JP6306403B2 - Transparent member forming composition and transparent member comprising cured product thereof - Google Patents

Description

  The present invention relates to a transparent member-forming composition and a transparent member comprising a cured product thereof.

  Plastics are lighter and less likely to break than glass, and are easy to process such as dyeing. Therefore, in recent years, it has become mainstream to use plastics such as polyethylene glycol bisallyl carbonate, polymethyl methacrylate, alicyclic polyolefin, and polycarbonate as the material of the transparent member. For example, Patent Document 1 discloses a monomer composition for plastic optical materials containing polyethylene glycol bisallyl carbonate.

JP 2005-15670 A

  A transparent member such as a lens is required to have a high refractive index, and is also required to have a high glass transition temperature so as not to be deformed in the operating temperature range.

  This invention is made | formed in view of said subject, and provides the transparent member which consists of a composition for transparent member formation which gives the hardened | cured material which has a high refractive index and a high glass transition temperature, and its hardened | cured material. Objective.

  The inventors of the present invention have made extensive studies to solve the above problems. As a result, it has been found that the above-mentioned problems can be solved by using a novel vinyl group-containing fluorene compound and a specific thiol group-containing compound together, and the present invention has been completed. Specifically, the present invention provides the following.

  A first aspect of the present invention is a composition for forming a transparent member comprising a vinyl group-containing compound represented by the following general formula (1) and a thiol group-containing compound having at least two thiol groups in one molecule. It is a thing.

（式中、Ｗ^１及びＷ^２は独立に下記一般式（２）で表される基、下記一般式（４）で表される基、水酸基、又は（メタ）アクリロイルオキシ基を示し、ただし、Ｗ^１及びＷ^２の少なくとも一方は上記一般式（２）で表される基であり、環Ｙ^１及び環Ｙ^２は同一の又は異なる芳香族炭化水素環を示し、Ｒは単結合、置換基を有してもよいメチレン基、置換基を有してもよく、２個の炭素原子間にヘテロ原子を含んでもよいエチレン基、−Ｏ−で示される基、−ＮＨ−で示される基、又は−Ｓ−で示される基を示し、Ｒ^３ａ及びＲ^３ｂは独立にシアノ基、ハロゲン原子、又は１価炭化水素基を示し、ｎ１及びｎ２は独立に０〜４の整数を示す。）

Wherein W ¹ and W ² independently represent a group represented by the following general formula (2), a group represented by the following general formula (4), a hydroxyl group, or a (meth) acryloyloxy group, At least one of W ¹ and W ² is a group represented by the above general formula (2), ring Y ¹ and ring Y ² represent the same or different aromatic hydrocarbon rings, R is a single bond, a substituent A methylene group which may have a substituent, an ethylene group which may have a substituent and may contain a hetero atom between two carbon atoms, a group represented by -O-, a group represented by -NH-, Or a group represented by -S-, R ^3a and R ^3b independently represent a cyano group, a halogen atom, or a monovalent hydrocarbon group, and n1 and n2 independently represent an integer of 0 to 4.)

（式中、環Ｚは芳香族炭化水素環を示し、Ｘは単結合又は−Ｓ−で示される基を示し、Ｒ^１は単結合又は炭素数１〜４のアルキレン基を示し、Ｒ^２は１価炭化水素基、水酸基、−ＯＲ^４ａで示される基、−ＳＲ^４ｂで示される基、アシル基、アルコキシカルボニル基、ハロゲン原子、ニトロ基、シアノ基、メルカプト基、カルボキシル基、アミノ基、カルバモイル基、−ＮＨＲ^４ｃで示される基、−Ｎ（Ｒ^４ｄ）_２で示される基、（メタ）アクリロイルオキシ基、スルホ基、又は１価炭化水素基、−ＯＲ^４ａで示される基、−ＳＲ^４ｂで示される基、アシル基、アルコキシカルボニル基、−ＮＨＲ^４ｃで示される基、若しくは−Ｎ（Ｒ^４ｄ）_２で示される基に含まれる炭素原子に結合した水素原子の少なくとも一部が１価炭化水素基、水酸基、−ＯＲ^４ａで示される基、−ＳＲ^４ｂで示される基、アシル基、アルコキシカルボニル基、ハロゲン原子、ニトロ基、シアノ基、メルカプト基、カルボキシル基、アミノ基、カルバモイル基、−ＮＨＲ^４ｃで示される基、−Ｎ（Ｒ^４ｄ）_２で示される基、（メタ）アクリロイルオキシ基、メシルオキシ基、若しくはスルホ基で置換された基を示し、Ｒ^４ａ〜Ｒ^４ｄは独立に１価炭化水素基を示し、ｍは０以上の整数を示す。）

(In the formula, ring Z represents an aromatic hydrocarbon ring, X represents a single bond or a group represented by -S-, R ¹ represents a single bond or an alkylene group having 1 to 4 carbon atoms, and R ² represents Monovalent hydrocarbon group, hydroxyl group, group represented by -OR ^4a , group represented by -SR ^4b , acyl group, alkoxycarbonyl group, halogen atom, nitro group, cyano group, mercapto group, carboxyl group, amino group, carbamoyl Group, a group represented by -NHR ^4c , a group represented by -N (R ^4d ) ₂ , a (meth) acryloyloxy group, a sulfo group, or a monovalent hydrocarbon group, a group represented by -OR ^4a , -SR ^4b At least a part of the hydrogen atoms bonded to the carbon atom contained in the group represented by the above formula, an acyl group, an alkoxycarbonyl group, a group represented by -NHR ^4c , or a group represented by -N (R ^4d ) ₂ are monovalent carbonized. hydrogen , Hydroxyl, a group represented by ^{-OR 4a,} a group represented by ^{-SR 4b,} an acyl group, an alkoxycarbonyl group, a halogen atom, a nitro group, a cyano group, a mercapto group, a carboxyl group, an amino group, a carbamoyl group, -NHR ^4c , A group represented by —N (R ^4d ) ₂ , a (meth) acryloyloxy group, a mesyloxy group, or a group substituted with a sulfo group, R ^{4a to} R ^4d are each independently a monovalent hydrocarbon And m represents an integer of 0 or more.)

（式中、環Ｚ、Ｘ、Ｒ^１、Ｒ^２、及びｍは上記の通りである。）
本発明の第二の態様は、上記透明部材形成用組成物の硬化物からなる透明部材である。

(In the formula, rings Z, X, R ¹ , R ² , and m are as described above.)
The 2nd aspect of this invention is a transparent member which consists of hardened | cured material of the said composition for transparent member formation.

  ADVANTAGE OF THE INVENTION According to this invention, the transparent member which consists of a composition for transparent member formation which gives the hardened | cured material which has a high refractive index and a high glass transition temperature, and the hardened | cured material can be provided.

<Transparent member forming composition>
The composition for forming a transparent member according to the present invention contains a vinyl group-containing compound represented by the general formula (1) and a thiol group-containing compound having at least two thiol groups in one molecule. Hereinafter, each component contained in the composition for forming a transparent member according to the present invention will be described in detail.

[Vinyl group-containing compound represented by the general formula (1)]
The vinyl group-containing compound contained in the composition according to the present invention is represented by the following general formula (1). The said vinyl group containing compound can be used individually or in combination of 2 or more types.

In the general formula (1), W ¹ and W ² are independently a group represented by the following general formula (2), a group represented by the following general formula (4), a hydroxyl group, or a (meth) acryloyloxy group. Wherein at least one of W ¹ and W ² is a group represented by the general formula (2). It is more preferable that both W ¹ and W ² are groups represented by the following general formula (2). In the present specification, the term “(meth) acryloyl” means both acryloyl and methacryloyl.

In the general formulas (2) and (4), examples of the ring Z include a benzene ring and a condensed polycyclic aromatic hydrocarbon ring [for example, a condensed bicyclic hydrocarbon ring (for example, C ₈ such as a naphthalene ring). _-20 condensed bicyclic hydrocarbon rings, preferably C _10-16 condensed bicyclic hydrocarbon rings), condensed tricyclic aromatic hydrocarbon rings (eg, anthracene ring, phenanthrene ring, etc.) 2-4 Cyclic aromatic hydrocarbon ring] and the like. Ring Z is preferably a benzene ring or a naphthalene ring, and more preferably a naphthalene ring. In addition, when both W ¹ and W ² are groups represented by the general formula (2), or ^one of W ¹ and W ² is a group represented by the general formula (2), and the other Is a group represented by the above general formula (4), the ring Z contained in W ¹ and the ring Z contained in W ² may be the same or different. For example, one ring is a benzene ring The other ring may be a naphthalene ring or the like, but it is particularly preferable that either ring is a naphthalene ring. The substitution position of the ring Z which both W ¹ and W ² are bonded via X to the carbon atoms directly connected is not particularly limited. For example, when the ring Z is a naphthalene ring, the group corresponding to the ring Z bonded to the carbon atom may be a 1-naphthyl group, a 2-naphthyl group, or the like.

  In the general formulas (2) and (4), X independently represents a single bond or a group represented by -S-, and is typically a single bond.

In the above general formulas (2) and (4), R ¹ is, for example, a single bond; a C 1-4 such as a methylene group, ethylene group, trimethylene group, propylene group, butane-1,2-diyl group, etc. include an alkylene group, a single _{bond; C 2-4} alkylene group (in particular, an ethylene group, _{C 2-3} alkylene group such as propylene) is more preferably a single bond. In addition, when both W ¹ and W ² are groups represented by the general formula (2), or ^one of W ¹ and W ² is a group represented by the general formula (2), and the other there is a group represented by the general formula (4), the R ¹ contained in R ¹ and W ² included in W ^1, may be the same or may be different.

In the above general formulas (2) and (4), R ² is, for example, an alkyl group (for example, a C _1-12 alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, preferably C _1-8 alkyl group, more preferably C _1-6 alkyl group, etc.), cycloalkyl group (C _5-10 cycloalkyl group such as cyclohexyl group, preferably C _5-8 cycloalkyl group, more preferably C _5-6 cycloalkyl group etc.), aryl group (for example, C _6-14 aryl group such as phenyl group, tolyl group, xylyl group, naphthyl group, etc., preferably C _6-10 aryl group, more preferably C _6-8 hydroxyl; alkoxy aryl group), a monovalent hydrocarbon group such as an aralkyl group (benzyl group, such as _{C 6-10} aryl _{-C 1-4} alkyl group such as a phenethyl group) Methoxy group, an ethoxy group, a propoxy group, _{C 1-12} alkoxy group or a butoxy group, preferably a _{C 1-8} alkoxy group, more preferably _{C 1-6} alkoxy group), cycloalkoxy groups (cyclohexyloxy group, etc. C _5-10 cycloalkoxy group etc.), aryloxy group (C _6-10 aryloxy group such as phenoxy group), aralkyloxy group (for example, C _6-10 aryl-C _1-4 alkyl such as benzyloxy group) A group represented by —OR ^4a such as an oxy group [wherein R ^4a represents a monovalent hydrocarbon group (such as the monovalent hydrocarbon group exemplified above)]. An alkylthio group (a C _1-12 alkylthio group such as a methylthio group, an ethylthio group, a propylthio group or a butylthio group, preferably a C _1-8 alkylthio group, more preferably a C _1-6 alkylthio group), a cycloalkylthio group ( C _5-10 cycloalkylthio group such as cyclohexylthio group), arylthio group (C _6-10 arylthio group such as phenylthio group), aralkylthio group (for example, C _6-10 aryl-C ₁₋ such as benzylthio group) _A group represented by —SR ^4b such as ₄ alkylthio group, wherein R ^4b represents a monovalent hydrocarbon group (such as the monovalent hydrocarbon group exemplified above). An acyl group (a C _1-6 acyl group such as an acetyl group); an alkoxycarbonyl group (a C _1-4 alkoxy-carbonyl group such as a methoxycarbonyl group); a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, Nitro group; cyano group; mercapto group; carboxyl group; amino group; carbamoyl group; alkylamino group (C _1-12 alkylamino such as methylamino group, ethylamino group, propylamino group, butylamino group) Group, preferably C _1-8 alkylamino group, more preferably C _1-6 alkylamino group, etc.), cycloalkylamino group (C _5-10 cycloalkylamino group such as cyclohexylamino group), arylamino group (C _6-10 arylamino group such as phenylamino group), aralkylamino group (for example, benzylamine) Groups represented by —NHR ^4c such as C _6-10 aryl-C _1-4 alkylamino group such as mino group] [wherein R ^4c is a monovalent hydrocarbon group (such as the monovalent hydrocarbon group exemplified above)] Indicates. Dialkylamino group (di (C _1-12 alkyl) amino group such as dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, preferably di (C _1-8 alkyl) amino group, more preferably Di (C _1-6 alkyl) amino group etc.), dicycloalkylamino group (di (C _5-10 cycloalkyl) amino group such as dicyclohexylamino group), diarylamino group (diphenylamino group etc. C _6-10 aryl) amino group), diaralkylamino group (for example, di (C _6-10 aryl-C _1-4 alkyl) amino group such as dibenzylamino group) and the like —N (R ^4d ) ₂ The group shown [in the formula, R ^4d independently represents a monovalent hydrocarbon group (such as the monovalent hydrocarbon group exemplified above). (Meth) acryloyloxy group; sulfo group; the above monovalent hydrocarbon group, group represented by -OR ^4a , group represented by -SR ^4b , acyl group, alkoxycarbonyl group, group represented by -NHR ^4c Or at least a part of the hydrogen atoms bonded to the carbon atom contained in the group represented by —N (R ^4d ) ₂ is the above monovalent hydrocarbon group, hydroxyl group, group represented by —OR ^4a , or —SR ^4b A group represented by the following formula: an acyl group, an alkoxycarbonyl group, a halogen atom, a nitro group, a cyano group, a mercapto group, a carboxyl group, an amino group, a carbamoyl group, a group represented by -NHR ^4c , represented by -N (R ^4d ) ₂ A group substituted with a group, a (meth) acryloyloxy group, a mesyloxy group, or a sulfo group [for example, an alkoxyaryl group (for example, a methoxyphenyl group, etc.) C _1-4 alkoxy _{C 6-10} aryl group), an alkoxycarbonyl aryl group (e.g., methoxycarbonyl phenyl group, _{C 1-4} alkoxy such as ethoxy carbonyl phenyl - mentioned carbonyl _{C 6-10} aryl group, etc.) and the like It is done.

Among these, R ² is typically a monovalent hydrocarbon group, a group represented by —OR ^4a , a group represented by —SR ^4b , an acyl group, an alkoxycarbonyl group, a halogen atom, a nitro group, a cyano group. , A group represented by -NHR ^4c , a group represented by -N (R ^4d ) ₂ , or the like.

Preferable R ² is a monovalent hydrocarbon group [eg, alkyl group (eg, C _1-6 alkyl group), cycloalkyl group (eg, C _5-8 cycloalkyl group), aryl group (eg, C _{6-6 10} aryl group), aralkyl group (for example, C _6-8 aryl-C _1-2 alkyl group) and the like], alkoxy group (C _1-4 alkoxy group and the like) and the like. In particular, R ^2a and R ^2b are monovalent hydrocarbons such as an alkyl group [C _1-4 alkyl group (particularly methyl group) and the like] and an aryl group [eg C _6-10 aryl group (particularly phenyl group) and the like]. A group (particularly an alkyl group) is preferred.

When m is an integer of 2 or more, R ² may be different from each other or the same. In addition, when both W ¹ and W ² are groups represented by the general formula (2), or ^one of W ¹ and W ² is a group represented by the general formula (2), and the other there is a group represented by the general formula (4), the R ² contained in R ² and W ² included in W ^1, may be the same or may be different.

In the general formulas (2) and (4), the number m of R ² can be selected according to the type of the ring Z, and is, for example, 0 to 4, preferably 0 to 3, more preferably 0 to 2. Also good. In addition, when both W ¹ and W ² are groups represented by the general formula (2), or ^one of W ¹ and W ² is a group represented by the general formula (2), and the other Is a group represented by the above general formula (4), m in W ¹ and m in W ² may be the same or different.

In the general formula (1), examples of the ring Y ¹ and the ring Y ² include a benzene ring, a condensed polycyclic aromatic hydrocarbon ring [for example, a condensed bicyclic hydrocarbon ring (for example, C such as a naphthalene ring). _8-20 condensed bicyclic hydrocarbon rings, preferably C _10-16 condensed bicyclic hydrocarbon rings), condensed tricyclic aromatic hydrocarbon rings (for example, anthracene ring, phenanthrene ring, etc.) Tetracyclic aromatic hydrocarbon ring] and the like. Ring Y ¹ and ring Y ² are preferably a benzene ring or a naphthalene ring. Ring Y ¹ and ring Y ² may be the same or different. For example, one ring may be a benzene ring and the other ring may be a naphthalene ring.

In the general formula (1), R represents a single bond, a methylene group which may have a substituent, an ethylene group which may have a substituent and may contain a hetero atom between two carbon atoms,- A group represented by O-, a group represented by -NH-, or a group represented by -S- is typically represented by a single bond. Here, as the substituent, for example, a cyano group, a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), a monovalent hydrocarbon group [for example, an alkyl group (methyl group, ethyl group, propyl group, isopropyl group, Butyl group, C _1-6 alkyl group such as t-butyl group), aryl group (C _6-10 aryl group such as phenyl group) and the like], and the hetero atom includes, for example, oxygen atom, nitrogen atom , Sulfur atom, silicon atom and the like.

In the general formula (1), R ^3a and R ^3b are usually non-reactive substituents such as cyano groups, halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, etc.), monovalent hydrocarbon groups [for example, , An alkyl group, an aryl group (C _6-10 aryl group such as a phenyl group), etc.], and the like. A cyano group or an alkyl group is preferable, and an alkyl group is particularly preferable. Examples of the alkyl group include C _1-6 alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a t-butyl group (for example, a C _1-4 alkyl group, particularly a methyl group). . In addition, when n1 is an integer greater than or equal to 2, ^R3a may mutually differ and may be the same. Moreover, when n2 is an integer greater than or equal to 2, ^R3b may mutually differ and may be the same. Further, R ^3a and R ^3b may be the same or different. Further, the bonding positions (substitution positions) of R ^3a and R ^{3b with} respect to ring Y ¹ and ring Y ² are not particularly limited. Preferred substitution numbers n1 and n2 are 0 or 1, in particular 0. Note that n1 and n2 may be the same as or different from each other.

Since the compound represented by the general formula (1) has a vinyloxy group and / or a (meth) acryloyloxy group while maintaining excellent optical properties and thermal properties, it has high reactivity. In particular, when ring Y ¹ and ring Y ² are benzene rings and R is a single bond, the compound represented by the above general formula (1) has a fluorene skeleton, and has optical and thermal characteristics. Even better. Since such a compound represented by the general formula (1) can be polymerized, it functions as a polymerizable monomer. In particular, when both W ¹ and W ² are groups represented by the above general formula (2), the compound represented by the above general formula (1) can be cationically polymerized. Function as. On the other hand, when both W ¹ and W ² are (meth) acryloyloxy groups, the compound represented by the general formula (1) functions as a radical polymerizable monomer because it can undergo radical polymerization. The compound represented by the general formula (1) is a vinyloxy group and / or when W ¹ and W ² are independently a group represented by the general formula (2) or a (meth) acryloyloxy group. Since two vinyl groups contained in the form of a (meth) acryloyloxy group can react with different molecules, they can be suitably used as a crosslinking agent. Furthermore, the compound represented by the general formula (1) gives a cured product having high hardness, and is preferable as a base material component in the composition. In addition, when the compound represented by the general formula (1) is contained in the negative photosensitive resin composition, good micropatterning characteristics can be obtained. The compound represented by the general formula (1) is used in various applications, for example, an alignment film and a planarization film (for example, an alignment film and a planarization film used for a liquid crystal display or an organic EL display); Resist underlayer films such as interlayer insulating films and carbon hard masks; spacers and partition walls of liquid crystal display displays and organic EL displays; color filter pixels and black matrices of liquid crystal display displays; display devices such as liquid crystal display displays and organic EL displays Optical members such as lenses (for example, microlenses), optical fibers, optical waveguides, prism sheets, holograms, high refractive films, retroreflective films; low moisture permeable films (for example, low moisture permeable films used as water vapor barrier layers) Optical materials; can be used for semiconductor materials.

  Among the compounds represented by the general formula (1), particularly preferred specific examples include compounds represented by the following formulas.

  It is preferable that content of the vinyl group containing compound represented by the said General formula (1) is 25-99 mass% with respect to the total mass of the composition for transparent member formation concerning this invention, 50-96. More preferably, it is mass%. When the content of the vinyl group-containing compound is within the above range, the film-forming ability of the resulting composition is easily improved, a cured product having a high refractive index and a high glass transition temperature and excellent curability. Easy to get.

[Method for Producing Vinyl Group-Containing Compound Represented by General Formula (1)]
The vinyl group-containing compound represented by the general formula (1) can be produced, for example, by the following production methods 1 to 3.

・ Production method 1
The vinyl group-containing compound represented by the general formula (1) is represented by the following general formula (13) in the presence of a transition element compound catalyst and an inorganic base, for example, according to the production method described in JP-A-2008-266169. It can be synthesized by reacting the vinyl ester compound represented with the hydroxyl group-containing compound represented by the following general formula (3). The inorganic base is preferably a solid inorganic base containing 10% by weight or more of particles having a particle diameter of less than 150 μm. Specifically, the vinyl group-containing compound represented by the general formula (1) can be synthesized as in Synthesis Examples 1 to 3 described later.

_{^{R 6 -CO-O-CH =}} CH 2 (13)
(In the formula, R ⁶ represents a hydrogen atom or an organic group.)

（式中、Ｗ^３及びＷ^４は独立に下記一般式（４）で表される基又は水酸基を示し、ただし、Ｗ^３及びＷ^４は同時に水酸基ではなく、環Ｙ^１、環Ｙ^２、Ｒ、Ｒ^３ａ、Ｒ^３ｂ、ｎ１、及びｎ２は上記の通りである。）

(W ³ and W ⁴ in the formula independently represent a group or a hydroxyl group represented by the following general formula (4), provided that W ³ and W ⁴ are not hydroxyl groups at the same time, but are represented by ring Y ¹ , ring Y ² , R , R ^3a , R ^3b , n1, and n2 are as described above.)

（式中、環Ｚ、Ｘ、Ｒ^１、Ｒ^２、及びｍは上記の通りである。）

(In the formula, rings Z, X, R ¹ , R ² , and m are as described above.)

  In addition, the compound represented by the general formula (3) includes, for example, a compound represented by the following general formula (14) and / or a compound represented by the following general formula (15) in the presence of an acid catalyst, It can be synthesized by reacting with a compound represented by the following general formula (16). The desired compound represented by the above general formula (3) is appropriately adjusted by adjusting the combination of the compound represented by the following general formula (14) and the compound represented by the following general formula (15), the amount of addition, etc. A hydroxyl group-containing compound can be obtained. Further, after the reaction, the target hydroxyl group-containing compound may be separated by a known separation method such as silica gel column chromatography.

（上記一般式（１４）、（１５）、及び（１６）中、環Ｙ^１、環Ｙ^２、環Ｚ、Ｒ、Ｒ^１、Ｒ^２、Ｒ^３ａ、Ｒ^３ｂ、ｍ、ｎ１、及びｎ２は上記の通りである。）

(In the above general formulas (14), (15), and (16), ring Y ¹ , ring Y ² , ring Z, R, R ¹ , R ² , R ^3a , R ^3b , m, n1, and n2 are As above.)

  Examples of the acid catalyst and reaction conditions used for the synthesis of the compound represented by the general formula (3) are described in claims in JP2011-201791A and JP2002-255929A, for example. What is described that it can be used for the manufacturing method of the made fluorene type compound is mentioned.

・ Production method 2
The compound represented by the general formula (1) is, for example, from the hydroxyl group-containing compound represented by the general formula (3) via the leaving group-containing compound represented by the following general formula (5), It is also possible to synthesize by a production method including obtaining a vinyl group-containing compound represented by the general formula (1).

（式中、Ｗ^５及びＷ^６は独立に下記一般式（６）で表される基又は水酸基を示し、ただし、Ｗ^５及びＷ^６は同時に水酸基ではなく、環Ｙ^１、環Ｙ^２、Ｒ、Ｒ^３ａ、Ｒ^３ｂ、ｎ１、及びｎ２は上記の通りである。）

(W ⁵ and W ⁶ in the formula independently represent a group or a hydroxyl group represented by the following general formula (6), provided that W ⁵ and W ⁶ are not hydroxyl groups at the same time, but are represented by ring Y ¹ , ring Y ² , R , R ^3a , R ^3b , n1, and n2 are as described above.)

（式中、Ｅは塩素原子、臭素原子、ヨウ素原子、メタンスルホニルオキシ基、トリフルオロメタンスルホニルオキシ基、パラトルエンスルホニルオキシ基、又はベンゼンスルホニルオキシ基で置換された炭素数１〜４のアルキルオキシ基を示し、環Ｚ、Ｘ、Ｒ^１、Ｒ^２、及びｍは上記の通りである。）

(In the formula, E represents a C1-C4 alkyloxy group substituted with a chlorine atom, a bromine atom, an iodine atom, a methanesulfonyloxy group, a trifluoromethanesulfonyloxy group, a paratoluenesulfonyloxy group, or a benzenesulfonyloxy group. And rings Z, X, R ¹ , R ² , and m are as described above.)

  The leaving group-containing compound represented by the general formula (5) can be synthesized, for example, by reacting the hydroxyl group-containing compound represented by the general formula (3) with the leaving group-containing compound. . Examples of the leaving group-containing compound include thionyl chloride, a compound represented by the following formula, and the like. Moreover, as reaction temperature, -20-150 degreeC, Preferably it is -10-140 degreeC, More preferably, 30-130 degreeC is mentioned.

  The vinyl group-containing compound represented by the general formula (1) can be synthesized, for example, by reacting the leaving group-containing compound represented by the general formula (5) with a vinylating agent. Examples of the vinylating agent include sodium hydroxide, triethylamine, diisopropylethylamine, 1,4-diazabicyclo [2.2.2] octane, diazabicycloundecene, sodium methoxide, sodium ethoxide, sodium ethoxide, potassium. -T-butoxide etc. are mentioned, Preferably diazabicycloundecene, sodium ethoxide, potassium-t-butoxide etc. are mentioned, More preferably, potassium-t-butoxide is mentioned. Moreover, as reaction temperature, -20-150 degreeC is preferable, Preferably it is -10-100 degreeC, More preferably, 0-60 degreeC is mentioned.

・ Production method 3
The compound represented by the general formula (1) is, for example, from a hydroxyalkyloxy group-containing compound represented by the following general formula (7) via a leaving group-containing compound represented by the above general formula (5). And it is also possible to synthesize | combine with the manufacturing method including obtaining the vinyl group containing compound represented by the said General formula (1).

（式中、Ｗ^７及びＷ^８は独立に下記一般式（８）で表される基又は水酸基を示し、ただし、Ｗ^７及びＷ^８は同時に水酸基ではなく、環Ｙ^１、環Ｙ^２、Ｒ、Ｒ^３ａ、Ｒ^３ｂ、ｎ１、及びｎ２は上記の通りである。）

(Wherein W ⁷ and W ⁸ independently represent a group or a hydroxyl group represented by the following general formula (8), provided that W ⁷ and W ⁸ are not hydroxyl groups at the same time, but are represented by ring Y ¹ , ring Y ² , R , R ^3a , R ^3b , n1, and n2 are as described above.)

（式中、ｌは１〜４の整数を示し、環Ｚ、Ｘ、Ｒ^１、Ｒ^２、及びｍは上記の通りである。）

(In the formula, l represents an integer of 1 to 4, and the rings Z, X, R ¹ , R ² , and m are as described above.)

  The hydroxyalkyloxy group-containing compound represented by the general formula (7) is represented by, for example, a compound represented by the following general formula (17) and / or the following general formula (18) in the presence of an acid catalyst. It can synthesize | combine by making a compound and the compound represented by the said General formula (16) react. The desired compound represented by the above general formula (7) is appropriately adjusted by adjusting the combination method and the amount of the compound represented by the following general formula (17) and the compound represented by the following general formula (18). A hydroxyalkyloxy group-containing compound can be obtained. Further, after the reaction, the target hydroxyalkyloxy group-containing compound may be separated by a known separation method such as silica gel column chromatography. Examples of the acid catalyst and reaction conditions used for the synthesis of the compound represented by the general formula (7) include those exemplified in the description of the method for synthesizing the compound represented by the general formula (3). It is done.

（上記一般式（１７）及び（１８）中、環Ｚ、Ｒ^１、Ｒ^２、及びｍは上記の通りである。）

(In the general formulas (17) and (18), the rings Z, R ¹ , R ² , and m are as described above.)

  The leaving group-containing compound represented by the general formula (5) is synthesized, for example, by reacting the hydroxyalkyloxy group-containing compound represented by the general formula (7) with the leaving group-containing compound. be able to. As a leaving group containing compound and reaction temperature, what was illustrated about the said manufacturing method 2 is mentioned, for example.

  The vinyl group-containing compound represented by the general formula (1) can be synthesized, for example, by reacting the leaving group-containing compound represented by the general formula (5) with a vinylating agent. As a vinylating agent and reaction temperature, what was illustrated about the said manufacturing method 2 is mentioned, for example.

[A thiol group-containing compound having at least two thiol groups in one molecule]
The composition for forming a transparent member according to the present invention contains a thiol group-containing compound having at least two thiol groups in one molecule. By reacting the thiol group-containing compound with the vinyl group-containing compound represented by the general formula (1), a cured product having a high refractive index and a high glass transition temperature and excellent in optical properties and heat resistance is obtained. It is formed. The said thiol group containing compound can be used individually or in combination of 2 or more types.

  The thiol group-containing compound having at least two thiol groups in one molecule is not particularly limited, but is preferably a liquid at room temperature, for example, a compound having a melting point of 30 ° C. or less at 1 atm. Preferably, the reactivity and compatibility with other components such as the vinyl group-containing compound represented by the general formula (1) are good, the refractive index of the cured product of the composition for forming a transparent member according to the present invention, and A compound that can maintain a high glass transition temperature is used. When a thiol group-containing compound that is liquid at room temperature is used as the thiol group-containing compound having at least two thiol groups in one molecule, the vinyl group-containing compound represented by the general formula (1) is such a thiol. Since it melt | dissolves in a group containing compound, the composition for transparent member formation which does not contain a solvent substantially can be prepared. In particular, a lens or the like can be suitably formed from the composition for forming a transparent member that does not substantially contain a solvent. In the present specification, “substantially no solvent” means that the content of the solvent is 1% by mass or less, preferably 0.8%, based on the total mass of the composition for forming a transparent member according to the present invention. 5 mass% or less, More preferably, it means 0.1 mass% or less.

  The thiol group-containing compound may have a sulfide bond, polysulfide bond, and other functional groups in addition to the thiol group, and may be a chain compound or a cyclic compound. Specific examples of the thiol group-containing compound include the following compounds, but are not limited thereto.

  Methanedithiol, 1,2-ethanedithiol, 1,1-propanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 2,2-propanedithiol, 1,6-hexanedithiol, 1,2,3 -Propanetrithiol, 1,1-cyclohexanedithiol, 1,2-cyclohexanedithiol, 2,2-dimethylpropane-1,3-dithiol, 3,4-dimethoxybutane-1,2-dithiol, 2-methylcyclohexane- 2,3-dithiol, 1,1-bis (mercaptomethyl) cyclohexane, bis (2-mercaptoethyl ester) thiomalate, 2,3-dimercapto-1-propanol (2-mercaptoacetate), 2,3-dimercapto- 1-propanol (3-mercaptopropionate), die Lenglycol bis (2-mercaptoacetate), diethylene glycol bis (3-mercaptopropionate), 1,2-dimercaptopropyl methyl ether, 2,3-dimercaptopropyl methyl ether, 2,2-bis (mercaptomethyl) -1,3-propanedithiol, bis (2-mercaptoethyl) ether, ethylene glycol bis (2-mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), trimethylolpropane bis (2-mercaptoacetate), Trimethylolpropane bis (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), tetrakis (mercapto) Chill) aliphatic polythiol compound such as methane.

  1,2-benzenedithiol, 1,3-benzenedithiol, 1,4-benzenedithiol, 1,2-bis (mercaptomethyl) benzene, 1,3-bis (mercaptomethyl) benzene, 1,4-bis (mercapto) Methyl) benzene, 1,2-bis (mercaptoethyl) benzene, 1,3-bis (mercaptoethyl) benzene, 1,4-bis (mercaptoethyl) benzene, 1,2,3-trimercaptobenzene, 1,2 , 4-trimercaptobenzene, 1,3,5-trimercaptobenzene, 1,2,3-tris (mercaptomethyl) benzene, 1,2,4-tris (mercaptomethyl) benzene, 1,3,5-tris (Mercaptomethyl) benzene, 1,2,3-tris (mercaptoethyl) benzene, 1,2,4-tris (mercapto) Chill) benzene, 1,3,5-tris (mercaptoethyl) benzene, 2,5-toluenedithiol, 3,4-toluenedithiol, 1,3-di (p-methoxyphenyl) propane-2,2-dithiol, 1,3-diphenylpropane-2,2-dithiol, phenylmethane-1,1-dithiol, 2,4-di (p-mercaptophenyl) pentane, 1,2-bis (mercaptoethylthio) benzene, 1,3 -Bis (mercaptoethylthio) benzene, 1,4-bis (mercaptoethylthio) benzene, 1,2,3-tris (mercaptomethylthio) benzene, 1,2,4-tris (mercaptomethylthio) benzene, 1,3 , 5-tris (mercaptomethylthio) benzene, 1,2,3-tris (mercaptoethylthio) benzene, 1, 4- tris (mercaptoethylthio) benzene, 1,3,5-tris aromatic polythiol compounds containing (mercaptoethylthio) aromatic polythiol compound and a sulfur atom in addition to mercapto group such as benzene.

  Bis (mercaptomethyl) sulfide, bis (mercaptoethyl) sulfide, bis (mercaptopropyl) sulfide, bis (mercaptomethylthio) methane, bis (2-mercaptoethylthio) methane, bis (3-mercaptopropylthio) methane, 1, 2-bis (2-mercaptoethylthio) ethane, 1,2-bis (3-mercaptopropyl) ethane, 1,3-bis (3-mercaptopropylthio) propane, 1,2,3-tris (2-mercapto Ethylthio) propane, 1,2,3-tris (3-mercaptopropylthio) propane, 1,2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane, 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-3,6,9-trithiaundecane, tetrakis (2-mercaptoethylthiomethyl) methane , Tetrakis (3-mercaptopropylthiomethyl) methane, bis (2,3-dimercaptopropyl) sulfide, bis (1,3-dimercaptopropyl) sulfide, 2,5-dimercapto-1,4-dithiane, 2, 5-dimercaptomethyl-1,4-dithiane, 2,5-dimercaptomethyl-2,5-dimethyl-1,4-dithiane, bis (mercaptoethyl) disulfide, bis (mercaptopropyl) disulfide, and the like Thioglycolic acid ester and mercaptopropionic acid ester.

  Hydroxymethyl sulfide bis (2-mercaptoacetate), hydroxymethyl sulfide bis (3-mercaptopropionate), hydroxyethyl sulfide bis (2-mercaptoacetate), hydroxyethyl sulfide bis (3-mercaptopropionate), hydroxypropyl Sulfide bis (2-mercaptoacetate), hydroxypropyl sulfide bis (3-mercaptopropionate), hydroxymethyl disulfide bis (2-mercaptoacetate), hydroxymethyl disulfide bis (3-mercaptopropionate), hydroxyethyl disulfide bis (2-mercaptoacetate), hydroxyethyl disulfide bis (3-mercaptopropionate), hydroxypropyl disulfide bis 2-mercaptoacetate), hydroxypropyl disulfide bis (3-mercaptopropionate), 2-mercaptoethyl ether bis (2-mercaptoacetate), 2-mercaptoethyl ether bis (3-mercaptopropionate), 1,4 Dithian-2,5-diol bis (2-mercaptoacetate), 1,4-dithian-2,5-diol bis (3-mercaptopropionate), thiodiglycolic acid bis (2-mercaptoethyl ester), thiodi Propionic acid bis (2-mercaptoethyl ester), 4,4-thiodibutyric acid bis (2-mercaptoethyl ester), dithiodiglycolic acid bis (2-mercaptoethyl ester), dithiodipropionic acid bis (2-mercaptoethyl ester) ), 4,4-dithio Dibutyl acid bis (2-mercaptoethyl ester), thiodiglycolic acid bis (2,3-dimercaptopropyl ester), thiodipropionic acid bis (2,3-dimercaptopropyl ester), dithioglycolic acid bis (2, 3-dimercaptopropyl ester), bis (2,3-dimercaptopropyl ester) dithiodipropionate, 1,1,3,3-tetrakis (mercaptomethylthio) propane, 1,1,2,2-tetrakis (mercapto) Methylthio) ethane, 3-mercaptomethyl-1,5-dimercapto-2,4-dithiapentane, 1,2,5-trimercapto-4-thiapentane, 3,3-dimercaptomethyl-1,5-dimercapto-2, 4-dithiapentane, 3-mercaptomethyl-1,5-dimercapto-2,4-di Thiapentane, 3-mercaptomethylthio-1,7-dimercapto-2,6-dithiaheptane, 3,6-dimercaptomethyl-1,9-dimercapto-2,5,8-trithianonane, 3,7-dimercaptomethyl-1 , 9-dimercapto-2,5,8-trithianonane, 4,6-dimercaptomethyl-1,9-dimercapto-2,5,8-trithianonane, 3-mercaptomethyl-1,6-dimercapto-2,5- Dithiahexane, 3-mercaptomethylthio-1,5-dimercapto-2-thiapentane, 1,1,2,2-tetrakis (mercaptomethylthio) ethane, 1,1,3,3-tetrakis (mercaptomethylthio) propane, 1,4 , 8,11-tetramercapto-2,6,10-trithiaundecane, 1,4,9,12-tetra Lucapto-2,6,7,11-tetrathiaddecane, 2,3-dithia-1,4-butanedithiol, 2,3,5,6-tetrathia-1,7-heptanedithiol, 2,3,5 6,8,9-hexathia-1,10-decanedithiol, 4,5-bis (mercaptomethylthio) -1,3-dithiolane, 4,6-bis (mercaptomethylthio) -1,3-dithiane, 2-bis (Mercaptomethylthio) methyl-1,3-dithietane, 2- (2,2-bis (mercaptomethylthio) ethyl) -1,3-dithietane, 2-mercaptomethyl-6-mercapto-1,4-dithiacycloheptane, etc. An aliphatic polythiol compound containing a sulfur atom in addition to the mercapto group.

  Heterocyclic compounds containing sulfur atoms in addition to mercapto groups such as 3,4-thiophenedithiol and 2,5-dimercapto-1,3,4-thiadiazole, glycerin di (mercaptoacetate), 2,4-dimercaptophenol, 3,4-dimercapto-2-propanol, 1,3-dimercapto-2-propanol, 2,3-dimercapto-1-propanol, 1,2-dimercapto-1,3-butanediol, pentaerythritol tris (3-mercapto Propionate), pentaerythritol bis (3-mercaptopropionate), pentaerythritol tris (thioglycolate), dipentaerythritol pentakis (3-mercaptopropionate), hydroxymethyl-tris (mercaptoethylthiomethyl) Methane Compounds containing a hydroxy group other than the mercapto group.

  2,5-bis (mercaptomethyl) -1,4-dithiane, 2,5-bis (2-mercaptoethyl) -1,4-dithiane, 2,5-bis (3-mercaptopropyl) -1,4- Dithian, 2- (2-mercaptoethyl) -5-mercaptomethyl-1,4-dithiane, 2- (2-mercaptoethyl) -5- (3-mercaptopropyl) -1,4-dithiane, 2-mercaptomethyl -5- (3-mercaptopropyl) -1,4-dithiane, 2,4-bis (mercaptomethyl) -1,3-dithiolane, 2-mercaptomethyl-5-mercapto-1,3-dithiolane, 2,2 -Bis (mercaptomethyl) -1,3-dithiolane, 2- (3-mercaptopropyl) -4-mercaptomethyl-1,3-dithiolane, 2,2-bis (mercaptomethyl) -1, , 5-trithiane, 2,4,5-tris (mercaptomethyl) -1,3-dithiolane, 2,2-bis (mercaptomethyl) -5-mercapto-1,3-dithiolane, 2- (1,2- Dimercaptoethyl) -4-mercaptomethyl-1,3-dithiolane, 2- (1,2-dimercaptoethyl) -4-mercapto-1,3,5-trithiane, 2- (3-mercaptopropyl) -4 , 5-bis (mercaptomethyl) -1,3-dithiolane, 2,2,4,5-tetrakis (mercaptomethyl) -1,3-dithiolane, 2- (1,2-dimercaptoethyl) -4,5 -Cyclic compounds such as bis (mercaptomethyl) -1,3-dithiolane.

  A thiol group-containing compound having at least two thiol groups in one molecule can be synthesized by a known method. Specifically, the method described in JP-A-7-252207 can be mentioned.

  Preferable examples of the thiol group-containing compound having at least two thiol groups in one molecule include thiol group-containing compounds represented by the following general formula (t1).

（式中、Ｒ^ｔ１は炭素鎖中に硫黄原子又は酸素原子を含有してもよい（ｋ１＋１）価の炭化水素基を示し、Ｒ^ｔ２は炭素鎖中に硫黄原子又は酸素原子を含有してもよい（ｋ２＋１）価の炭化水素基を示し、ｋ１及びｋ２は独立に１以上の整数を示す。Ｒ^ｔ１及びＲ^ｔ２中の炭素原子が互いに結合して環が形成されていてもよい。）

(In the formula, R ^t1 represents a (k1 + 1) -valent hydrocarbon group that may contain a sulfur atom or an oxygen atom in the carbon chain, and R ^t2 may contain a sulfur atom or an oxygen atom in the carbon chain. A good (k2 + 1) -valent hydrocarbon group, k1 and k2 independently represent an integer of 1 or more, and carbon atoms in R ^t1 and R ^t2 may be bonded to each other to form a ring.

R ^t1 is not particularly limited, and examples thereof include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a combination of two or more of these, and the valence is (k1 + 1) valence. And the carbon chain may contain a sulfur atom or an oxygen atom. R ^t2 is not particularly limited, and examples thereof include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a combination of two or more of these, and the valence is (k2 + 1). ) And a carbon chain may contain a sulfur atom or an oxygen atom. As carbon number of an aliphatic hydrocarbon group, 1-12 are mentioned, for example, 1-8 are preferable and 1-6 are more preferable. As carbon number of an alicyclic hydrocarbon group, 3-12 are mentioned, for example, 3-8 are preferable and 3-6 are more preferable. As carbon number of an aromatic hydrocarbon group, 6-18 are mentioned, for example, 6-14 are preferable and 6-10 are more preferable.

k1 and k2 independently represent an integer of 1 or more, preferably an integer of 1 to 6, and more preferably 1 or 2.
Specific examples of the thiol group-containing compound represented by the general formula (t1) include compounds represented by the following formula.

  Other preferable examples of the thiol group-containing compound having at least two thiol groups in one molecule include thiol group-containing compounds represented by the following general formula (t2).

（式中、Ｒ^ｔ３は炭素鎖中にヘテロ原子を含有してもよいｋ３価の炭化水素基を示し、Ｒ^ｔ４はアルキレン基を示し、ｋ３は２以上の整数を示す。）

(In the formula, R ^t3 represents a k3-valent hydrocarbon group that may contain a hetero atom in the carbon chain, R ^t4 represents an alkylene group, and k3 represents an integer of 2 or more.)

R ^t3 is not particularly limited, and examples thereof include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and combinations of two or more thereof, and the valence is k3. And those that may contain heteroatoms in the carbon chain. The carbon number of the aliphatic hydrocarbon group, alicyclic hydrocarbon group, and aromatic hydrocarbon group is the same as that described for R ^t1 and R ^t2 . Examples of the hetero atom include an oxygen atom, a sulfur atom, and a nitrogen atom. The oxygen atom may be contained in the carbon chain as a carbonyl group, and the sulfur atom is contained in the carbon chain as a thiocarbonyl group. It may be.

Examples of R ^t4 include an alkylene group having 1 to 6 carbon atoms, preferably 2 to 4 carbon atoms. Specific examples include a methylene group, an ethylene group, a propylene group, a methylethylene group, a dimethylmethylene group, and a butylene group. Etc.
k3 shows an integer greater than or equal to 2, Preferably it is an integer of 2-6, More preferably, it is an integer of 2-4.
Specific examples of the thiol group-containing compound represented by the general formula (t2) include compounds represented by the following formula.

  Still another preferred example of the thiol group-containing compound having at least two thiol groups in one molecule includes a thiol group-containing compound represented by the following general formula (t3).

（式中、Ｒ^ｔ５は、２価の炭化水素基を表し、エピスルフィド系化合物の開環反応に関与しない置換基を有していてもよく、その炭素鎖中にヘテロ原子又は環構造を含有していてもよく、更にＲ^ｔ５は、１つの分子鎖内において、同一でも異なっていてもよい。ｋ４は、式（ｔ３）で表される化合物の数平均分子量が２００〜２５００となるように選ばれる数である。）

(In the formula, R ^t5 represents a divalent hydrocarbon group, may have a substituent that does not participate in the ring-opening reaction of the episulfide compound, and contains a heteroatom or a ring structure in the carbon chain. Furthermore, R ^t5 may be the same or different in one molecular chain, and k4 is selected so that the number average molecular weight of the compound represented by the formula (t3) is 200 to 2500. Number.)

  The thiol group-containing compound represented by the general formula (t3) is polythiocarbonate dithiol, and has two thiol groups in one molecule. This thiol group-containing compound is usually used as a mixture of compounds having different numbers of repeating units, and the number average molecular weight is 200 to 2500.

  The thiol group-containing compound represented by the general formula (t3), that is, polythiocarbonate dithiol is preferably produced by transesterification using a carbonate compound and a dithiol compound as raw materials in the presence of a transesterification catalyst. . In this case, the hydrocarbon group and the terminal thiol group in the polythiocarbonate dithiol are derived from the raw material dithiol compound used. Therefore, polythiocarbonate dithiol will be described while explaining its production method.

  Examples of the carbonate compound as a raw material include dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, di-n-butyl carbonate, diisobutyl carbonate; diaryl carbonates such as diphenyl carbonate; alkylene carbonates such as ethylene carbonate and propylene carbonate; and methylphenyl carbonate Examples thereof include alkylaryl carbonate. Among these carbonate compounds, diaryl carbonate is preferable, and diphenyl carbonate is particularly preferable.

  As a raw material dithiol compound (that is, a compound having two or more thiol groups), a dithiol compound corresponding to the diol compound used in the production of polycarbonate diol can be used. Specifically, the compound which the mercapto group couple | bonded with the bivalent hydrocarbon group is mentioned. This hydrocarbon group is an aliphatic (including alicyclic) hydrocarbon group (preferably having 2 to 14 carbon atoms) or an aromatic (including araliphatic) hydrocarbon group (preferably having 6 to 14 carbon atoms). Any of them may have a substituent (alkyl group, alkoxy group, etc.) which does not participate in the ring-opening reaction of the episulfide compound, and a hetero atom (oxygen atom, sulfur atom, nitrogen) in the carbon chain. Atoms or atoms that do not participate in the ring-opening reaction of episulfide compounds such as ring structures (alicyclic structures, aromatic ring structures, heterocyclic structures). Among the divalent hydrocarbon groups, an aliphatic group is preferable, the hetero atom is preferably a sulfur atom or an oxygen atom, and the ring structure is preferably an alicyclic structure or a saturated heterocyclic structure.

  Examples of the dithiol compound in which the hydrocarbon group is an aliphatic hydrocarbon group include 1,2-ethanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 1,5-pentanedithiol, 1,6 -Hexanedithiol, 1,7-heptanedithiol, 1,8-octanedithiol, 1,9-nonanedithiol, 1,10-decanedithiol, 1,12-dodecanedithiol, 2,2-dimethyl-1,3-propane Alkanedithiols such as dithiol, 3-methyl-1,5-pentanedithiol, 2-methyl-1,8-octanedithiol; Cycloalkanedithiols such as 1,4-cyclohexanedithiol, 1,4-bis (mercaptomethyl) cyclohexane ;

  Alkanedithiols having heteroatoms such as bis (2-mercaptoethyl) ether, bis (2-mercaptoethyl) sulfide, bis (2-mercaptoethyl) disulfide, 2,2 ′-(ethylenedithio) diethanethiol; And cycloalkanedithiol having a heteroatom such as 5-bis (mercaptomethyl) -1,4-dioxane and 2,5-bis (mercaptomethyl) -1,4-dithiane.

  Examples of the dithiol compound in which the hydrocarbon group is an aromatic hydrocarbon group include 1,2-benzenedithiol, 1,3-benzenedithiol, 1,4-benzenedithiol, and 1,2-bis (mercaptomethyl). ) Arenedithiols (aromatic dithiols) such as benzene, 1,3-bis (mercaptomethyl) benzene, 1,4-bis (mercaptomethyl) benzene, toluene-3,4-dithiol.

Although a dithiol compound may be used independently, you may use it by multiple types (at least 2 types). When used alone, the resulting polythiocarbonate dithiol has one type of repeating unit represented by the general formula (t3), and the polythiocarbonate dithiol obtained when two or more types are used In the general formula (t3), R ^t5 has a plurality of (at least two) repeating units (copolymers). When a plurality of dithiol compounds are used, for example, if a dithiol compound having the following combination is used, it has a low melting point and a low crystallization temperature and is liquid at a temperature of 40 ° C., preferably liquid at a temperature of 30 ° C. Polythiocarbonate dithiol can be obtained, and among the dithiol compounds, the following combinations are listed as examples. In a specific embodiment, it is possible to obtain polythiocarbonate dithiol that is liquid at a temperature of 20 ° C., and further polythiocarbonate dithiol that is liquid at 10 ° C. or liquid at 0 ° C. The use ratio of the plurality of dithiol compounds is not particularly limited as long as a liquid polycarbonate dithiol is obtained. Such a liquid polythiocarbonate dithiol is practically very useful, such as enabling cast polymerization at room temperature.

-Combinations of aliphatic straight chain dithiols with different chain lengths: 1,5-pentanedithiol and 1,6-hexanedithiol, bis (mercaptoalkyl) sulfide (eg bis (2-mercaptoethyl) sulfide) And a combination of 1,6-hexanedithiol and the like.
-Combination of aliphatic linear dithiol and aliphatic branched dithiol: Combination of 1,6-hexanedithiol and 3-methyl-1,5-pentanedithiol, etc.
-Combination of aliphatic linear dithiol or aliphatic branched dithiol and alkanedithiol having an aliphatic hydrocarbon ring: combination of 1,6-hexanedithiol and 1,4-bis (mercaptomethyl) cyclohexane.
A combination of an aliphatic linear dithiol or an aliphatic branched dithiol and an alkanedithiol having a heteroatom and an aliphatic hydrocarbon ring: 1,6-hexanedithiol and 2,5-bis (mercaptomethyl) -1,4-dithiane Combination with etc.

  In the production of polythiocarbonate dithiol, an ester exchange reaction is carried out while continuously extracting alcohol (especially aryl alcohol) produced as a by-product from the carbonate compound (especially diaryl carbonate) and dithiol compound in the presence of a transesterification catalyst. It is preferable. At this time, the amount of the dithiol compound used is 0.8 to 3.0 times mol with respect to the carbonate compound so that all or almost all terminals of the resulting polythiocarbonate dithiol molecular chain are mercapto groups. It is preferable that it is 0.85-2.5 times mole, especially 0.9-2.5 times mole. Moreover, it is preferable that the usage-amount of a transesterification catalyst is 1-5000 ppm on a molar basis with respect to a dithiol compound, Furthermore, it is preferable that it is 10-1000 ppm.

In the transesterification reaction, diphenyl carbonate is preferably used as the diaryl carbonate, and the hydrocarbon group R ^t5 preferably has 4 to 14 carbon atoms. The amount of the dithiol compound having 4 to 14 carbon atoms of the hydrocarbon group R ^t5 is 1.05 to 3.0 times mol, particularly 1.1 to 2.5 times mol to diphenyl carbonate. preferable. If it does in this way, the ratio of terminal groups other than a thiol group among terminal groups can be 5 mol% or less, Furthermore, 2 mol% or less, Especially 1 mol% or less can be made. When diaryl carbonate (for example, diphenyl carbonate) is used, the terminal group other than the thiol group is an aryloxy group (for example, phenoxy group). By appropriately selecting the conditions as described above, a polythio having a low coloring degree (that is, APHA of 60 or less, further 40 or less, particularly 20 or less) and all or almost all of the molecular chain terminals are mercapto groups. Carbonate dithiol can be obtained. By controlling the ratio of the aryloxy group in the terminal group, it is possible to obtain a transparent member excellent in mechanical properties in addition to optical properties. In addition, APHA represents the hue at the time of heating and melting, and the ratio of the aryloxy group is on a molar basis (the same applies hereinafter).

The conditions of the transesterification reaction (temperature, pressure, time) are not particularly limited as long as the target product can be generated, but the carbonate compound and the dithiol compound are esterified so that the target product can be generated efficiently. In the presence of the exchange catalyst, the reaction is carried out at 110 to 200 ° C. for about 1 to 24 hours under normal pressure or reduced pressure, and then at 110 to 240 ° C. (especially 140 to 240 ° C.) for about 0.1 to 20 hours under reduced pressure. It is preferable to carry out the reaction for about 0.1 to 20 hours under a reduced pressure that finally becomes 20 mmHg (2.7 kPa) or less while gradually increasing the degree of vacuum at the same temperature. When a plurality of dithiol compounds are used, the corresponding polythiocarbonate dithiol may be produced by transesterifying the carbonate compound and the dithiol compound under the same conditions, and this may be reacted with another dithiol compound. At this time, if the carbonate compound is diphenyl carbonate, diphenyl carbonate and a dithiol compound having 4 to 14 carbon atoms in R ^t5 are subjected to an ester exchange reaction, and then the polythiocarbonate dithiol to be generated and R ^t5 have 2 to 2 carbon atoms. It is preferable to react the dithiol compound 4 to produce the target product. In order to extract the by-product alcohol, it is preferable to provide a distillation apparatus in the reactor, and the reaction may be performed under a flow of an inert gas (nitrogen, helium, argon, etc.).

  The transesterification catalyst is not particularly limited as long as it is a compound that catalyzes the transesterification reaction. For example, basic compounds such as potassium carbonate, sodium alkoxide (sodium methoxide, sodium ethoxide, etc.), quaternary ammonium salt (tetraalkylammonium hydroxide such as tetrabutylammonium hydroxide); titanium tetrachloride, tetraalkoxy titanium ( Titanium compounds such as tetra-n-butoxy titanium and tetraisopropoxy titanium); tin such as metal tin, tin hydroxide, tin chloride, dibutyltin dilaurate, dibutyltin oxide, butyltin tris (2-ethylhexanoate) Compounds.

Among transesterification catalysts, basic compounds such as potassium carbonate, sodium alkoxide (sodium methoxide, sodium ethoxide, etc.), quaternary ammonium salts (tetraalkylammonium hydroxide such as tetrabutylammonium hydroxide); and tetraalkoxy Titanium (tetra-n-butoxy titanium, tetraisopropoxy titanium, etc.) is preferred. The transesterification catalyst may be any catalyst as long as it can control the de-COS reaction, the degree of coloring, and the amount of the remaining catalyst within a range where the optical properties and mechanical properties of the cured product (that is, the transparent member) can be maintained at a high level. Among them, the basic compound can increase the reaction rate, APHA is 60 or less, the coloring degree is low, and the de-COS reaction at the thiocarbonate structure (—S— (C═O) —S—) moiety. A high-quality polythiocarbonate dithiol in which the ratio of the thioether structure (—R ^t5 —S—R ^t5 —) produced by the above is 3 mol% or less of the total of the remaining thiocarbonate structure and the thioether structure on a molar basis (hereinafter the same) Is particularly preferable. In the basic compound, a quaternary ammonium salt (particularly, a tetraalkylammonium hydroxide such as tetrabutylammonium hydroxide) may contain a metal component having an APHA of 60 or less and a proportion of the thioether structure of 1 mol% or less. More preferred since it provides less polythiocarbonate dithiol. By controlling the de-COS reaction in this way, the S content of the polythiocarbonate dithiol and the thiocarbonate structure can be maintained at a high level. The residual thiocarbonate structure refers to a thiocarbonate structure that has not undergone de-COS reaction.

  In the present invention, the polythiocarbonate dithiol preferably has a number average molecular weight (Mn) of 200 to 2500, more preferably 400 to 2000. When the number average molecular weight is within this range, the optical properties and mechanical properties of the resulting cured product tend to be satisfactory. That is, when the number average molecular weight is 200 or more, the tilt strength of the cured product tends to increase, and when it is 2500 or less, the melting point and the crystallization temperature do not become too high, and the vinyl represented by the above general formula (1). Good compatibility with other components such as a group-containing compound is maintained, and the light transmittance of the cured product (that is, the transparent member) is likely to be improved. For this reason, the amounts of carbonate compound and dithiol compound used are adjusted so as to achieve the target molecular weight. When the molecular weight is large, it is preferable to adjust the molecular weight by adding a dithiol compound and further performing a transesterification reaction.

  After adjusting the molecular weight, if necessary, it is preferable to deactivate the transesterification catalyst remaining in the polythiocarbonate dithiol. When tetraalkoxytitanium is used, the transesterification catalyst can be deactivated by a known method of adding a phosphorus compound (phosphoric acid, butyl phosphate, dibutyl phosphate, etc.). When used, it can be carried out by adding an equimolar amount of an inorganic or organic acid (sulfuric acid, paratoluenesulfonic acid, etc.) to the catalyst under heating at 40 ° C to 150 ° C. When an insoluble salt precipitates upon acid addition, it is preferably removed by washing with water.

  In addition, the obtained polythiocarbonate dithiol can be washed with water, and the degree of coloring (APHA) can be further lowered. For example, when tetraalkylammonium hydroxide is used as a transesterification catalyst, APHA of the resulting polythiocarbonate dithiol is already 60 or less, but it can be lowered to 40 or less, and further to 20 or less (10 or less) by washing with water. it can. When the catalyst is a titanium compound, the APHA (over 100) of the polythiocarbonate dithiol can be similarly reduced. The washing with water can be performed by dissolving polythiocarbonate dithiol in a good solvent such as methylene chloride, adding an appropriate amount of water, and mixing or stirring uniformly. This operation may be performed a plurality of times as necessary. Moreover, if a basic compound or a titanium compound is used as a transesterification catalyst, the amount of residual catalyst in polythiocarbonate dithiol can be reduced to 10 ppm or less (more preferably 2 ppm or less) on a mass basis (the same applies hereinafter) by washing with water. it can. By controlling the residual catalyst amount in this way, the optical properties and mechanical properties of the cured product (that is, the transparent member) can be maintained at a high level.

  In addition, the thiol group containing compound represented by the said general formula (t3), ie, polythiocarbonate dithiol, may contain polythiocarbonate polythiol as needed within the range of the compounding quantity. The polythiocarbonate polythiol is produced using a trithiol or higher polythiol compound instead of the above-mentioned dithiol compound. Examples of the polythiol compound include 1,1,1-tris (mercaptomethyl) ethane, 2-ethyl-2- Alkanetrithiols such as mercaptomethyl-1,3-propanedithiol; tetrakis (mercaptomethyl) methane, 3,3′-thiobis (propane-1,2-dithiol), 2,2′-thiobis (propane-1,3) -Alkanetetrathiol such as -dithiol); and arenetrithiol (aromatic trithiol) such as 1,3,5-benzenetrithiol and 1,3,5-tris (mercaptomethyl) benzene. However, when a polythiol compound is used, branching and / or cross-linking structures in the polymer increase, and therefore, it is preferable to select and use them appropriately in consideration of the physical properties of the obtained polythiocarbonate polythiol.

  The content of the thiol group-containing compound having at least two thiol groups in one molecule is preferably 1 to 75% by mass, more preferably 4 with respect to the total mass of the composition for forming a transparent member according to the present invention. -50 mass%. When the content of the thiol group-containing compound is within the above range, it is easy to obtain a cured product having a high refractive index and a high glass transition temperature.

[Episulfide compounds]
The composition for forming a transparent member according to the present invention may contain an episulfide compound. The episulfide compound expresses a good balance between the high refractive index and the high Abbe number of the transparent member, and has at least one structure represented by the following general formula (u1) in one molecule. If it does not specifically limit. The episulfide compounds can be used alone or in combination of two or more.

In the formula, R ^u1 represents a hydrocarbon group having 1 to 10 carbon atoms, R ^u2 , R ^u3 and R ^u4 each independently represent a hydrocarbon group having 1 to 10 carbon atoms or hydrogen, and J represents O , S, Se, or Te, s = 0 to 5, an integer of t = 0 or 1, and u = 1 to 5.

Examples of the hydrocarbon group having 1 to 10 carbon atoms of R ^u1 include alkylene groups such as methylene and ethylene. Examples of the hydrocarbon group having 1 to 10 carbon atoms of R ^u2 , R ^u3 , and R ^u4 include alkyl groups such as a methyl group, an ethyl group, and a propyl group. J represents O, S, Se, or Te, and S, Se, or Te is preferable if a higher refractive index is desired. u represents an integer of 1 to 5, preferably 1 or 2, and more preferably 1. s represents an integer of 0 to 5, preferably an integer of 0 to 4, more preferably 0 or 1. t represents 0 or 1, and is preferably 1.

  Episulfide compounds include all compounds having one or more structures represented by the above general formula (u1) in one molecule. Specific examples of preferred compounds include (a) an organic compound having an epithio group. Compound, (b) an organic compound having an epithioalkyloxy group, (c) an organic compound having an epithioalkylthio group, (d) an organic compound having an epithioalkylseleno group, (e) having an epithioalkyltelluro group An organic compound is mentioned.

  The organic compounds (a), (b), (c), (d) and (e) are chain compounds, branched compounds, aliphatic cyclic compounds, aromatic compounds, or nitrogen, oxygen, sulfur, selenium. And / or a heterocyclic compound containing a tellurium atom as a main skeleton, and at least two kinds of an epithio group, an epithioalkyloxy group, an epithioalkylthio group, an epithioalkylseleno group, and an epithioalkyltelluro group May be simultaneously contained in one molecule. Furthermore, these compounds may contain bonds such as sulfide, selenide, telluride, ether, sulfone, ketone, ester, amide, urethane and the like in the molecule.

  (A) A preferred specific example of an organic compound having one or more epithio groups is a compound obtained by substituting one or more epoxy groups of an epoxy group (not a glycidyl group) with an epithio group as a representative example. More specifically, the following compounds can be given as typical examples.

  Organic compounds having a chain aliphatic skeleton: 1,1-bis (epithioethyl) methane, 1- (epithioethyl) -1- (β-epithiopropyl) methane, 1,1-bis (β-epithiopropyl) methane 1- (epithioethyl) -1- (β-epithiopropyl) ethane, 1,2-bis (β-epithiopropyl) ethane, 1- (epithioethyl) -3- (β-epithiopropyl) butane, , 3-bis (β-epithiopropyl) propane, 1- (epithioethyl) -4- (β-epithiopropyl) pentane, 1,4-bis (β-epithiopropyl) butane, 1- (epithioethyl)- 5- (β-epithiopropyl) hexane, 1- (epithioethyl) -2- (γ-epithiobutylthio) ethane, 1- (epithioethyl) -2- [2- (γ-epithiobutylthio) ) Ethylthio] ethane, tetrakis (β-epithiopropyl) methane, 1,1,1-tris (β-epithiopropyl) propane, 1,3-bis (β-epithiopropyl) -1- (β-epi Thiopropyl) -2-thiapropane, 1,5-bis (β-epithiopropyl) -2,4-bis (β-epithiopropyl) -3-thiapentane, and the like.

  Compounds having an aliphatic cyclic skeleton: 1,3 or 1,4-bis (epithioethyl) cyclohexane, 1,3 or 1,4-bis (β-epithiopropyl) cyclohexane, 2,5-bis (epithioethyl) -1 , 4-dithiane, 2,5-bis (β-epithiopropyl) -1,4-dithiane, 4-epithioethyl-1,2-cyclohexene sulfide, 4-epoxy-1,2-cyclohexene sulfide, etc. Compounds having one structure, 2,2-bis [4- (epithioethyl) cyclohexyl] propane, 2,2-bis [4- (β-epithiopropyl) cyclohexyl] propane, bis [4- (epithioethyl) cyclohexyl ] Methane, bis [4- (β-epithiopropyl) cyclohexyl] methane, bis [4- (β-epithiopropyl) silane Examples thereof include compounds having two aliphatic cyclic structures such as cyclohexyl] sulfide and bis [4- (epithioethyl) cyclohexyl] sulfide.

  Compound having an aromatic skeleton: a compound having one aromatic skeleton such as 1,3 or 1,4-bis (epithioethyl) benzene, 1,3 or 1,4-bis (β-epithiopropyl) benzene, Bis [4- (epithioethyl) phenyl] methane, bis [4- (β-epithiopropyl) phenyl] methane, 2,2-bis [4- (epithioethyl) phenyl] propane, 2,2-bis [4- ( β-epithiopropyl) phenyl] propane, bis [4- (epithioethyl) phenyl] sulfide, bis [4- (β-epithiopropyl) phenyl] sulfide, bis [4- (epithioethyl) phenyl] sulfone, bis [4 -(Β-epithiopropyl) phenyl] sulfone, 4,4′-bis (epithioethyl) biphenyl, 4,4′-bis (β-epithiopro) Le) compounds having two aromatic skeleton such biphenyl. Furthermore, compounds in which at least one hydrogen of the epithio group of these compounds is substituted with a methyl group are also included.

  (B) Preferred specific examples of organic compounds having one or more epithioalkyloxy groups are compounds in which one or more glycidyl groups of an epoxy compound derived from epihalohydrin are substituted with epithioalkyloxy groups (thioglycidyl groups) Can be cited as a representative example. Specific examples of the epoxy compound are produced by condensation of a polyhydric phenol compound such as hydroquinone, catechol, resorcin, bisphenol A, bisphenol F, bisphenol sulfone, bisphenol ether, bisphenol sulfide, halogenated bisphenol A, novolac resin and epihalohydrin. A phenolic epoxy compound; ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, Neopentyl glycol, glycerin, trimethylolpropane trimethacrylate, pentaerythritol, 1,3- Is a polyhydric alcohol compound such as 1,4-cyclohexanediol, 1,3- or 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, bisphenol A / ethylene oxide adduct, bisphenol A / propylene oxide adduct, and epihalohydrin Alcoholic epoxy compounds produced by condensation of adipic acid, sebacic acid, dodecanedicarboxylic acid, dimer acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, hexahydrophthalic acid, hexahydroisophthalic acid Acid, hexahydroterephthalic acid, het acid, nadic acid, maleic acid, succinic acid, fumaric acid, trimellitic acid, benzenetetracarboxylic acid, benzophenonetetracarboxylic acid, naphthalene dicarboxylic acid, diphth A glycidyl ester epoxy compound produced by condensation of a polyvalent carboxylic acid compound such as nildicarboxylic acid and an epihalohydrin; ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,2-diaminobutane, 1, 3-diaminobutane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, bis- (3-aminopropyl) ether, 1,2-bis- (3-aminopropoxy) ethane, 1,3-bis- (3-aminopropoxy) -2,2′-dimethylpropane, 1,2-, 1,3- or 1,4-bis Aminocyclohexane, 1,3- or 1,4-bisaminomethylcyclohexane, 1,3- or 1,4-bisaminoethylcyclo Hexane, 1,3- or 1,4-bisaminopropylcyclohexane, hydrogenated 4,4′-diaminodiphenylmethane, isophoronediamine, 1,4-bisaminopropylpiperazine, m- or p-phenylenediamine, 2,4- Or 2,6-tolylenediamine, m- or p-xylylenediamine, 1,5- or 2,6-naphthalenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 2,2- Primary diamine such as (4,4′-diaminodiphenyl) propane, 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-diamino Heptane, N, N′-diethylethylenediamine, N, N′-diethyl-1,2-diaminopropane, N, N′-diethyl-1,3-diaminopropane, N, N′-diethyl-1,2-diamino Butane, N, N′-diethyl-1,3-diaminobutane, N, N′-diethyl-1,4-diaminobutane, N, N′-diethyl-1,6-diaminohexane, piperazine, 2-methylpiperazine 2,5- or 2,6-dimethylpiperazine, homopiperazine, 1,1-di- (4-piperidyl) -methane, 1,2-di- (4-piperidyl) -ethane, 1,3-di Amine-based epoxy compounds produced by condensation of secondary diamines such as (4-piperidyl) -propane and 1,4-di- (4-piperidyl) -butane with epihalohydrins, the above-mentioned polyhydric alcohols, phenol compounds and diisocyanates And urethane-based epoxy compounds produced from glycidol and the like.

  (B) Specific examples of organic compounds having one or more epithioalkyloxy groups include the following compounds.

  Organic compounds having a chain aliphatic skeleton: bis (β-epithiopropyl) ether, bis (β-epithiopropyloxy) methane, 1,2-bis (β-epithiopropyloxy) ethane, 1,3- Bis (β-epithiopropyloxy) propane, 1,2-bis (β-epithiopropyloxy) propane, 1- (β-epithiopropyloxy) -2- (β-epithiopropyloxymethyl) propane, 1,4-bis (β-epithiopropyloxy) butane, 1,3-bis (β-epithiopropyloxy) butane, 1- (β-epithiopropyloxy) -3- (β-epithiopropyloxy) Methyl) butane, 1,5-bis (β-epithiopropyloxy) pentane, 1- (β-epithiopropyloxy) -4- (β-epithiopropyloxymethyl) pentane, 1,6-bis (β-epithiopropyloxy) hexane, 1- (β-epithiopropyloxy) -5- (β-epithiopropyloxymethyl) hexane, 1- (β-epithiopropyloxy)- 2-[(2-β-epithiopropyloxyethyl) oxy] ethane, 1- (β-epithiopropyloxy) -2-[[2- (2-β-epithiopropyloxyethyl) oxyethyl] oxy] Ethane, tetrakis (β-epithiopropyloxymethyl) methane, 1,1,1-tris (β-epithiopropyloxymethyl) propane, 1,5-bis (β-epithiopropyloxy) -2- (β -Epithiopropyloxymethyl) -3-thiapentane, 1,5-bis (β-epithiopropyloxy) -2,4-bis (β-epithiopropyloxymethyl) -3- Apentane, 1- (β-epithiopropyloxy) -2,2-bis (β-epithiopropyloxymethyl) -4-thiahexane, 1,5,6-tris (β-epithiopropyloxy) -4- (Β-epithiopropyloxymethyl) -3-thiahexane, 1,8-bis (β-epithiopropyloxy) -4- (β-epithiopropyloxymethyl) -3,6-dithiaoctane, 1,8- Bis (β-epithiopropyloxy) -4,5bis (β-epithiopropyloxymethyl) -3,6-dithiaoctane, 1,8-bis (β-epithiopropyloxy) -4,4-bis ( β-epithiopropyloxymethyl) -3,6-dithiaoctane, 1,8-bis (β-epithiopropyloxy) -2,4,5-tris (β-epithiopropyloxymethyl) -3, 6-dithiaoctane, 1,8-bis (β-epithiopropyloxy) -2,5-bis (β-epithiopropyloxymethyl) -3,6-dithiaoctane, 1,9-bis (β-epithiopropyl) Oxy) -5- (β-epithiopropyloxymethyl) -5-[(2-β-epithiopropyloxyethyl) oxymethyl] -3,7-dithianonane, 1,10-bis (β-epithiopropyl) Oxy) -5,6-bis [(2-β-epithiopropyloxyethyl) oxy] -3,6,9-trithiadecane, 1,11-bis (β-epithiopropyloxy) -4,8-bis (Β-epithiopropyloxymethyl) -3,6,9-trithiaundecane, 1,11-bis (β-epithiopropyloxy) -5,7-bis (β-epithiopropyloxymethyl) -3 , 6,9-trithiaundecane, 1,11-bis (β-epithiopropyloxy) -5,7-[(2-β-epithiopropyloxyethyl) oxymethyl] -3,6,9-trithia Examples include undecane, 1,11-bis (β-epithiopropyloxy) -4,7-bis (β-epithiopropyloxymethyl) -3,6,9-trithiaundecane, and the like.

  Compounds having an aliphatic cyclic skeleton: 1,3 or 1,4-bis (β-epithiopropyloxy) cyclohexane, 1,3 or 1,4-bis (β-epithiopropyloxymethyl) cyclohexane, bis [4 -(Β-epithiopropyloxy) cyclohexyl] methane, 2,2-bis [4- (β-epithiopropyloxy) cyclohexyl] propane, bis [4- (β-epithiopropyloxy) cyclohexyl] sulfide, 2 , 5-bis (β-epithiopropyloxymethyl) -1,4-dithiane, 2,5-bis (β-epithiopropyloxyethyloxymethyl) -1,4-dithiane, and the like.

  Compounds having an aromatic skeleton: aromatics such as 1,3 or 1,4-bis (β-epithiopropyloxy) benzene, 1,3 or 1,4-bis (β-epithiopropyloxymethyl) benzene Compounds having one skeleton, bis [4- (β-epithiopropyl) phenyl] methane, 2,2-bis [4- (β-epithiopropylthio) phenyl] propane, bis [4- (β- Compounds having two aromatic skeletons such as epithiopropylthio) phenyl] sulfide, bis [4- (β-epithiopropylthio) phenyl] sulfone, 4,4′-bis (β-epithiopropylthio) biphenyl Is mentioned. Furthermore, the compound by which at least 1 of the hydrogen of the epithio group of these compounds was substituted by the methyl group can be illustrated.

  (C) A preferred specific example of an organic compound having one or more epithioalkylthio groups is an epoxyalkylthio group (specifically, β-epoxypropylthio group) of an epoxy compound derived from a compound having a mercapto group and an epihalohydrin. As a representative example, a compound in which one or more of ()) is substituted with an epithioalkylthio group can be given. More specifically, the following compounds can be given as typical examples.

  Organic compounds having a chain aliphatic skeleton: bis (β-epithiopropyl) sulfide, bis (β-epithiopropyl) disulfide, bis (β-epithiopropyl) trisulfide, bis (β-epithiopropylthio) Methane, bis (β-epithiopropyldithio) methane, bis (β-epithiopropyldithio) ethane, bis (β-epithiopropyldithioethyl) sulfide, bis (β-epithiopropyldithioethyl) disulfide, 1, 2-bis (β-epithiopropylthio) ethane, 1,3-bis (β-epithiopropylthio) propane, 1,2-bis (β-epithiopropylthio) propane, 1- (β-epithio Propylthio) -2- (β-epithiopropylthiomethyl) propane, 1,4-bis (β-epithiopropylthio) butane, 1,3- Bis (β-epithiopropylthio) butane, 1- (β-epithiopropylthio) -3- (β-epithiopropylthiomethyl) butane, 1,5-bis (β-epithiopropylthio) pentane, 1- (β-epithiopropylthio) -4- (β-epithiopropylthiomethyl) pentane, 1,6-bis (β-epithiopropylthio) hexane, 1- (β-epithiopropylthio)- 5- (β-epithiopropylthiomethyl) hexane, 1- (β-epithiopropylthio) -2-[(2-β-epithiopropylthioethyl) thio] ethane, 1- (β-epithiopropyl) Thio) -2-[[2- (2-β-epithiopropylthioethyl) thioethyl] thio] ethanetetrakis (β-epithiopropylthiomethyl) methane, tetrakis (β-epithiopropyldithiome) L) Methane, 1,1,1-tris (β-epithiopropylthiomethyl) propane, 1,2,3-tris (β-epithiopropyldithio) propane, 1,5-bis (β-epithiopropyl) Thio) -2- (β-epithiopropylthiomethyl) -3-thiapentane, 1,5-bis (β-epithiopropylthio) -2,4-bis (β-epithiopropylthiomethyl) -3- Thiapentane, 1,6-bis (β-epithiopropyldithiomethyl) -2- (β-epithiopropyldithioethylthio) -4-thiahexane, 1- (β-epithiopropylthio) -2,2-bis (Β-epithiopropylthiomethyl) -4-thiahexane, 1,5,6-tris (β-epithiopropylthio) -4- (β-epithiopropylthiomethyl) -3-thiahexane, 1,8- Screw β-epithiopropylthio) -4- (β-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (β-epithiopropylthio) -4,5bis (β-epithiopropyl) Thiomethyl) -3,6-dithiaoctane, 1,8-bis (β-epithiopropylthio) -4,4-bis (β-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (Β-epithiopropylthio) -2,4,5-tris (β-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (β-epithiopropylthio) -2,5- Bis (β-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,9-bis (β-epithiopropylthio) -5- (β-epithiopropylthiomethyl) -5-[(2-β -Epithiopropylthioeth ) Thiomethyl] -3,7-dithianonane, 1,10-bis (β-epithiopropylthio) -5,6-bis [(2-β-epithiopropylthioethyl) thio] -3,6,9- Trithiadecane, 1,11-bis (β-epithiopropylthio) -4,8-bis (β-epithiopropylthiomethyl) -3,6,9-trithiaundecane, 1,11-bis (β-epi Thiopropylthio) -5,7-bis (β-epithiopropylthiomethyl) -3,6,9-trithiaundecane, 1,11-bis (β-epithiopropylthio) -5,7-[( 2-β-epithiopropylthioethyl) thiomethyl] -3,6,9-trithiaundecane, 1,11-bis (β-epithiopropylthio) -4,7-bis (β-epithiopropylthiomethyl) ) -3,6,9-trithiaun A decane etc. are mentioned.

  Chain compounds having an ester group and an epithioalkylthio group: tetra [2- (β-epithiopropylthio) acetylmethyl] methane, 1,1,1-tri [2- (β-epithiopropylthio) acetyl Methyl] propane, tetra [2- (β-epithiopropylthiomethyl) acetylmethyl] methane, 1,1,1-tri [2- (β-epithiopropylthiomethyl) acetylmethyl] propane and the like.

  Compounds having an aliphatic cyclic skeleton: 1,3 or 1,4-bis (β-epithiopropylthio) cyclohexane, 1,3 or 1,4-bis (β-epithiopropylthiomethyl) cyclohexane 2,5- Bis (β-epithiopropylthiomethyl) -1,4-dithiane, 2,5-bis (β-epithiopropyldithiomethyl) -1,4-dithiane, 2,5-bis (β-epithiopropylthiol) A compound having one aliphatic cyclic skeleton such as ethylthiomethyl) -1,4-dithiane, bis [4- (β-epithiopropylthio) cyclohexyl] methane, 2,2-bis [4- (β- Epithiopropylthio) cyclohexyl] propane, bis [4- (β-epithiopropylthio) cyclohexyl] sulfide, 2,2-bis [4- (β-epithiopropylthio) cyclohexyl ] Propane, bis [4-(beta-epithiopropylthio) cyclohexyl] compounds having two aliphatic cyclic skeleton such sulfides and the like.

  Compound having aromatic skeleton: 1,3 or 1,4-bis (β-epithiopropylthio) benzene, 1,3 or 1,4-bis (β-epithiopropylthiomethyl) benzene, 1,3 or Compounds having one aromatic skeleton such as 1,4-bis (β-epithiopropyldithiomethyl) benzene, bis [4- (β-epithiopropylthio) phenyl] methane, 2,2-bis [4 -(Β-epithiopropylthio) phenyl] propane, bis [4- (β-epithiopropylthio) phenyl] sulfide, bis [4- (β-epithiopropylthio) phenyl] sulfone, 4,4′- Examples thereof include compounds having two aromatic skeletons such as bis (β-epithiopropylthio) biphenyl. Furthermore, compounds in which at least one of the hydrogen atoms in the β-epithiopropyl group of these compounds is substituted with a methyl group are also exemplified.

  (D) Preferable specific examples of the organic compound having an epithioalkylseleno group include an epoxy derived from a selenium compound such as metal selenium, alkali metal selenide, alkali metal selenol, alkyl (aryl) selenol, hydrogen selenide and epihalohydrin. A representative example is a compound in which one or more of the epoxyalkylseleno groups (specifically, β-epoxypropylseleno group) of the compound are substituted with epithioalkylseleno groups. More specifically, the following can be given as representative examples.

  Organic compounds having a chain aliphatic skeleton: bis (β-epithiopropyl) selenide, bis (β-epithiopropyl) diselenide, bis (β-epithiopropyl) triselenide, bis (β-epithiopropylseleno) methane 1,2-bis (β-epithiopropylseleno) ethane, 1,3-bis (β-epithiopropylseleno) propane, 1,2-bis (β-epithiopropylseleno) propane, 1- (β -Epithiopropylseleno) -2- (β-epithiopropylselenomethyl) propane, 1,4-bis (β-epithiopropylseleno) butane, 1,3-bis (β-epithiopropylseleno) butane, 1- (β-epithiopropylseleno) -3- (β-epithiopropylselenomethyl) butane, 1,5-bis (β-epithiopropylseleno) pentane, 1- (Β-epithiopropylseleno) -4- (β-epithiopropylselenomethyl) pentane, 1,6-bis (β-epithiopropylseleno) hexane, 1- (β-epithiopropylseleno) -5 (Β-epithiopropylselenomethyl) hexane, 1- (β-epithiopropylseleno) -2-[(2-β-epithiopropylselenoethyl) thio] ethane, 1- (β-epithiopropylseleno) 2-[[2- (2-β-epithiopropylselenoethyl) selenoethyl] thio] ethane, tetrakis (β-epithiopropylselenomethyl) methane, 1,1,1-tris (β-epithiopropylseleno) Methyl) propane, 1,5-bis (β-epithiopropylseleno) -2- (β-epithiopropylselenomethyl) -3-thiapentane, 1,5-bis (β-epi) Thiopropylseleno) -2,4-bis (β-epithiopropylselenomethyl) -3-thiapentane, 1- (β-epithiopropylseleno) -2,2-bis (β-epithiopropylselenomethyl)- 4-thiahexane, 1,5,6-tris (β-epithiopropylseleno) -4- (β-epithiopropylselenomethyl) -3-thiahexane, 1,8-bis (β-epithiopropylseleno)- 4- (β-epithiopropylselenomethyl) -3,6-dithiaoctane, 1,8-bis (β-epithiopropylseleno) -4,5bis (β-epithiopropylselenomethyl) -3,6- Dithiaoctane, 1,8-bis (β-epithiopropylseleno) -4,4-bis (β-epithiopropylselenomethyl) -3,6-dithiaoctane, 1,8-bis (β-epithio) Lopyrseleno) -2,4,5-tris (β-epithiopropylselenomethyl) -3,6-dithiaoctane, 1,8-bis (β-epithiopropylseleno) -2,5-bis (β-epithio) Propylselenomethyl) -3,6-dithiaoctane, 1,9-bis (β-epithiopropylseleno) -5- (β-epithiopropylselenomethyl) -5-[(2-β-epithiopropylselenoethyl) ) Selenomethyl] -3,7-dithianonane, 1,10-bis (β-epithiopropylseleno) -5,6-bis [(2-β-epithiopropylselenoethyl) thio] -3,6,9- Trithiadecane, 1,11-bis (β-epithiopropylseleno) -4,8-bis (β-epithiopropylselenomethyl) -3,6,9-trithiaundecane, 1,11-bis (β-epi Opropylseleno) -5,7-bis (β-epithiopropylselenomethyl) -3,6,9-trithiaundecane, 1,11-bis (β-epithiopropylseleno) -5,7-[( 2-β-epithiopropylselenoethyl) selenomethyl] -3,6,9-trithiaundecane, 1,11-bis (β-epithiopropylseleno) -4,7-bis (β-epithiopropylselenomethyl) ) -3,6,9-trithiaundecane, tetra [2- (β-epithiopropylseleno) acetylmethyl] methane, 1,1,1-tri [2- (β-epithiopropylseleno) acetylmethyl] Propane, tetra [2- (β-epithiopropylselenomethyl) acetylmethyl] methane, 1,1,1-tri [2- (β-epithiopropylselenomethyl) acetylmethyl] propa Bis (5,6-epithio-3-selenohexyl) selenide, 2,3-bis (6,7-thioepoxy-1-selena-4-selenoheptyl) -1- (3,4-thioepoxy-1-selenobutyl ) Propane, 1,1,3,3-tetrakis (4,5-thioepoxy-2-selenopentyl) -2-selenapropane, bis (4,5-thioepoxy-2-selenopentyl) -3,6,9 -Triselenaundecane-1,11-bis (3,4-thioepoxy-1-selenobutyl), 1,4-bis (3,4-thioepoxy-1-selenobutyl) -2,3-bis (6,7-thioepoxy -1-selena-4-selenoheptyl) butane, tris (4,5-thioepoxy-2-selenopentyl) -3-selena-6-thiaoctane-1,8-bis (3,4-thioepoxy) -1-selenobutyl), bis (5,6-epithio-3-selenohexyl) telluride, 2,3-bis (6,7-thioepoxy-1-tellura-4-selenoheptyl) -1- (3,4 Thioepoxy-1-selenobutyl) propane, 1,1,3,3-tetrakis (4,5-thioepoxy-2-selenopentyl) -2-tellapropane, bis (4,5-thioepoxy-2-selenopentyl)- 3,6,9-triteraoundedecane-1,11-bis (3,4-thioepoxy-1-selenobutyl), 1,4-bis (3,4-thioepoxy-1-selenobutyl) -2,3-bis ( 6,7-thioepoxy-1-tellla-4-selenoheptyl) butane, tris (4,5-thioepoxy-2-selenopentyl) -3-tella-6-thiaoctane-1,8-bis ( , 4-thioepoxy-1-Serenobuchiru) and the like.

  Compounds having an aliphatic cyclic skeleton: (1,3 or 1,4) -bis (β-epithiopropylseleno) cyclohexane, (1,3 or 1,4) -bis (β-epithiopropylselenomethyl) cyclohexane Bis [4- (β-epithiopropylseleno) cyclohexyl] methane, 2,2-bis [4- (β-epithiopropylseleno) cyclohexyl] propane, bis [4- (β-epithiopropylseleno) cyclohexyl ] Sulfide, 2,5-bis (β-epithiopropylselenomethyl) -1,4-dithiane, 2,5-bis (β-epithiopropylselenoethylthiomethyl) -1,4-dithiane, (2, 3 or 2,5 or 2,6) -bis (3,4-epithio-1-selenobutyl) -1,4-diselenane, (2,3 or 2,5 or 2,6) -bis (4 -Epithio-2-selenopentyl) -1,4-diselenane, (2,4 or 2,5 or 5,6) -bis (3,4-epithio-1-selenobutyl) -1,3-diselenane, (2 , 4 or 2,5 or 5,6) -bis (4,5-epithio-2-selenopentyl) -1,3-diselenan, (2,3 or 2,5 or 2,6 or 3,5)- Bis (3,4-epithio-1-selenobutyl) -1-thia-4-selenane, (2,3 or 2,5 or 2,6 or 3,5) -bis (4,5-epithio-2-seleno Pentyl) -1-thia-4-selenane, (2,4 or 4,5) -bis (3,4-epithio-1-selenobutyl) -1,3-diselenolane, (2,4 or 4,5)- Bis (4,5-epithio-2-selenopentyl) -1,3-diselenolane, (2,4 or 2,5 Or 4,5) -bis (3,4-epithio-1-selenobutyl) -1-thia-3-selenolane, (2,4 or 2,5 or 4,5) -bis (4,5-epithio-2) -Selenopentyl) -1-thia-3-selenolane, 2,6-bis (4,5-epithio-2-selenopentyl-1,3,5-triselenane, bis (3,4-epithio-1-selenobutyl) Tricycloselenaoctane, bis (3,4-epithio-1-selenobutyl) dicycloselenanane, (2,3 or 2,4 or 2,5 or 3,4) -bis (3,4-epithio-1- Selenobutyl) selenophan, (2,3 or 2,4 or 2,5 or 3,4) -bis (4,5-epithio-2-selenopentyl) selenophan, 2- (4,5-thioepoxy-2- Selenopentyl) -5- (3,4-thioe) Xyl-1-selenobutyl) -1-selenacyclohexane, (2,3 or 2,4 or 2,5 or 2,6 or 3,4 or 3,5 or 4,5) -bis (3,4-thioepoxy- 1-selenobutyl) -1-selenacyclohexane, (2,3 or 2,4 or 2,5 or 2,6 or 3,4 or 3,5 or 4,5) -bis (4,5-thioepoxy-2- Selenopentyl) -1-selenacyclohexane, (2,3 or 2,5 or 2,6) -bis (3,4-epithio-1-selenobutyl) -1,4-diterlan, (2,3 or 2,5 Or 2,6) -bis (4,5-epithio-2-selenopentyl) -1,4-diterlan, (2,4 or 2,5 or 5,6) -bis (3,4-epithio-1- Selenobutyl) -1,3-diterlan, (2,4 or 2,5 or 5,6 -Bis (4,5-epithio-2-selenopentyl) -1,3-diterlan, (2,3 or 2,5 or 2,6 or 3,5) -bis (3,4-epithio-1-selenobutyl ) -1-thia-4-terlan, (2,3 or 2,5 or 2,6 or 3,5) -bis (4,5-epithio-2-selenopentyl) -1-thia-4-terlan, (2,4 or 4,5) -bis (3,4-epithio-1-selenobutyl) -1,3-ditellolane, (2,4 or 4,5) -bis (4,5-epithio-2-seleno Pentyl) -1,3-ditellolane, (2,4 or 2,5 or 4,5) -bis (3,4-epithio-1-selenobutyl) -1-thia-3-tellurolane, (2,4 or 2) , 5 or 4,5) -bis (4,5-epithio-2-selenopentyl) -1-thia-3-ter Lorane, 2,6-bis (4,5-epithio-2-selenopentyl-1,3,5-triterulan, bis (3,4-epithio-1-selenobutyl) tricyclotellaoctane, bis (3,4 (Epithio-1-selenobutyl) dicyclotellanonane, (2,3 or 2,4 or 2,5 or 3,4) -bis (3,4-epithio-1-selenobutyl) tellophane, (2,3 or 2, 4 or 2,5 or 3,4) -bis (4,5-epithio-2-selenopentyl) tellurophane, 2- (4,5-thioepoxy-2-selenopentyl) -5- (3,4-thioepoxy- 1-selenobutyl) -1-tellulacyclohexane, (2,3 or 2,4 or 2,5 or 2,6 or 3,4 or 3,5 or 4,5) -bis (3,4-thioepoxy-1- Selenobutyl) -1-te Lacyclohexane, (2,3 or 2,4 or 2,5 or 2,6 or 3,4 or 3,5 or 4,5) -bis (4,5-thioepoxy-2-selenopentyl) -1-tellula And cyclohexane.

  Compounds having an aromatic skeleton: (1,3 or 1,4) -bis (β-epithiopropylseleno) benzene, (1,3 or 1,4) -bis (β-epithiopropylselenomethyl) benzene, Bis [4- (β-epithiopropylseleno) phenyl] methane, 2,2-bis [4- (β-epithiopropylseleno) phenyl] propane, bis [4- (β-epithiopropylseleno) phenyl] Examples thereof include sulfide, bis [4- (β-epithiopropylseleno) phenyl] sulfone, 4,4′-bis (β-epithiopropylseleno) biphenyl, and the like. Furthermore, compounds in which at least one of the hydrogen atoms in the β-epithiopropyl group of these compounds is substituted with a methyl group are also exemplified.

  (E) Preferred specific examples of the organic compound having an epithioalkyltelluro group include epoxy derived from a tellurium compound such as metal tellurium, alkali metal telluride, alkali metal tellurol, alkyl (aryl) tellurol, hydrogen telluride and epihalohydrin. A representative example is a compound obtained by substituting one or more epoxyalkyltelluro groups (specifically, β-epoxypropyltelluro group) of the compound with an epithioalkyltelluro group. More specifically, the following compounds can be given as typical examples.

  Organic compounds having a chain aliphatic skeleton: bis (β-epithiopropyl) telluride, bis (β-epithiopropyl) ditelluride, bis (β-epithiopropyl) tritellide, bis (β-epithiopropyltelluro) methane 1,2-bis (β-epithiopropyltelluro) ethane, 1,3-bis (β-epithiopropyltelluro) propane, 1,2-bis (β-epithiopropyltelluro) propane, 1- (β -Epithiopropyltelluro) -2- (β-epithiopropyltelluromethyl) propane, 1,4-bis (β-epithiopropyltelluro) butane, 1,3-bis (β-epithiopropyltelluro) butane, 1- (β-epithiopropyltelluro) -3- (β-epithiopropyltelluromethyl) butane, 1,5-bis (β-epithiopropyltelluro) pentane, 1- (Β-epithiopropyltelluro) -4- (β-epithiopropyltelluromethyl) pentane, 1,6-bis (β-epithiopropyltelluro) hexane, 1- (β-epithiopropyltelluro) -5- (Β-epithiopropyltelluromethyl) hexane, 1- (β-epithiopropyltelluro) -2-[(2-β-epithiopropyltelluroethyl) thio] ethane, 1- (β-epithiopropyltelluro) 2-[[2- (2-β-epithiopropyltelluroethyl) telluroethyl] thio] ethane, tetrakis (β-epithiopropyltelluromethyl) methane, 1,1,1-tris (β-epithiopropyltelluro) Methyl) propane, 1,5-bis (β-epithiopropyltelluro) -2- (β-epithiopropyltelluromethyl) -3-thiapentane, 1,5-bis (β-epi Thiopropyltelluro) -2,4-bis (β-epithiopropyltelluromethyl) -3-thiapentane, 1- (β-epithiopropyltelluro) -2,2-bis (β-epithiopropyltelluromethyl)- 4-thiahexane, 1,5,6-tris (β-epithiopropyltelluro) -4- (β-epithiopropyltelluromethyl) -3-thiahexane, 1,8-bis (β-epithiopropyltelluro)- 4- (β-epithiopropyltelluromethyl) -3,6-dithiaoctane, 1,8-bis (β-epithiopropyltelluro) -4,5bis (β-epithiopropyltelluromethyl) -3,6- Dithiaoctane, 1,8-bis (β-epithiopropyltelluro) -4,4-bis (β-epithiopropyltelluromethyl) -3,6-dithiaoctane, 1,8-bis (β-epithio) Lopyrteluro) -2,4,5-tris (β-epithiopropyltelluromethyl) -3,6-dithiaoctane, 1,8-bis (β-epithiopropyltelluro) -2,5-bis (β-epithio) Propyltelluromethyl) -3,6-dithiaoctane, 1,9-bis (β-epithiopropyltelluro) -5- (β-epithiopropyltelluromethyl) -5-[(2-β-epithiopropyltelluroethyl) ) Selenomethyl] -3,7-dithianonane, 1,10-bis (β-epithiopropyltelluro) -5,6-bis [(2-β-epithiopropyltelluroethyl) thio] -3,6,9- Trithiadecane, 1,11-bis (β-epithiopropyltelluro) -4,8-bis (β-epithiopropyltelluromethyl) -3,6,9-trithiaundecane, 1,11-bis (β-epi Opropyltelluro) -5,7-bis (β-epithiopropyltelluromethyl) -3,6,9-trithiaundecane, 1,11-bis (β-epithiopropyltelluro) -5,7-[( 2-β-epithiopropyltelluroethyl) selenomethyl] -3,6,9-trithiaundecane, 1,11-bis (β-epithiopropyltelluro) -4,7-bis (β-epithiopropyltelluromethyl) ) -3,6,9-trithiaundecane, tetra [2- (β-epithiopropyltelluro) acetylmethyl] methane, 1,1,1-tri [2- (β-epithiopropyltelluro) acetylmethyl] Propane, tetra [2- (β-epithiopropyltelluromethyl) acetylmethyl] methane, 1,1,1-tri [2- (β-epithiopropyltelluromethyl) acetylmethyl] propa Bis (5,6-epithio-3-tellulohexyl) selenide, 2,3-bis (6,7-thioepoxy-1-selena-4-telloheptyl) -1- (3,4-thioepoxy-1-tellulobutyl) propane 1,1,3,3-tetrakis (4,5-thioepoxy-2-tellopentyl) -2-selenapropane, bis (4,5-thioepoxy-2-tellopentyl) -3,6,9-triselenaundecane -1,11-bis (3,4-thioepoxy-1-tellulobutyl), 1,4-bis (3,4-thioepoxy-1-tellulobutyl) -2,3-bis (6,7-thioepoxy-1-selena -4-telloheptyl) butane, tris (4,5-thioepoxy-2-tellopentyl) -3-selena-6-thiaoctane-1,8-bis (3,4-thioepoxy) -1-tellulobutyl), bis (5,6-epithio-3-tellurohexyl) telluride, 2,3-bis (6,7-thioepoxy-1-tellla-4-telluroheptyl) -1- (3,4-thioepoxy- 1-tellulobutyl) propane, 1,1,3,3, -tetrakis (4,5-thioepoxy-2-tellopentyl) -2-tellapropane, bis (4,5-thioepoxy-2-tellopentyl) -3,6 9-triteraoundedecane-1,11-bis (3,4-thioepoxy-1-tellulobutyl), 1,4-bis (3,4-thioepoxy-1-tellulobutyl) -2,3-bis (6,7- Thioepoxy-1-tellla-4-telluroheptyl) butane, tris (4,5-thioepoxy-2-tellopentyl) -3-tella-6-thiaoctane-1,8-bis ( , 4-thioepoxy-1-Terurobuchiru) and the like.

  Compounds having an aliphatic cyclic skeleton: (1,3 or 1,4) -bis (β-epithiopropyltelluro) cyclohexane, (1,3 or 1,4) -bis (β-epithiopropyltelluromethyl) cyclohexane Bis [4- (β-epithiopropyltelluro) cyclohexyl] methane, 2,2-bis [4- (β-epithiopropyltelluro) cyclohexyl] propane, bis [4- (β-epithiopropyltelluro) cyclohexyl] ] Sulfide, 2,5-bis (β-epithiopropyltelluromethyl) -1,4-dithiane, 2,5-bis (β-epithiopropyltelluroethylthiomethyl) -1,4-dithiane, (2, 3 or 2,5 or 2,6) -bis (3,4-epithio-1-tellulobutyl) -1,4-diselenane, (2,3 or 2,5 or 2,6) -bis (4 -Epithio-2-telluropentyl) -1,4-diselenane, (2,4 or 2,5 or 5,6) -bis (3,4-epithio-1-tellulobutyl) -1,3-diselenane, (2, 4 or 2,5 or 5,6) -bis (4,5-epithio-2-terlopentyl) -1,3-diselenane, (2,3 or 2,5 or 2,6 or 3,5) -bis ( 3,4-epithio-1-tellulobutyl) -1-thia-4-selenane, (2,3 or 2,5 or 2,6 or 3,5) -bis (4,5-epithio-2-telluropentyl)- 1-thia-4-selenane, (2,4 or 4,5) -bis (3,4-epithio-1-tellulobutyl) -1,3-diselenolane, (2,4 or 4,5) -bis (4 , 5-epithio-2-terlopentyl) -1,3-diselenolane, (2,4 or 2,5 Or 4,5) -bis (3,4-epithio-1-tellulobutyl) -1-thia-3-selenolane, (2,4 or 2,5 or 4,5) -bis (4,5-epithio-2) -Telluropentyl) -1-thia-3-selenolane, 2,6-bis (4,5-epithio-2-tellopentyl-1,3,5-triselenane, bis (3,4-epithio-1-tellurobutyl) tricyclo Selenaoctane, bis (3,4-epithio-1-tellulobutyl) dicycloselenanane, (2,3 or 2,4 or 2,5 or 3,4) -bis (3,4-epithio-1-tellulobutyl) Selenophan, (2,3 or 2,4 or 2,5 or 3,4) -bis (4,5-epithio-2-terlopentyl) selenophan, 2- (4,5-thioepoxy-2-terlopentyl)- 5- (3,4-thioe Xyl-1-tellulobutyl) -1-selenacyclohexane, (2,3 or 2,4 or 2,5 or 2,6 or 3,4 or 3,5 or 4,5) -bis (3,4-thioepoxy- 1-tellurobutyl) -1-selenacyclohexane, (2,3 or 2,4 or 2,5 or 2,6 or 3,4 or 3,5 or 4,5) -bis (4,5-thioepoxy-2- Telluropentyl) -1-selenacyclohexane, (2,3 or 2,5 or 2,6) -bis (3,4-epithio-1-tellulobutyl) -1,4-ditellan, (2,3 or 2,5 or 2,6) -bis (4,5-epithio-2-telluropentyl) -1,4-diterlan, (2,4 or 2,5 or 5,6) -bis (3,4-epithio-1-tellulobutyl) -1,3-diterlan, (2,4 or 2,5 or 5,6 -Bis (4,5-epithio-2-telluropentyl) -1,3-diterlan, (2,3 or 2,5 or 2,6 or 3,5) -bis (3,4-epithio-1-tellulobutyl) -1-thia-4-tellrane, (2,3 or 2,5 or 2,6 or 3,5) -bis (4,5-epithio-2-telluropentyl) -1-thia-4-tellane, (2 , 4 or 4,5) -bis (3,4-epithio-1-tellulobutyl) -1,3-ditellurolane, (2,4 or 4,5) -bis (4,5-epithio-2-telluropentyl)- 1,3-ditellolane, (2,4 or 2,5 or 4,5) -bis (3,4-epithio-1-tellulobutyl) -1-thia-3-tellurolane, (2,4 or 2,5 or 4,5) -Bis (4,5-epithio-2-terlopentyl) -1-thia-3-ter Lorane, 2,6-bis (4,5-epithio-2-tellopentyl-1,3,5-triterulan, bis (3,4-epithio-1-tellulobutyl) tricyclotellaoctane, bis (3,4-epithio) -1-tellulobutyl) dicyclotelllanonane, (2,3 or 2,4 or 2,5 or 3,4) -bis (3,4-epithio-1-tellulobutyl) tellophane, (2,3 or 2,4 Or 2,5 or 3,4) -bis (4,5-epithio-2-terlopentyl) tellophane, 2- (4,5-thioepoxy-2-tellopentyl) -5- (3,4-thioepoxy-1-tellulobutyl ) -1-tellulacyclohexane, (2,3 or 2,4 or 2,5 or 2,6 or 3,4 or 3,5 or 4,5) -bis (3,4-thioepoxy-1-tellulobutyl)- 1-te Racyclohexane, (2,3 or 2,4 or 2,5 or 2,6 or 3,4 or 3,5 or 4,5) -bis (4,5-thioepoxy-2-tellopentyl) -1-tellacyclohexane Etc.

  Compounds having an aromatic skeleton: (1,3 or 1,4) -bis (β-epithiopropyltelluro) benzene, (1,3 or 1,4) -bis (β-epithiopropyltelluromethyl) benzene, Bis [4- (β-epithiopropyltelluro) phenyl] methane, 2,2-bis [4- (β-epithiopropyltelluro) phenyl] propane, bis [4- (β-epithiopropyltelluro) phenyl] Examples thereof include sulfide, bis [4- (β-epithiopropyltelluro) phenyl] sulfone, 4,4′-bis (β-epithiopropyltelluro) biphenyl, and the like. Furthermore, compounds in which at least one of the hydrogen atoms in the β-epithiopropyl group of these compounds is substituted with a methyl group are also exemplified.

  Further, the organic compounds (a) to (e) described above may have an unsaturated group, and preferred specific examples thereof include vinylphenylthioglycidyl ether, vinylbenzylthioglycidyl ether, thiol. Examples thereof include glycidyl methacrylate, thioglycidyl acrylate, and allyl thioglycidyl ether.

  Of these, (b) an organic compound having an epithioalkyloxy group, (c) an organic compound having an epithioalkylthio group, (d) an organic compound having an epithioalkylseleno group, (e) Organic compounds having an epithioalkyltelluro group, particularly preferred are (c) an organic compound having an epithioalkylthio group, and (d) an organic compound having an epithioalkylseleno group. Specific examples of particularly preferable examples include the above-described specific examples of a chain compound having a β-epithiopropylthio group or β-epithiopropylseleno group, a branched compound, an aliphatic cyclic compound, an aromatic compound, and a hetero compound. It is a ring compound.

  The compound having one or more structures represented by the general formula (u1) used in the present invention in one molecule can be synthesized by a known method. Specifically, JP-A-9-71580, JP-A-9-110799, JP-A-9-255781, JP-A-2000-281787, JP-A-2000-186086, JP-A-2000-186087, JP-A-2000. The methods described in JP-A No. -309584, JP-A No. 2001-163871, JP-A No. 2001-163872, and JP-A No. 2001-163874 can be mentioned.

  When the composition for forming a transparent member according to the present invention contains an episulfide compound, the content of the episulfide compound is preferably 0.1 to 40% by mass with respect to the total mass of the composition for forming a transparent member. More preferably, it is 1-20 mass%. When the content of the episulfide compound is within the above range, it is easy to obtain a cured product having a high refractive index and a high glass transition temperature and maintaining good light resistance.

[Inorganic substance having sulfur atom and / or selenium atom]
The composition for forming a transparent member according to the present invention may contain an inorganic substance having a sulfur atom and / or a selenium atom. The said inorganic substance consists of an inorganic compound which has a sulfur simple substance, a selenium simple substance, and a sulfur atom and / or a selenium atom. In this specification, an inorganic compound is a compound as described in the “Standard Chemical Glossary” (edited by the Chemical Society of Japan (1991) Maruzen), and it is compared even if it contains carbon and a compound that does not contain carbon. A simple compound. For example, carbon disulfide and potassium thiocyanate, which are relatively simple compounds containing carbon, are treated as inorganic compounds. In the composition for forming a transparent member according to the present invention, it is possible to further increase the refractive index of the cured product by increasing the content of the inorganic substance. The said inorganic substance can be used individually or in combination of 2 or more types.

  The inorganic substance having a sulfur atom and / or selenium atom includes all inorganic substances having one or more sulfur atoms and selenium atoms in total, but the total amount of sulfur atoms and selenium atoms in the inorganic substance is 30 mass. % Or more is preferable. When this amount is 30% by mass or more, compared with the case where this amount is less than 30% by mass, when the inorganic substance is added to the composition for forming a transparent member, sulfur atoms in the composition and Since the increase in the total mass of selenium atoms becomes larger, the effect of increasing the refractive index of the cured product is likely to be improved.

  Specific examples of the inorganic substance having a sulfur atom include sulfur, hydrogen sulfide, carbon disulfide, carbon selenosulfide, ammonium sulfide, sulfur oxide (for example, sulfur dioxide, sulfur trioxide, etc.), thiocarbonate, sulfuric acid and its Salt, hydrogen sulfate, sulfite, hyposulfite, persulfate, thiocyanate, thiosulfate, sulfur halide (eg, sulfur dichloride, thionyl chloride, thiophosgene, etc.), boron sulfide, nitrogen sulfide, silicon sulfide , Phosphorus sulfide, arsenic sulfide, metal sulfide, metal hydrosulfide and the like. Among these, sulfur, carbon disulfide, phosphorus sulfide, selenium sulfide, metal sulfide, and metal hydrosulfide are preferable, sulfur, carbon disulfide, and selenium sulfide are more preferable, and sulfur is particularly preferable.

  Specific examples of inorganic substances having selenium atoms include selenium sulfide, hydrogen selenide, selenium dioxide, carbon diselenide, and ammonium selenide, except for carbon selenide and selenium sulfide, which are listed as specific examples of inorganic substances having sulfur atoms. Selenium oxide (for example, selenium dioxide), selenic acid and its salt, selenious acid and its salt, hydrogen selenate, selenosulfuric acid and its salt, selenopyrosulfuric acid and its salt, selenium halide (for example, four odors) Selenide, selenium oxychloride, etc.), selenocyanate, boron selenide, phosphorus selenide, arsenic selenide, metal selenide and the like. Among these, selenium, carbon diselenide, phosphorus selenide, and metal selenides are preferable, and selenium and carbon diselenide are particularly preferable.

  When the composition for forming a transparent member according to the present invention contains an inorganic substance having a sulfur atom and / or a selenium atom, the content of the inorganic substance is 0 with respect to the total mass of the composition for forming a transparent member. 0.1-30 mass% is preferable, More preferably, it is 5-20 mass%. When the content of the inorganic substance is within the above range, the viscosity of the resulting composition is unlikely to increase, and it is easy to obtain a cured product having a high refractive index and a high glass transition temperature and maintaining good light resistance. .

[catalyst]
The composition for forming a transparent member according to the present invention increases the reaction rate between the vinyl group-containing compound represented by the general formula (1) and the thiol group-containing compound having at least two thiol groups in one molecule. In order to do so, a catalyst may be contained. A catalyst can be used individually or in combination of 2 or more types. Catalysts include quaternary onium salts such as tetrabutylphosphonium bromide; acid catalysts such as sulfuric acid, hydrochloric acid, p-toluenesulfonic acid, pyridium p-toluenesulfonate, boron trifluoride; or amine compounds such as tertiary amines And a base catalyst. Among these, hydrochloric acid, p-toluenesulfonic acid, pyridium p-toluenesulfonate, and the like are particularly preferably used. The amount of the catalyst to be used is preferably 0.01 to 10 mol%, more preferably 0.05 to 5 mol%, relative to the vinyl group-containing compound represented by the general formula (1).

[Conditioning agent]
The composition for forming a transparent member according to the present invention may contain a regulator for the purpose of extending pot life, dispersing polymerization heat generation, and the like. A regulator can be used individually or in combination of 2 or more types. Examples of the adjusting agent include tin compounds such as dibutyltin dichloride, dimethyltin dichloride, and dibutyltin dilaurate. The usage-amount of a regulator is 0.005-10 mass% preferably in the composition for transparent member formation concerning this invention, More preferably, it is 0.01-5 mass%.

[solvent]
The composition for forming a transparent member according to the present invention may contain a solvent. A solvent can be used individually or in combination of 2 or more types. Examples of the solvent include known solvents. From the viewpoint of suppressing side reactions with reactants such as the vinyl group-containing compound represented by the above general formula (1) and a catalyst described later, a solvent that is not reactive with these substances is used. Is preferred. Specific examples include tetrahydrofuran, cyclocyclohexanone, propylene glycol monomethyl ether acetate, hydrocarbon solvents (for example, aliphatic hydrocarbon solvents such as hexane, and aromatic hydrocarbon solvents such as toluene).

  However, for example, when forming a lens etc. as a transparent member, it is preferable that the composition for transparent member formation concerning this invention does not contain a solvent substantially. When a thiol group-containing compound that is liquid at room temperature is used as the thiol group-containing compound having at least two thiol groups in one molecule, the vinyl group-containing compound represented by the general formula (1) is such a thiol. Since it melt | dissolves in a group containing compound, the composition for transparent member formation which does not contain a solvent substantially can be prepared. In particular, a lens or the like can be suitably formed from a composition for forming a transparent member that does not substantially contain a solvent.

  When using a solvent, the content of the solvent is preferably such that the total concentration of components other than the solvent in the composition according to the present invention is 1 to 50% by mass, and more preferably 5 to 30% by mass. .

[Other ingredients]
The composition for forming a transparent member according to the present invention may contain a dye and / or a pigment for reducing initial color defects or yellowing or redness due to light irradiation, if necessary. Although it does not specifically limit as a dye and / or a pigment for reduction of the initial color defect or yellowing or redness by light irradiation, The dye currently used for the transparent member can be used conveniently. Specific examples include bluing agents that are commercially available for spectacle lens materials.

  Furthermore, the composition for forming a transparent member according to the present invention may contain an antioxidant, an internal mold release agent or an internal adhesion improver, a known performance improving additive, and the like, if necessary.

<Transparent material>
The transparent member according to the present invention comprises a cured product of the transparent member forming composition according to the present invention. Since this cured product has a high refractive index and a high glass transition temperature and is excellent in optical properties and heat resistance, the transparent member according to the present invention is also excellent in optical properties and heat resistance. Examples of transparent members include optical members such as lenses (for example, microlenses), optical fibers, optical waveguides, prism sheets, holograms, high refractive films, retroreflective films, pixels of color filters for liquid crystal displays, LEDs, and semiconductors. Examples include sealing members for optical elements such as lasers, photodiodes, phototransistors, solar cells, and CCDs, and lenses are particularly preferable.

  The transparent member according to the present invention is, for example, an object for injecting the transparent member forming composition of the present invention containing a catalyst as necessary into a glass or metal mold or forming a transparent member. It can be obtained by applying to (for example, an optical element) and curing at a temperature of preferably -20 to 200 ° C, more preferably -10 to 160 ° C. The curing time may be set appropriately, and is, for example, about 5 minutes to 100 hours. In particular, the lens can be obtained from the composition for forming a transparent member of the present invention which does not substantially contain a solvent.

  EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated further more concretely, the scope of the present invention is not limited to these Examples.

<Compound represented by the above general formula (1) and comparative compound>
As the compound represented by the general formula (1), compounds 1 to 3 represented by the following formula were prepared. Moreover, the comparison compound 1 represented by a following formula was prepared for the comparison.

  Synthesis methods of Compounds 1 to 3 are shown below (Synthesis Examples 1 to 3). The materials used in the synthesis examples are as follows.

[Inorganic base]
(1) Light ash sodium carbonate particle size distribution: 250 μm or more; 3% by weight
150 μm or more and less than 250 μm; 15% by weight
75 μm or more and less than 150 μm; 50% by weight
<75 μm; 32% by weight
In addition, the above particle size distribution is classified by using 60 mesh (250 μm), 100 mesh (150 μm), and 200 mesh (75 μm) sieves, and finally obtained on the sieving component and the sieving component. Calculated by measuring the weight.

[Transition element compound catalyst]
(1) Di-μ-chlorobis (1,5-cyclooctadiene) diiridium (I): [Ir (cod) Cl] ₂

[Hydroxy compounds]
(1) 9,9'-bis (6-hydroxy-2-naphthyl) fluorene (2) 9,9'-bis (4-hydroxyphenyl) fluorene

[Vinyl ester compounds]
(1) Vinyl propionate

[Synthesis Example 1] Synthesis of Compound 1 Into a 1000 ml reaction vessel equipped with a cooling tube and a decanter for separating the condensate and returning the organic layer to the reaction vessel and discharging the aqueous layer out of the system, -Chlorobis (1,5-cyclooctadiene) diiridium (I) [Ir (cod) Cl] ₂ (839 mg, 1.25 mmol), light ash sodium carbonate (12.7 g, 0.12 mol), 9,9 ' -After charging bis (6-hydroxy-2-naphthyl) fluorene (225 g, 0.5 mol), vinyl propionate (125 g, 1.25 mol), and toluene (300 ml), a stirring blade having a surface area of 10 cm ² was used. The number of revolutions was set to 250 rpm, and the temperature was gradually raised and refluxed while stirring. The reaction was carried out for 5 hours under reflux while removing by-product water with a decanter. When the reaction solution was analyzed by gas chromatography, the conversion of 9,9′-bis (6-hydroxy-2-naphthyl) fluorene was 100%, and 9,9′-bis (6-hydroxy-2-naphthyl). ) Based on fluorene, 9,9′-bis (6-vinyloxy-2-naphthyl) fluorene (Compound 1) was produced in a yield of 81% and bis6-naphtholfluorene monovinyl ether in a yield of 4%.
¹ H-NMR (CDCl ₃ ): 4.47 (dd, 2H, J = 1.5 Hz, 5.0 Hz), 4.81 (dd, 2H, J = 3.5 Hz, 12.0 Hz), 6.71 (Dd, 2H, J = 6.0 Hz), 7.12-7.82 (m, 20H)

[Synthesis Example 2] Synthesis (isolation) of Compound 2
The reaction product obtained in Synthesis Example 1 was subjected to silica gel column chromatography for separation and purification, and bis6-naphtholfluorene monovinyl ether (Compound 2) was isolated.
¹ H-NMR (CDCl ₃ ): 4.55 (dd, 1H, J = 6.0 Hz), 4.88 (dd, 1H, J = 3.5 Hz), 6.79 (dd, 1H, J = 6) 0.0Hz, 14.0Hz), 7.20-7.89 (m, 20H)

[Synthesis Example 3] Synthesis of Compound 3 In a 1000 ml reaction vessel equipped with a decanter for separating the cooling pipe and the condensate, returning the organic layer to the reaction vessel and discharging the aqueous layer out of the system, di-μ was added. -Chlorobis (1,5-cyclooctadiene) diiridium (I) [Ir (cod) Cl] ₂ (839 mg, 1.25 mmol), light ash sodium carbonate (12.7 g, 0.12 mol), 9,9 ' -After charging bis (4-hydroxyphenyl) fluorene (186 g, 0.5 mol), vinyl propionate (125 g, 1.25 mol), and toluene (300 ml), the rotational speed was adjusted using a stirring blade with a surface area of 10 cm ^2. The temperature was set to 250 rpm, and the temperature was gradually raised and refluxed while stirring. The reaction was carried out for 5 hours under reflux while removing by-product water with a decanter. When the reaction solution was analyzed by gas chromatography, the conversion of 9,9′-bis (4-hydroxyphenyl) fluorene was 100%. Based on 9,9′-bis (4-hydroxyphenyl) fluorene, 9,9′-bis (4-vinyloxyphenyl) fluorene (Compound 3) was produced in a yield of 72% and bis-4-phenolfluorene monovinyl ether in a yield of 9%.
¹ H-NMR (CDCl ₃ ): 4.47 (dd, 2H), 4.81 (dd, 2H), 6.71 (dd, 2H), 7.12-7.82 (m, 16H)

<Thiol group-containing compound>
Thiol group-containing compound 1: bis (2-mercaptoethyl) sulfide (a thiol group-containing compound having two thiol groups in one molecule represented by the following formula)
Thiol group-containing compound 2: 4,7-dimercaptomethyl-1,11-mercapto-3,6,9-trithiaundecane (thiol group having four thiol groups in one molecule represented by the following formula: Containing compound)

Thiol group-containing compound 3: Polycarbonate dithiol (thiol group-containing compound having two thiol groups in one molecule obtained in Synthesis Example 4)
[Synthesis Example 4] Synthesis of polycarbonate dithiol 1,6-hexane was added to a 500 mL glass reactor equipped with a stirrer, a thermometer, and a distillation column (equipped with a fractionation tube, a reflux head, and a condenser at the top of the column). 90.1 g (0.599 mol) of dithiol, 77.2 g (0.500 mol) of bis (2-mercaptoethyl) sulfide, 155 g (0.725 mol) of diphenyl carbonate, and 10% by weight tetrabutylammonium hydroxide-methanol A solution (catalyst) of 0.861 g (0.332 mmol) was charged and maintained at 200 mmHg (27 kPa) at 160 ° C. for 1 hour while refluxing. Next, the pressure was gradually reduced to 50 mmHg over 6 hours while distilling off the phenol, and when the phenol stopped distilling, the pressure was gradually increased from 30 mmHg (4.0 kPa) to 15 mmHg (2.0 kPa) over 3 hours. The target polythiocarbonate dithiol was obtained by reducing the pressure and reacting while distilling a mixture of phenol, 1,6-hexanedithiol and bis (2-mercaptoethyl) sulfide.

  To this polythiocarbonate dithiol, equimolar amount of p-toluenesulfonic acid monohydrate was added to the above catalyst and stirred at 130 ° C. for 2 hours to inactivate the catalyst. Next, 430 g of methylene chloride was added to dissolve the polythiocarbonate dithiol, and the solution was washed three times with the same amount of water, dried over anhydrous magnesium sulfate, the solid matter was removed by filtration, and methylene chloride was distilled off. Left. The physical properties of the finally obtained polythiocarbonate dithiol are shown in Table 1. In Table 1, the thioether structure represents that produced by the de-COS reaction.

In addition, the physical property in Table 1 followed the following measuring method.
1. Mercapto group value (SH value; mgKOH / g): A sample is weighed in a 100 mL sample bottle (the mass is accurately read to the fourth decimal place in grams), and acetic anhydride-tetrahydrofuran solution (4 g of acetic anhydride in 100 ml of the solution). 5 mL) and 10 mL of 4-dimethylaminopyridine-tetrahydrofuran solution (containing 1 g of 4-dimethylaminopyridine in 100 mL of solution) were added exactly to completely dissolve the sample, and then allowed to stand at room temperature for 1 hour. 1 mL of pure water was accurately added, left at room temperature for 30 minutes with occasional stirring, and titrated with a 0.25 M potassium hydroxide-ethanol solution (indicator: phenolphthalein). The SH value was calculated by the following formula.
SH value (mgKOH / g) = 14.025 × (BA) × f / S
(Wherein S is the amount of sample collected (g), A is the amount of 0.25M potassium hydroxide-ethanol solution required for titration of the sample (mL), B is 0.25M potassium hydroxide required for the blank test- (Amount of ethanol solution (mL), f represents a factor of 0.25M potassium hydroxide-ethanol solution)

2. Number average molecular weight (Mn): calculated by the following formula.
2. Mn = 112200 / SH value Acid value (mgKOH / g): The sample was dissolved in 200 mL of a toluene-ethanol solution (equal volume mixed solution) and titrated with a 0.1 M potassium hydroxide-ethanol solution (indicator: phenolphthalein). The acid value was calculated by the following formula.
Acid value (mgKOH / g) = 5.61 (C−D) f ′ / S ′
(In the formula, S ′ is the amount of sample collected (g), C is the amount of 0.1 M potassium hydroxide-ethanol solution required for titration of the sample (ml), and D is 0.1 M potassium hydroxide required for the blank test. -Amount of ethanol solution (ml), f 'represents a factor of 0.1M potassium hydroxide-ethanol solution.
4). Viscosity (mPa · sec): Measured at 100 ° C. using an E-type rotational viscometer (trade name: Programmable Digital Viscometer DV-II +, manufactured by Brookfield).

5. Melting point (° C.) and crystallization temperature (° C.): Using a differential scanning calorimeter (trade name: DSC-50, manufactured by Shimadzu Corporation), raising the temperature in a range of −100 to 100 ° C. in a nitrogen gas atmosphere The measurement was performed at a rate of 10 ° C./min and a temperature decrease rate of 10 ° C./min.
6). Hue (APHA): Measured according to JIS-K1557.
7). Ratio of aryloxy group in terminal group (mol%): The ratio of phenoxy group to all terminal groups (molar basis) was determined from the integrated value of 1H-NMR.
8). Ratio of thioether structure (generated by de-COS reaction) (mol%): From the integrated value of 1H-NMR, the total amount (mole) of the remaining thiocarbonate structure and the thioether structure generated by the de-COS reaction was determined. The ratio (mol basis) of the thioether structure to the amount was determined.
9. Residual catalyst amount (ppm by mass): A 30% by mass chloroform solution of polythiocarbonate dithiol was prepared, and tetrabutylammonium hydroxide in the solution was extracted with the same volume of water and measured by high performance liquid chromatography.

  Thiol group-containing compound 4: 1-dodecanethiol (thiol group-containing compound having one thiol group in one molecule)

<Episulfide compounds>
Episulfide compound 1: Episulfide compound represented by the following formula

<Inorganic substance having sulfur atom and / or selenium atom>
S: Sulfur alone <Catalyst>
Tetrabutylphosphonium bromide <regulator>
Dibutyltin dichloride

<Preparation of transparent member forming composition and cured product thereof>
The materials shown in Table 2 are mixed in the amounts (unit: mass%) shown in Table 2 to obtain a mixture, and a catalyst and a regulator are added to the mixture to obtain a transparent member forming composition as a uniform liquid. It was. In addition, the quantity of the catalyst and the quantity of the regulator were both 0.02 mass% with respect to the said mixture.
The composition for forming a transparent member was degassed at 600 Pa for 0.5 hour. After degassing, the transparent member-forming composition was filtered with a 1 μm Teflon (registered trademark) filter. The filtered composition for forming a transparent member was poured into a glass mold assembled by fixing the glass member with a tape under a normal temperature environment (20 ° C.). This glass mold was put into an oven, heated from 20 ° C. to 100 ° C. over 24 hours, and then the transparent member forming composition was cured at 100 ° C. for 5 hours. After the curing was completed, the glass mold was taken out from the oven, and released from the glass mold and annealed at 120 ° C. for 30 minutes to obtain a colorless and transparent cured product.

<Measurement of refractive index>
The refractive index of the obtained cured product was measured at 20 ° C. using a Purfrich refractometer. The results are shown in Table 2.
<Measurement of glass transition temperature (Tg)>
The glass transition temperature of the obtained cured product was measured using the TMA method. The results are shown in Table 2.

  As can be seen from Table 1, obtained from the compositions of Examples 1 to 9 containing the compound represented by the general formula (1) and a thiol group-containing compound having at least two thiol groups in one molecule. The cured product had a high refractive index and a high glass transition temperature, and was excellent in optical properties and heat resistance. In Examples 7 and 8, the refractive index was further improved by adding sulfur as an inorganic substance to the composition.

  On the other hand, although it contains a thiol group-containing compound having at least two thiol groups in one molecule, the curing obtained from the compositions of Comparative Examples 1 and 2 that does not contain the compound represented by the general formula (1) The product had a low glass transition temperature and poor heat resistance. Moreover, although it contains the thiol group containing compound which has at least 2 thiol group in 1 molecule, it contains the comparative compound 1 which is an epoxy group containing compound instead of the compound represented by the said General formula (1). The cured product obtained from the composition of Comparative Example 3 had a low refractive index and a low glass transition temperature, and was inferior in optical properties and heat resistance. Further, a thiol having one thiol group in one molecule instead of a thiol group-containing compound having at least two thiol groups in one molecule, although containing the compound represented by the general formula (1) The composition of Comparative Example 4 containing the group-containing compound was not cured, and the refractive index and glass transition temperature could not be evaluated.

Claims (4)

A composition for forming a transparent member comprising a vinyl group-containing compound represented by the following general formula (1) and a thiol group-containing compound having at least two thiol groups in one molecule.

Wherein W ¹ and W ² independently represent a group represented by the following general formula (2), a group represented by the following general formula (4), a hydroxyl group, or a (meth) acryloyloxy group, At least one of W ¹ and W ² is a group represented by the general formula (2), ring Y ¹ and ring Y ² represent the same or different aromatic hydrocarbon rings, and R is a single bond or a substituent. A methylene group which may have a substituent, an ethylene group which may have a substituent and may contain a hetero atom between two carbon atoms, a group represented by -O-, a group represented by -NH-, Or a group represented by -S-, R ^3a and R ^3b independently represent a cyano group, a halogen atom, or a monovalent hydrocarbon group, and n1 and n2 independently represent an integer of 0 to 4.)

(Wherein ring Z represents an aromatic hydrocarbon ring, X is a group represented by a single bond or -S-, R ¹ represents a Tan'yui case, R ² is a monovalent hydrocarbon group, a hydroxyl group, -OR ^4a group, -SR ^4b group, acyl group, alkoxycarbonyl group, halogen atom, nitro group, cyano group, mercapto group, carboxyl group, amino group, carbamoyl group, -NHR ^4c A group, a group represented by -N (R ^4d ) ₂ , a (meth) acryloyloxy group, a sulfo group, or a monovalent hydrocarbon group, a group represented by -OR ^4a , a group represented by -SR ^4b , an acyl group, At least a part of the hydrogen atoms bonded to the carbon atom contained in the alkoxycarbonyl group, the group represented by —NHR ^4c , or the group represented by —N (R ^4d ) ₂ is a monovalent hydrocarbon group, hydroxyl group, —OR ^4a Indicated by Group, a group represented by ^{-SR 4b,} an acyl group, an alkoxycarbonyl group, a halogen atom, a nitro group, a cyano group, a mercapto group, a carboxyl group, an amino group, a carbamoyl group, a group represented by -NHR ^4c, -N (R ^4d ) represents a group represented by ₂ , a (meth) acryloyloxy group, a mesyloxy group, or a sulfo group, R ^{4a to} R ^4d independently represent a monovalent hydrocarbon group, and m represents 0 or more. Indicates an integer.)

(In the formula, rings Z, X, R ¹ , R ² , and m are as described above.)   The composition for forming a transparent member according to claim 1, wherein the ring Z is a benzene ring or a naphthalene ring. The transparent member which consists of hardened | cured material of the composition for transparent member formation of Claim 1 or 2 . The transparent member according to claim 3 , which is a lens.