3-epithiopropyloxy) benzene, 1,3-bis (2,3-epithiopropyloxy) benzene, 1,4-bis (2,3-epithiopropyloxy) benzene 1,2-bis (2,3-epithiopropyloxymethyl) benzene, 1,3-bis (2,3-epithiopropyloxymethyl) benzene, 1,4-bis (2,3-epithiopropyl) Oxymethyl) benzene, bis [4- (2,3-epithiopropyloxy) phenyl] methane, 2,2-bis [4- (2,3-epithiopropyloxy) phenyl] propane, bis [4- ( 2,3-epithiopropyloxy) phenyl] sulfide, bis [4- (2,3-epithiopropyloxy) phenyl] sulfone, 4,4′-bis (2,3-epithiopropyloxy) bi Examples include aromatic 2,3-epithiopropyloxy compounds such as phenyl, but are not limited to the exemplified compounds.

Among these exemplified compounds, preferred compounds include bis (1,2-epithioethyl) sulfide, bis (1,2-epithioethyl) disulfide, bis (2,3-epithiopropyl) sulfide, and bis (2,3-epithio). Propylthio) methane and bis (2,3-epithiopropyl) disulfide, and more preferred compounds are bis (1,2-epithioethyl) sulfide, bis (1,2-epithioethyl) disulfide, bis (2,3- Epithiopropyl) sulfide and bis (2,3-epithiopropyl) disulfide. Further more preferred compounds are bis (2,3-epithiopropyl) sulfide and bis (2,3-epithiopropyl) disulfide.
Here, in the polymerizable composition, the total weight of the epithio compound and the total weight of the thiol compound (“other (poly) other than the thiol compound and the composition obtained by the above-described production methods (I) to (IV)” In the case of including “thiols”, the total weight including other (poly) thiols ”is 100, and from the viewpoint of increasing the refractive index, the content (% by weight) of the thiol compound is 1.0% or more and 30% or less, preferably 2.0% or more and 20% or less, more preferably 5.0% or more and 15% or less. If it is the said range, heat resistance and a hue can be made favorable reliably.

  In addition, the polymerizable composition of this embodiment may have both the isocyanate compound and epithio compound mentioned above, and may have an epoxy compound and a thietane compound.

  Moreover, the polymerizable composition of the present invention may contain a bluing agent as necessary. The bluing agent has an absorption band in the wavelength range from orange to yellow in the visible light region, and has a function of adjusting the hue of the resin. More specifically, the bluing agent contains a substance exhibiting a blue to purple color.

  The bluing agent used in the polymerizable composition of the present invention is not particularly limited, and specific examples include dyes, fluorescent whitening agents, fluorescent pigments, and inorganic pigments. Of those that can be used, it is appropriately selected according to the physical properties and resin hue required for the optical component. These bluing agents may be used alone or in combination of two or more.

  Among these bluing agents, dyes are preferred from the viewpoint of solubility in the polymerizable composition and the transparency of the resulting resin. Among the dyes, a dye containing one or more dyes selected from blue dyes and violet dyes is preferable, but in some cases, other color dyes may be mixed and used. For example, in addition to blue and violet dyes, gray, brown, red and orange dyes can also be used. Specific examples of such a combination of bluing agents include a combination of a blue dye and a red dye, and a combination of a violet dye and a red dye.

From the viewpoint of the absorption wavelength, a dye having a maximum absorption wavelength of 520 nm to 600 nm is preferable, and a dye having a maximum absorption wavelength of 540 nm to 580 nm is more preferable.
From the viewpoint of the structure of the compound, anthraquinone dyes are preferable.

  Specific examples of dyes include “PS Blue RR”, “PS Violet RC”, “PET Blue 2000”, “PS Brilliant Red HEY”, “MLP RED V-1” (each trade name of Dystar Japan) ) And the like.

  The amount of blueing agent used varies depending on the type of monomer, the presence or absence of various additives, the type and amount of additives used, the polymerization method, and the polymerization conditions. Used at a ratio of 0.001 ppm to 500 ppm, preferably 0.005 ppm to 100 ppm, more preferably 0.01 ppm to 10 ppm, based on the total weight of the polymerizable compound contained in the product. The If the amount of the bluing agent added is too large, the entire optical component may become too blue, which may be undesirable. If it is too small, the hue improving effect may not be sufficiently exerted, which may be undesirable.

  The method for adding the bluing agent is not particularly limited, and it is desirable to add it to the monomer system in advance. As a method for this, a method of dissolving in a monomer, or a method of preparing a master solution containing a high concentration of bluing agent and diluting the master solution with a monomer or other additive to be added. Various methods can be adopted.

  The polymerizable composition in the present invention has a viscosity that does not hinder handling properties. Here, the viscosity can be evaluated by, for example, the viscosity of the monomer mixture at the temperature at the time of preparation measured with a B-type viscometer. From the viewpoint that the viscosity immediately after the preparation of the composition, the defoaming treatment under reduced pressure and other steps through the injection of all the monomers is important, and the handling property is good, for example, As a guide, the viscosity immediately after the composition of the composition is 100 mPa · s or less, preferably 50 mPa · s or less, more preferably 30 mPa · s or less. In addition, when an optical material is molded by cast polymerization described later, the viscosity at the time of injection is preferably 200 mPa · s or less as a measured value at the temperature at the time of injection, particularly for a lens having a very thin center thickness. For production, a further low viscosity, for example 100 mPa · s or less, is more preferred. The temperature at the time of preparation and injection is appropriately selected according to the monomer component to be added.

  When the polymerizable composition of the present invention is cured and molded, if necessary, a catalyst such as dibutyltin dichloride or dimethyltin dichloride, a UV absorber such as benzotriazole, an acid, and the like in a known molding method. Add substances such as internal release agents such as phosphate esters, light stabilizers, antioxidants, reaction initiators such as radical reaction initiators, chain extenders, crosslinking agents, anti-coloring agents, oil-soluble dyes, fillers, etc. May be.

  When the polymerizable composition of the present invention contains an isocyanate compound, a catalyst, a release agent, and other additives are mixed with a reaction catalyst, a release agent, and other additives to prepare an injection solution. Depending on the solubility in the compound and the thiol compound, it may be added and dissolved in the isocyanate compound in advance, or may be added and dissolved in the thiol compound, or may be added and dissolved in a mixture of the isocyanate compound and the thiol compound. Or you may add this, after making it melt | dissolve in a part of isocyanate compound or thiol compound to be used and preparing a master liquid. The order of addition is not limited to these exemplified methods, and is appropriately selected in consideration of operability, safety, convenience and the like.

  The mixing is usually performed at a temperature at which mixing is possible, and is appropriately selected according to the melting point of the monomer component to be added. From the viewpoint of the pot life of the mixture, it may be preferable to lower the temperature. In addition, when additives such as catalysts and mold release agents do not show good solubility in isocyanate compounds and thiol compounds, they may be preheated and dissolved in isocyanate compounds, thiol compounds or mixtures thereof. is there.

  Furthermore, depending on the physical properties required for the obtained plastic lens, it is often preferable to perform a defoaming treatment under reduced pressure, a filtration treatment under pressure, reduced pressure, or the like, if necessary.

  In molding the lens, the lens casting mold into which the polymerizable composition of the present invention is injected is heated in a heatable apparatus such as an oven or in water for several hours to several tens of hours with a predetermined temperature program. Then harden and mold.

  The polymerization curing temperature is not limited because the conditions vary depending on the composition of the mixture, the type of the catalyst, the shape of the mold, and the like, but is approximately -50 to 200 ° C. for 1 to 100 hours.

  Usually, it is generally started at a temperature in the range of 25 ° C. to 60 ° C., and then gradually raised to a range of 80 ° C. to 130 ° C. and heated at that temperature for 1 to 4 hours.

  A plastic lens can be obtained by taking out from the lens casting mold after completion of the curing molding.

  The plastic lens obtained from the optical material of the present embodiment is preferably subjected to annealing treatment by heating the released lens for the purpose of alleviating distortion due to polymerization. The annealing temperature is usually in the range of 80 to 150 ° C, preferably in the range of 100 to 130 ° C, more preferably in the range of 110 to 130 ° C. The annealing time is usually in the range of 0.5 to 5 hours, preferably in the range of 1 to 4 hours.

  The plastic lens obtained from the optical material of the present embodiment is used with a coating layer on one side or both sides as required. Examples of the coating layer include a primer layer, a hard coat layer, an antireflection film layer, an antifogging coat layer, a stainproof layer, and a water repellent layer. These coating layers may be used singly or in a multilayered form. When a coating layer is applied to both sides, a similar coating layer or a different coating layer may be applied to each surface.

  Each of these coating layers has an ultraviolet absorber for the purpose of protecting the lens and eyes from ultraviolet rays, an infrared absorber for the purpose of protecting the eyes from infrared rays, a light stabilizer and an antioxidant for the purpose of improving the light resistance of the lens, Dyes and pigments for the purpose of enhancing the fashionability of the lens, photochromic dyes and photochromic pigments, antistatic agents, and other known additives may be used in combination for the purpose of enhancing the performance of the lens. Various leveling agents may be used for the purpose of improving coatability.

  The primer layer is generally composed of a lens substrate (an optical material obtained from the polymerizable composition of the present invention) and a hard coat layer for the purpose of improving adhesion of the hard coat layer and impact resistance of the plastic lens. The film thickness is usually about 0.1 to 10 μm.

  The primer layer is formed by, for example, a coating method or a dry method. In the application method, a primer layer is formed by applying the primer composition by a known application method such as spin coating or dip coating, followed by solidification. In the dry method, it is formed by a known dry method such as a CVD method or a vacuum deposition method. When forming the primer layer, the surface of the lens may be subjected to pretreatment such as alkali treatment, plasma treatment, or ultraviolet treatment as necessary for the purpose of improving adhesion.

  The primer composition is preferably a material in which the solidified primer layer has high adhesion to the lens substrate (an optical material obtained from the polymerizable composition of the present invention), and is usually a urethane resin, an epoxy resin, or a polyester resin. , A melanin resin, a primer composition mainly composed of polyvinyl acetal, and the like are used. The primer composition can be used in the absence of a solvent, but an appropriate solvent that does not affect the lens may be used for the purpose of adjusting the viscosity of the composition.

  The hard coat layer is a coating layer intended to give the lens surface functions such as scratch resistance, abrasion resistance, moisture resistance, warm water resistance, heat resistance, weather resistance, etc. It is about 0.3 to 30 μm.

  The hard coat layer is usually formed by applying a hard coat composition by a known application method such as spin coating or dip coating, followed by curing. Examples of the curing method include thermal curing, a curing method by irradiation with energy rays such as ultraviolet rays and visible rays, and the like. When forming the hard coat layer, the coated surface (lens substrate or primer layer) may be subjected to pretreatment such as alkali treatment, plasma treatment, and ultraviolet treatment as necessary for the purpose of improving adhesion. .

  As hard coat compositions, generally, there are curable organosilicon compounds and fine oxide particles such as Si, Al, Sn, Sb, Ta, Ce, La, Fe, Zn, W, Zr, In, and Ti. A mixture of (including complex oxide fine particles) is often used. In addition to these, amines, amino acids, metal acetylacetonate complexes, organic acid metal salts, perchloric acids, perchloric acid salts, acids, metal chlorides and polyfunctional epoxy compounds may also be used. Good. The hard coat composition can be used without a solvent, but an appropriate solvent that does not affect the lens may be used.

The antireflection layer is usually formed on the hard coat layer as necessary. The antireflection layer includes an inorganic type and an organic type. In the case of an inorganic type, generally, an inorganic oxide such as SiO ₂ or TiO ₂ is used for vacuum deposition, sputtering, ion plating, ion It is often formed by a dry method such as a beam assist method or a CVD method. In the case of an organic type, generally, it is often formed by a wet process using a composition containing an organosilicon compound and silica-based fine particles having internal cavities.

The antireflection layer may be a single layer or a multilayer, but when used as a single layer, the refractive index is preferably at least 0.1 lower than the refractive index of the hard coat layer. In order to effectively exhibit the antireflection function, it is preferable to use a multilayer antireflection film. In that case, a low refractive index film and a high refractive index film are usually laminated alternately. Also in this case, the refractive index difference between the low refractive index film and the high refractive index film is preferably 0.1 or more. Examples of the high refractive index film include ZnO, TiO ₂ , CeO ₂ , Sb ₂ O ₅ , SnO ₂ , ZrO ₂ , and Ta ₂ O ₅ , and examples of the low refractive index film include an SiO ₂ film. It is done. The film thickness is usually about 50 to 150 nm.

  Furthermore, the plastic lens made of the optical material of the present embodiment may be subjected to back surface polishing, antistatic treatment, dyeing treatment, light control treatment, and the like, if necessary.

  The resin obtained by polymerizing the polymerizable composition of the present invention has a high refractive index, and is useful as a resin used for optical parts such as plastic lenses.

Examples of optical components include various plastic lenses such as eyeglass lenses for correcting vision, lenses for imaging devices, Fresnel lenses for liquid crystal projectors, lenticular lenses, and contact lenses;
Sealing material for light emitting diode (LED);
Optical waveguide;
Optical adhesive used for bonding optical lenses and optical waveguides;
Anti-reflective film used for optical lenses;
Examples thereof include a transparent coating or a transparent substrate used for liquid crystal display device members such as a substrate, a light guide plate, a film, and a sheet.

The optical properties (refractive index, Abbe number), heat resistance, hue, and strength of the resins produced in Examples and Comparative Examples were evaluated by the following test methods.
Refractive index (ne), Abbe number (νe): Measured at 20 ° C. using a Purfrich refractometer.
-Heat resistance: Measured by TMA penetration method (50 g load, pin tip 0.5 mmφ, heating rate 10 ° C / min). The temperature at the intersection of the tangent of the TMA curve at the time of thermal expansion and the tangent of the TMA curve at the time of dropping was defined as the thermal deformation start temperature.
-Bending test: Measured with AUTOGRAPH AGS-J manufactured by Shimadzu Corporation. Using a resin test piece with a thickness of 3.0mm, a length of 75mm and a width of 25.0mm, measure the maximum point stress (N / mm ² ) when a load is applied to the center of the test piece at a descending speed of 1.2mm / min did.
・ Tensile strength test (drilling test for drilling): Using AUTOGRAPH AGS-J manufactured by Shimadzu Corporation, a two-point frame processing was performed on a resin flat plate adjusted to a lens diameter of 45 mm and a thickness of 2.5 mm with a drill. Drill a 1.6mm diameter hole in two locations, pass a 1.6mm metal shaft through the hole, attach both ends of the sample to the fixture, and then pull at a speed of 5mm / min to measure the maximum point test force. Then, a value (kgf / mm) obtained by dividing the obtained maximum point test force by the resin thickness was calculated.
・ SHV: Number of milliequivalents of mercapto group contained in 1g of compound (meq / g)

[Production Example 1]
A polythiol composition A containing 1,1,3,3-tetrakis (mercaptomethylthio) propane as a main component was synthesized according to the method described in Production Example 2 of JP-A-2004-2820.
Into a flask with a 2-liter bottomed cock equipped with a stirring blade, thermometer, distillation column, and capillary for introducing nitrogen, 164.2 g (1 mol) of 1,1,3,3-tetramethoxypropane, 488.8 g of acetylthiomethylthiol ( 4 mol) and 7.6 g (0.04 mol) of paratoluenesulfonic acid were added, and the mixture was heated to 40 ° C. with stirring under vacuum of 1 kPa or less. Heating was continued for about 18 hours until the distillation of methanol stopped. After cooling, release the vacuum, attach a condenser instead of a distillation column, add 400 ml of methanol, 400 ml of chloroform, and 200 ml of 36% hydrochloric acid, and heat to 60 ° C. to perform alcoholysis. A polythiol composition A containing 3,3-tetrakis (mercaptomethylthio) propane as a main component was synthesized.
An appropriate amount of water and chloroform were added for liquid separation, and the chloroform layer was washed with water several times. After removing the solvent to remove chloroform and low-boiling components, 340.0 g of polythiol composition A was obtained after filtration through a 3 μm Teflon (registered trademark) filter. The analysis results of 1,1,3,3-tetrakis (mercaptomethylthio) propane are as follows. Furthermore, two components of the pothiol compound component were detected by LC analysis of the polythiol composition A (9.8% and 9.8% in chromatogram area ratio, respectively). When these components were purified and analyzed by preparative LC, 4,6-bis (mercaptomethylthio) -1,3-dithiane, 2- (2,2-bis (mercaptomethylthio) ethyl) -1,3- Dithietan. The analysis results are shown below.
Further, the SHV of the polythiol composition A (including the two by-products described above) was measured by the following method. A 0.05 mol / L iodine solution was gradually added dropwise to a mixed solvent solution of 95.1 mg of polythiol composition A in 30 ml of chloroform and 30 ml of methanol. When 9.7 ml was dropped, the brown color of the dropped iodine did not disappear, and the amount of SH groups contained in the polythiol composition A was calculated using this point as an equivalence point, resulting in 9.64 meq / g.
i) 1,1,3,3-Tetrakis (mercaptomethylthio) propane
¹ H-NMR δ (CDCl ₃ ): 2.18 (t, 4H), 2.49 (t, 2H), 3.78-3.90 (m, 8H), 4.64 (t, 2H)
¹³ C-NMR δ (CDCl ₃ ): 26.7, 41.3, 48.7
FT-IR: 538cm ^-1
MS: m / z = 356 (M ⁺ )
ii) 4,6-bis (mercaptomethylthio) -1,3-dithiane
¹ H-NMR δ (CDCl ₃ ): 2.02 (t, 2H), 2.56 (t, 2H), 3.77-3.91 (m, 8H), 3.97 (s, 2H), 4.66 (t, 2H)
¹³ C-NMR δ (CDCl ₃ ): 27.1, 28.8, 38.1, 44.6
FT-IR: 2538cm ^-1
MS: m / z = 276 (M ⁺ )
iii) 2- (2,2-bis (mercaptomethylthio) ethyl) -1,3-dithietane
¹ H-NMR δ (CDCl ₃ ): 2.03 (t, 2H), 2.13-2.21 (m, 1H), 2.75.2.80 (m, 1H), 3.79-3.84 (m, 1H), 3.90-3.96 (m, 3H), 4.32-4.35 (m, 2H)
¹³ C-NMR δ (CDCl ₃ ): 27.2, 32.3, 38.9, 46.2
FT-IR: 2538cm ^-1
MS: m / z = 276 (M ⁺ )

[Example 1]
102.99 g (SH group content 1.0 mol) of polythiol composition A synthesized by the method described in Production Example 1 and 40.09 g (0.5 mol) of methanedithiol were suspended in a mixed solvent of 1000 ml of chloroform and 100 ml of methanol. After adding 1000 ml of 0.5 mol / L iodine aqueous solution (iodine content 0.5 mol) at 25 ° C. over 1 hour, the mixture was stirred for 15 minutes. The aqueous phase was removed by a liquid separation operation, and the chloroform phase was washed with 200 g of distilled water. Further, the chloroform phase was washed with 200 g of 35% hydrochloric acid. Subsequently, it was washed with 200 g of distilled water three times, and the chloroform phase was dried and dehydrated with anhydrous magnesium sulfate. Chloroform was distilled off from the solution obtained by filtering off anhydrous magnesium sulfate under reduced pressure to obtain 123.1 g of polythiol composition B (light yellow slightly turbid viscous liquid) (yield 87%). The SHV was 6.67 meq / g.
In Example 1, each thiol compound (1,1,3,3-tetrakis (mercaptomethylthio) propane, 4,6-bis (mercaptomethylthio) -1,3-dithiane, 2- ( 2,2-bis (mercaptomethylthio) ethyl) -1,3-dithietane) is presumed to have undergone an oxidative addition reaction with methanedithiol to produce multiple types of thiol compounds.

[Example 2]
102.7 g (SH group content: 1.0 mol) of polythiol composition A synthesized by the method described in Production Example 1 and 40.09 g (0.5 mol) of methanedithiol were suspended in a mixed solvent of 1000 ml of chloroform and 100 ml of methanol. After adding 1000 ml of 0.5 mol / L iodine aqueous solution (iodine content 0.5 mol) at 25 ° C. over 1 hour, the mixture was stirred for 15 minutes. The aqueous phase was removed by a liquid separation operation, and the chloroform phase was washed with 200 g of distilled water. Further, the chloroform phase was washed with 200 g of 35% hydrochloric acid. Subsequently, it was washed with 200 g of distilled water three times, and the chloroform phase was dried and dehydrated with anhydrous magnesium sulfate. After filtering off anhydrous magnesium sulfate and distilling off chloroform under reduced pressure, the mixture was filtered through a 3 μm PTFE filter to obtain 100.3 g of polythiol composition C (light yellow viscous liquid) (yield 71%). The SHV was 6.74 meq / g.
In Example 2, each thiol compound (1,1,3,3-tetrakis (mercaptomethylthio) propane, 4,6-bis (mercaptomethylthio) -1,3-dithiane, 2- ( 2,2-bis (mercaptomethylthio) ethyl) -1,3-dithietane) is presumed to have undergone an oxidative addition reaction with methanedithiol to produce multiple types of thiol compounds.

[Example 3]
7.38 g (SH group content 71.1 mol) of polythiol composition A synthesized by the method described in Production Example 1 and 2.85 g (35.5 mol) of methanedithiol were suspended in a mixed solvent of 200 ml of chloroform and 200 ml of methanol. 71.1 ml of 0.5 mol / L iodine aqueous solution (iodine content 35.5 mmol) was dripped in the range of 25-30 degreeC over 30 minutes, Then, it stirred for 30 minutes. After adding 70 ml of distilled water, the aqueous phase was removed by a liquid separation operation, and the chloroform phase was washed 4 times with 100 g of distilled water. Subsequently, after the chloroform phase was dried and dehydrated with anhydrous magnesium sulfate, chloroform was distilled off under reduced pressure from the solution obtained by filtering off anhydrous magnesium sulfate to obtain 8.43 g of polythiol composition D (light yellow, slightly viscous liquid). (Yield 83%). The SHV was 5.80 meq / g.
In Example 3, each thiol compound (1,1,3,3-tetrakis (mercaptomethylthio) propane, 4,6-bis (mercaptomethylthio) -1,3-dithiane, 2- ( 2,2-bis (mercaptomethylthio) ethyl) -1,3-dithietane) is presumed to have undergone an oxidative addition reaction with methanedithiol to produce multiple types of thiol compounds.

[Example 4]
Tolylene-2,4-diisocyanate (11.02 g) and 6 mg of dibutyltin dichloride as a curing catalyst were mixed and dissolved at 20 ° C. Subsequently, 18.98 g of polythiol composition B synthesized by the method described in Example 1 was added. This suspension was heated and stirred at 60 ° C. for 20 minutes to obtain a homogeneous solution (the molar ratio of mercapto group and isocyanato group in the monomer mixture was SH / NCO = 1.0). After degassing under reduced pressure for 10 minutes, the mixture was poured into a mold composed of a glass mold and a tape. The mold was put into an oven and polymerized by gradually raising the temperature from 60 ° C. to 120 ° C. over 26 hours. After completion of the polymerization, the mold was removed from the oven and released to obtain a resin. The obtained resin was further annealed at 120 ° C. for 4 hours. Table 1 shows the physical properties of the obtained resin.

[Examples 5 to 8]
In Examples 5 to 8, resins were obtained in the same manner as in Example 4 except that the monomer composition and SH group / NCO group molar ratio shown in Table 1 were used.
Specifically, in Example 5, the same polythiol composition B as in Example 4 was used, and resinification was performed in the same manner as in Example 4.
In Examples 6 and 7, the polythiol composition C obtained in Example 2 was used in place of the polythiol composition B. In addition, resinization was performed in the same manner as in Example 4 except that 4,4′-diphenylmethane diisocyanate was used instead of tolylene-2,4-diisocyanate.
In Example 8, the polythiol composition D produced in Example 3 was used instead of the polythiol composition B. Further, m-xylylene diisocyanate was used instead of tolylene-2,4-diisocyanate, and resinification was carried out in the same manner as in Example 4.
Table 1 shows the physical properties of the resin.

[Example 9]
Bis (2,3-epithiopropyl) disulfide 9.0 g and UV absorber (trade name: Tinuvin PS) 99 mg were mixed and dissolved at 20 ° C. to obtain a uniform solution. To this solution, 0.90 g of polythiol composition C synthesized by the method described in Example 2 was added and mixed and dissolved. Subsequently, 9.0 mg of dicyclohexylmethylamine and 1.8 mg of dimethylcyclohexylamine were added to this solution, mixed and dissolved, subjected to vacuum degassing for 10 minutes, and then poured into a mold composed of a glass mold and a tape. This mold was put into a polymerization oven and polymerized by gradually raising the temperature from 30 ° C. to 80 ° C. over 21 hours. After completion of the polymerization, the mold was removed from the oven and released to obtain a resin. The obtained resin was further annealed at 100 ° C. for 3 hours. Table 1 shows the physical properties of the obtained resin.

[Comparative Example 1]
Tolylene-2,4-diisocyanate 18.23 g, polythiol composition A 21.77 g synthesized by the method described in Production Example 1, dibutyltin dichloride 8 mg as a curing catalyst, internal mold release agent (trade name: ZelecUN, manufactured by STEPAN) 20 mg and UV absorber (trade name: viosorb-583, manufactured by Kyodo Yakuhin Co., Ltd.) 20 mg were mixed and stirred at 60 ° C. for 10 minutes to obtain a uniform monomer mixture solution (mercapto group in the monomer mixture) The molar ratio of isocyanato groups is SH / NCO = 1.0). This monomer mixture is degassed under reduced pressure for 10 minutes, filtered through a 3 μm PTFE filter, poured into a mold consisting of a glass mold and tape, and gradually heated from 60 ° C. to 120 ° C. over 20 hours for polymerization. It was. After completion of the polymerization, the glass mold was released to obtain a resin. The obtained resin was further annealed at 120 ° C. for 2 hours. Table 1 shows the physical properties of the resin.

[Comparative Examples 2-3]
Resinization was carried out in the same manner as described in Comparative Example 1 with the monomer composition and SH group / NCO group molar ratio described in Table 1.
Comparative Example 2 is the same as Comparative Example 1 except that the contents of tolylene-2,4-diisocyanate and polythiol composition A are as shown in Table 1.
In Comparative Example 3, 4,4′-diphenylmethane diisocyanate was used without using tolylene-2,4-diisocyanate. The contents of 4,4′-diphenylmethane diisocyanate and polythiol composition A were as shown in Table 1. Other points are the same as those of Comparative Example 1.
Table 1 shows the physical properties of the resin.

[Comparative Example 4]
23.77 g of m-xylylene diisocyanate, 10 mg of dibutyltin dichloride, 60 mg of internal mold release agent (trade name: ZelecUN, manufactured by STEPA), UV absorber (trade name: viosorb-583, manufactured by Kyodo Yakuhin Co., Ltd.) 25 mg was mixed and dissolved at 20 ° C. to obtain a uniform solution. To this homogeneous solution, 26.23 g of polythiol composition A synthesized by the method described in Production Example 1 was added and mixed and dissolved at 20 ° C. to obtain a monomer mixed solution (the molar ratio of mercapto group and isocyanato group in the monomer mixture is , SH / NCO = 1.0). This monomer mixture is degassed under reduced pressure for 1 hour, filtered through a 1 μm PTFE filter, poured into a mold consisting of a glass mold and tape, and gradually heated from 40 ° C. to 100 ° C. over 21 hours for polymerization. It was. After completion of the polymerization, the glass mold was released to obtain a resin. The obtained resin was further annealed at 100 ° C. for 4 hours. The obtained resin physical properties are shown in Table 1.

[Comparative Example 5]
Bis (2,3-epithiopropyl) disulfide 63.6 g and ultraviolet absorber (trade name: Tinuvin PS) 0.7 g were mixed and dissolved at 20 ° C. to obtain a uniform solution. 6.4 g of FSH (4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane) was added to this solution, mixed and dissolved, and then filtered through a 3 μm PTFE filter. Subsequently, 64 mg of dicyclohexylmethylamine and 13 mg of dimethylcyclohexylamine were added to this solution, mixed and dissolved, and then poured into a mold composed of a glass mold and a tape. This mold was put into a polymerization oven and polymerized by gradually raising the temperature from 30 ° C. to 80 ° C. over 21 hours. After completion of the polymerization, the mold was removed from the oven and released to obtain a resin. The obtained resin was further annealed at 120 ° C. for 3 hours. Table 1 shows the physical properties of the obtained resin.

  Table 2 shows the data of the drilling tensile test.

In Examples 4 to 9, a resin having a high refractive index could be obtained. Furthermore, in Examples 4, 5, 6, and 7, resins having good strength could be obtained.
Comparative Examples 1 and 2 were systems in which the thiol compound was changed with respect to Examples 4 and 5, respectively, but the refractive index was lowered. Comparative Example 3 is a system in which the thiol compound is changed with respect to Example 6, but the refractive index similarly decreased. Comparative Example 4 is a system in which the thiol compound is changed with respect to Example 8, but the refractive index similarly decreased. Comparative Example 5 was a system in which the thiol compound was changed with respect to Example 9, but the refractive index was similarly lowered.

Claims (14)

A compound represented by formula (1);
Methanedithiol,
A composition obtained by reacting with an oxidizing agent.

A compound represented by formula (1);
R ₁ —S—CH ₂ —SH (2)
A methanedithiol derivative represented by
The composition obtained by reacting an oxidizing agent, composition obtained by alcoholysis or hydrolysis.
(In the above formula (2), R ₁ represents an alkyl group having 1 to 6 carbon atoms, or an acyl group having 2 to 6 carbon atoms.)

A compound represented by formula (1);
A composition comprising formula (3) and at least one of the compounds represented by formula (4);
Methanedithiol,
A composition obtained by reacting with an oxidizing agent.

A compound represented by formula (1);
A composition comprising formula (3) and at least one of the compounds represented by formula (4);
R ₁ —S—CH ₂ —SH (2)
A methanedithiol derivative represented by
A composition obtained by reacting with an oxidizing agent and then decomposing or hydrolyzing the alcohol.
(In the above formula (2), R ₁ represents an alkyl group having 1 to 6 carbon atoms, or an acyl group having 2 to 6 carbon atoms.)

The composition according to claim 1 or 2, or the composition according to claim 3 or 4,
A polymerizable composition comprising an isocyanate compound. The polymerizable composition according to claim 5,
A mercapto group;
A polymerizable composition having a molar ratio of an isocyanate group (SH group / NCO group) of 1.0 to 1.5 in the isocyanate compound. The polymerizable composition according to claim 5 or 6,
A polymerizable composition, wherein the isocyanate compound is an isocyanate compound having an aromatic ring. The polymerizable composition according to claim 7,
Isocyanate compound having an aromatic ring,
A polymerizable composition which is at least one selected from the group consisting of tolylene diisocyanate, phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and triphenylmethane triisocyanate, naphthalene diisocyanate. The composition according to claim 1 or 2 , or the composition according to claim 3 or 4,
A polymerizable composition comprising an epithio compound.   A method for producing a resin, comprising a step of cast polymerization of the polymerizable composition according to claim 5 to obtain a resin.   A resin obtained by polymerizing the polymerizable composition according to claim 5.   An optical component made of the resin according to claim 11. A compound represented by formula (1);
Methanedithiol,
Processes for making compositions to obtain a composition by reacting an oxidizing agent.

A compound represented by formula (1);
R ₁ —S—CH ₂ —SH (2)
A methanedithiol derivative represented by
Method for producing a composition obtained by reacting the oxidizing agent composition to obtain the alcoholysis or hydrolysis to the composition.
(In the above formula (2), R ₁ represents an alkyl group having 1 to 6 carbon atoms, or an acyl group having 2 to 6 carbon atoms.)