JP4596851B2 - High refractive index thietane compound - Google Patents

Description

  The present invention relates to a thietane compound suitably used in the field of resins such as optical materials that require high refractive index and high transparency, and a cured resin thereof.

In recent years, plastic lenses are rapidly spreading to optical elements such as spectacle lenses and camera lenses because they are lighter and harder to break than inorganic lenses and can be dyed.
The performance required for these plastic lenses is high refractive index and high Abbe number as optical performance, and high heat resistance and low specific gravity as physical properties.

  Currently, polythiourethane resins in which sulfur atoms are introduced into the resin are known as resins that satisfy these required performances to some extent. The polythiourethane resin is a resin having an excellent balance such as a high refractive index and good impact resistance (see, for example, Patent Document 1).

  However, there is a demand for higher refractive index and higher Abbe number, but on the other hand, both the refractive index and Abbe number are contradictory properties that the Abbe number decreases as the refractive index increases. It is very difficult to improve at the same time. In view of this, studies have been actively conducted to increase the refractive index while suppressing the decrease in the Abbe number.

The most representative proposal among these studies is a method using an episulfide compound. (For example, see Patent Document 2 and Patent Document 3)
A method of using a thietane compound as a compound different from episulfide has been proposed. (For example, see Patent Document 4)
JP-A-63-46213 WO-89 / 10575 publication Japanese Patent Laid-Open No. 9-110979 JP 2003-327583 A

  According to the methods of Patent Documents 3 and 4, it is considered that a high refractive index can be realized while having a relatively high Abbe number. Patent Document 4 exemplifies a number of novel thietane compounds, and the production method thereof is also described in detail. However, although the cured resin obtained from the compound described in the patent document has a refractive index of about 1.68 to 1.74, and is a material that is satisfactory to some extent, the dyeability and heat resistance of the cured resin, The strength was not satisfactory. Therefore, development of a material having a high refractive index and a high Abbe number equal to or higher than those described in Patent Document 4 and having high performance satisfying high dyeability, high heat resistance, and high strength is required. ing.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have succeeded in producing a novel thietane compound, and the resin obtained by curing the compound has a high refractive index and also has an Abbe number. The present inventors have found that excellent optical physical properties such as high, and further excellent physical properties such as high dyeability and heat resistance and high tensile strength can be obtained.
That is, the present invention
Relates thietane compound having one or more skeleton and two or more thietanyl groups selected dithio acetal skeleton or dithioketal bone rated or found in the molecule, in particular at most.

[1] a thietane compound having one or more skeleton and two or more thietanyl groups selected from dithio acetal skeleton and dithioketal bone skeleton or Ranaru group in the molecule, represented by the following formula (1) Structure A thietane compound having:

（式中、Ｒ１、およびＲ２は、それぞれ独立に、水素原子、フェニル基、チエニル基または下記式（＊）に示す基を表す。ただし、Ｒ１とＲ２が共に水素原子となることはない。）

［２］ Ｒ１及び／またはＲ２が芳香族環及び／または複素環を有する構造である［１］に記載のチエタン化合物。
［３］ 前記チエタン化合物が２−［１，１−ビス（３−チエタニルチオ）メチル］チオフェン、３−［１，１−ビス（３−チエタニルチオ）メチル］チオフェン、１−［１，１−ビス（３−チエタニルチオ）メチル］ベンゼン、１，４−ビス［１，１−ビス（３−チエタニルチオ）メチル］ベンゼンのいずれかである［１］または［２］に記載のチエタン化合物。
［４］ ［１］乃至［３］のいずれか１項に記載のチエタン化合物を含有する重合性組成物。
［５］ さらに単体の硫黄を含有する［４］に記載の重合性組成物。
［６］ ［４］または［５］に記載の重合性組成物を硬化させて得られた樹脂。
［７］ ［６］に記載の樹脂からなる光学材料。ここで、「からなる」とは、当該光学材料の全部が当該樹脂で構成されている場合、および、当該光学材料の一部が当該樹脂で構成されている場合、の双方を含む趣旨である。
［８］ ［４］または［５］に記載の重合性組成物を注型重合する工程を含む、樹脂の製造方法。
［９］ ３−メルカプトチエタンと、アルデヒド基またはケト基を１つ以上有する化合物とを原料として［１］乃至［３］のいずれか１項に記載のチエタン化合物を製造する方法。ここで、後者の化合物は、アルデヒド基またはケト基の１種類のみを１つ以上有していても良いし、２種類以上を組み合わせて（１つ以上）有していても良い。
［１０］上記アルデヒド基またはケト基を１つ以上有する化合物が、アルデヒド基またはケト基を合計で少なくとも２つ有するものである［９］に記載の製造方法。ここで、後者の化合物は、アルデヒド基またはケト基の１種類のみを２つ以上有していても良いし、２種類以上を組み合わせて有していてもよい。
［１１］上記アルデヒド基またはケト基を１つ以上有する化合物が、更に、芳香環及び／または複素環を有するものである［９］または［１０］に記載の製造方法。
［１２］ 温度を０〜１２０℃の範囲内とし、触媒としてプロトン酸及び／またはルイス酸を使用して共沸脱水反応を行うことを特徴とする［９］乃至［１１］のいずれか１項に記載の製造方法。

(In the formula, R 1 and R 2 each independently represent a hydrogen atom, a phenyl group, a thienyl group or a group represented by the following formula (*). However, R 1 and R 2 are not both hydrogen atoms.)

[2] The thietane compound according to [1], wherein R1 and / or R2 has a structure having an aromatic ring and / or a heterocyclic ring.
[3] before Symbol thietane compound 2- [1,1-bis (3-thietanylthio) methyl] thiophene, 3- [1,1-bis (3-thietanylthio) methyl] thiophene, 1- [1,1-bis The thietane compound according to [1] or [2], which is any one of (3-thietanylthio) methyl] benzene and 1,4-bis [1,1-bis (3-thietanylthio) methyl] benzene.
[4] A polymerizable composition containing the thietane compound according to any one of [1] to [3].
[5] The polymerizable composition according to [4], further containing a single sulfur.
[6] A resin obtained by curing the polymerizable composition according to [4] or [5].
[7] An optical material comprising the resin according to [6]. Here, “consisting of” means that both the case where the entire optical material is made of the resin and the case where a part of the optical material is made of the resin are included. .
[8] A method for producing a resin, comprising a step of cast polymerization of the polymerizable composition according to [4] or [5].
[9] 3-Mel and mercapto Chie Tan, a method for producing a thietane compound according to any one of [1] to [3] and a compound having an aldehyde group or keto group one or more as a raw material. Here, the latter compound may have one or more of only one kind of aldehyde group or keto group, or may have two or more kinds in combination (one or more).
[10] The production method according to the compound having the aldehyde group or keto group one or more, those having at least two aldehyde or keto group in total [9]. Here, the latter compound may have two or more of only one kind of aldehyde group or keto group, or may have two or more kinds in combination.
[11] The production method according to [9] or [10], wherein the compound having one or more aldehyde groups or keto groups further has an aromatic ring and / or a heterocyclic ring.
[12] Any one of [9] to [11], wherein the azeotropic dehydration reaction is performed using a proton acid and / or a Lewis acid as a catalyst at a temperature in the range of 0 to 120 ° C. The manufacturing method as described in.

  According to the present invention, a compound useful as a raw material for a novel optical material in the field of high refractive index is obtained, and the optical physical properties of the resin obtained by polymerization and curing are very high, and the dyeability and heat resistance are also high. Contributes to high refractive index and thinning in the field of eyeglass lenses.

  Hereinafter, the present invention will be described in detail. First, the thietane compound of the present invention will be described.

Thietane compounds of the present invention relates to compounds having one or more skeleton and two or more thietanyl groups selected dithio acetal skeleton or dithioketal bone rated or found in the molecule.

  Here, the dithioacetal skeleton means a structure represented by the following formula (2).

（式中Ｒ３は、チエタニル基を含まない場合は、直鎖もしくは分岐の炭素数１〜４のチア化されていても良い炭化水素基、環状の炭素数３〜６のチア化されていても良い炭化水素基、１，４−ジチアン基、アリーレン基、または、アラルキレン基を表し、チエタニル基を含む場合は、直鎖もしくは分岐の炭素数３〜６のチア化されていても良い炭化水素基、または、環状の炭素数３〜１２のチア化されていても良い炭化水素基を表す。なお、ここでいう炭素数は、チア化されている場合にあっては、チア化後の炭素数を示す。）
また、ジチオケタール骨格とは、下記式（３）で表される構造を意味する。

(In the formula, when R3 does not contain a thietanyl group, it may be a linear or branched hydrocarbon group having 1 to 4 carbon atoms that may be thiated or a cyclic group having 3 to 6 carbon atoms. A good hydrocarbon group, a 1,4-dithiane group, an arylene group, or an aralkylene group, and when containing a thietanyl group, a linear or branched hydrocarbon group having 3 to 6 carbon atoms that may be thiated Or a cyclic hydrocarbon group having 3 to 12 carbon atoms which may be thiated, and the number of carbons herein refers to the number of carbons after thialation. Is shown.)
The dithioketal skeleton means a structure represented by the following formula (3).

（式中Ｒ４、Ｒ５は、それぞれ独立に、チエタニル基を含まない場合は、直鎖もしくは分岐の炭素数１〜４のチア化されていても良い炭化水素基、環状の炭素数３〜６のチア化されていても良い炭化水素基、１，４−ジチアン基、アリーレン基、または、アラルキレン基を表し、チエタニル基を含む場合は、直鎖もしくは分岐の炭素数３〜６のチア化されていても良い炭化水素基、または、環状の炭素数３〜１２のチア化されていても良い炭化水素基を表す。なお、ここでいう炭素数は、チア化されている場合にあっては、チア化後の炭素数を示す。）

(In the formula, each of R4 and R5 independently represents a linear or branched hydrocarbon group having 1 to 4 carbon atoms which may be thiated, or a cyclic group having 3 to 6 carbon atoms, when it does not contain a thietanyl group. Represents a hydrocarbon group, 1,4-dithiane group, arylene group, or aralkylene group that may be thiated, and when it contains a thietanyl group, it is a straight or branched thiated with 3 to 6 carbon atoms. Or a cyclic hydrocarbon group having 3 to 12 carbon atoms which may be thiated, and the number of carbons herein is a thiated group. Indicates the number of carbons after thialation. )

  Further, the thietanyl group is a hydrocarbon group having a 4-membered ring structure, and refers to a group in which one of the four carbons is substituted with sulfur. For example, a thietanyl group in which the 3-position carbon is substituted with sulfur is referred to as a 3-thietanyl group. If the number of thietanyl groups is increased, the heat resistance of the resulting cured resin is preferably improved, but if there are five or more, the refractive index of the resulting cured resin will be lowered, and therefore 3 to 4 functional groups may be preferable. .

  The thietane compound of the present invention has a high refractive index and a high Abbey when the molecular weight is 1000 or less, unlike, for example, a dithioacetal or dithioketal bond and a thietanyl group at the end of a long-chain alkyl structure. It is advantageous to satisfy the purpose such as number. Moreover, when handling property at the time of manufacturing a resin or an optical material is taken into consideration, the molecular weight is desirably 1000 or less. Therefore, the molecular weight is more preferably 950 or less, and even more preferably 900 or less. The molecular weight is preferably 250 or more in consideration of the possibility that the workability is more stable due to the relationship with volatility and the like. If it is 280 or more, it is more preferable.

The thietane compound of the present invention specifically, have a structure represented by the following general formula (1) in the following general formula (1), R1, and R2 are each independently a hydrogen atom, phenyl Represents a group, a thienyl group or a group represented by the above formula (*). However, R1 and R2 are not both hydrogen atoms.

（式中、Ｒ１、Ｒ２は、それぞれ独立に、チエタニル基を含まない場合、水素原子、直鎖もしくは分岐の炭素数１〜４のチア化されていても良い炭化水素基、環状の炭素数３〜６のチア化されていても良い炭化水素基、１，４−ジチアン基、アリーレン基、またはアラルキレン基を表し、チエタニル基を含む場合、直鎖もしくは分岐の炭素数３〜６のチア化されていても良い炭化水素基、または環状の炭素数３〜１２のチア化されていても良い炭化水素基を表す。ただし、Ｒ１とＲ２が共に水素原子となることはない。なお、ここでいう炭素数は、チア化されている場合にあっては、チア化後の炭素数を示す。）
Ｒ１とＲ２が共に水素である場合、目的の高屈折率が満足されない為、共に水素である場合は好ましい化合物（１）には該当しない。また、Ｒ１、Ｒ２中にはチエタン環を含んでいても良い。チエタン環を有する場合と有さない場合では、許容される分子の構造が異なる為、Ｒ１とＲ２の規定については、それぞれを分けて規定する。

(In the formula, each of R1 and R2 independently represents a hydrogen atom, a linear or branched hydrocarbon group having 1 to 4 carbon atoms which may be thiated, or a cyclic carbon number of 3 when it does not contain a thietanyl group. -6 represents a thiated hydrocarbon group, 1,4-dithiane group, arylene group, or aralkylene group, and when it contains a thietanyl group, it is a straight chain or branched thiocyanate having 3 to 6 carbon atoms. Represents a hydrocarbon group that may be substituted or a cyclic hydrocarbon group having 3 to 12 carbon atoms that may be thiated, provided that R1 and R2 are not both hydrogen atoms. (The number of carbons indicates the number of carbons after thialation if it is thialated.)
When R1 and R2 are both hydrogen, the target high refractive index is not satisfied. Therefore, when both R1 and R2 are hydrogen, it is not a preferable compound (1). R1 and R2 may contain a thietane ring. In the case of having a thietane ring and in the case of not having a thietane ring, the permissible molecular structure is different.

  When R1 does not contain a thietanyl group, R1 may be hydrogen, a linear or branched hydrocarbon group having 1 to 4 carbon atoms which may be thiated, or a cyclic group having 3 to 6 carbon atoms. Represents a good hydrocarbon group, 1,4-dithiane group, arylene group or aralkylene group. R1 may be thiated in any case, but the thietanyl group does not fall into this category. Therefore, R1 is preferably a structure containing a sulfur atom such as a thiane group, a thiolane group, a dithiane group, a dithiolane group, and a dithietane group, Those having such an aromatic ring or heterocyclic ring are mentioned. Furthermore, it is more preferable to increase the sulfur content.

  When R1 contains a thietanyl group, R1 is a linear or branched hydrocarbon group having 3 to 6 carbon atoms which may be thiated, or a cyclic hydrocarbon group having 3 to 12 carbon atoms which may be thiated. Represents. Preferred examples of R1 include those described above, and further include a thietanyl group. Furthermore, it may have a dithioacetal skeleton and may have two thietanylthio groups. When the dithio structure of the dithioacetal skeleton is composed of two thiotanylthio group thiostructures, the thietane compound of the present invention is a tetrafunctional thietane compound having four thietanylthio groups.

  In this case, if the number of thietanyl groups is increased, the heat resistance of the obtained cured resin is preferably improved, but if it has 5 or more, the refractive index of the obtained cured resin is lowered, and therefore 3 to 4 functional groups are preferred. There is a case.

  R2 preferably has the same structure as R1, and when R1 is not a hydrogen atom, R2 may be a hydrogen atom.

  Here, among the compounds having the structure represented by the formula (1), specific examples of particularly preferable compounds include 2- [1,1-bis (3-thietanylthio) methyl] thiophene, 3- [1,1- Bis (3-thietanylthio) methyl] thiophene, 1- [1,1-bis (3-thietanylthio) methyl] benzene, 1,4-bis [1,1-bis (3-thietanylthio) methyl] benzene, 1,2 -Bis [1,1-bis (3-thietanylthio) methyl] benzene, 1,1,1-tris (3-thietanylthio) methane, 2- [1,1-bis (3-thietanylthio) methylthio] thiophene, 1, 1-bis (3-thietanylthio) -1- (1,3-dithiolane-2-thio) methane, 1,1,1,1-tetrakis (3-thietanylthio) methane, 1,1,2,2-tetra S (3-thietanylthio) ethane, 1,1,3,3-tetrakis (3-thietanylthio) propane, 1,1-bis (3-thietanylthio) -2- (3-thietanylthio) ethane and the like can be mentioned. However, it is not limited only to these exemplary compounds.

  Of these compounds, a compound having an aromatic ring or a heterocyclic ring is preferable because it often has excellent dyeability of a resin obtained by polymerization and curing. Other compounds are preferable because they are very high in heat resistance and often have very high strength such as impact resistance as compared with conventional thietane compounds. In addition, these compounds have good reactivity to the polymerization catalyst, can be polymerized from a relatively low temperature range, hardly cause striae of optical materials made of resin obtained by polymerization and curing, and may improve yield. Is expensive.

  Then, it describes about the manufacturing method of the thietane compound of this invention.

As a method for producing a thietane compound having one or more dithioacetal skeleton or dithioketal skeleton and two or more thietanyl groups in the molecule of the present invention, a compound and a mercapto compound having an aldehyde or carbonyl group such as ketone the condensation reaction and acetal occurs between, and a method of utilizing the acetal exchange reaction occurs between the compound and the mercapto compound having a group such as Keta Le. At this time, when an inorganic base or an organic base, a proton acid such as an inorganic acid or an organic acid, a Lewis acid, or the like is used as a catalyst, the target product may be produced with higher purity or higher yield. Of these, protonic acids and Lewis acids are particularly preferred.

The reaction solvent to be used in performing the reaction without solvent or in a polar solvent alone or a compound or an acetal with a source of aldehyde and carbonyl groups such as ketone, a compound a mercapto group with a group such as Keta Le Any compound can be used as long as the compound can be dissolved, but it is also possible to use a mixed solvent of a polar solvent and a nonpolar solvent. Specific examples of the polar solvent here include alcohols such as water, methanol and ethanol, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, esters such as methyl acetate, ethyl acetate, propyl acetate and butyl acetate, Examples include ethers such as diethyl ether and tetrahydrofuran, and aprotic polar solvents such as dimethylformamide, dimethylimidazolidinone, and dimethyl sulfoxide, but are not limited to the exemplified compounds. Specific examples of nonpolar solvents include aromatic hydrocarbons such as benzene, toluene and xylene and their halogen substitution products, aliphatic hydrocarbons such as hexane and cyclohexane, and halogenation such as dichloromethane, chloroform and carbon tetrachloride. Although hydrocarbons etc. are mentioned, it is not necessarily limited to an exemplary compound.

  In order to advance the reaction by azeotropic dehydration, it is preferable to use a nonpolar solvent rather than a polar solvent, and a solvent having an azeotropic property to water may be selected.

  Examples of catalysts that can be used here include, as inorganic bases, alkali metal or alkaline earth metal hydroxides, alkali metal or alkaline earth metal carbonates, alkali metal or alkaline earth metal bicarbonates. And organic bases include tertiary amines, secondary amines, primary amines, metal alkoxides, trialkyl phosphines, triaryl phosphines, quaternary ammonium salts, quaternary phosphonium salts, and the like. Examples of the protonic acid include inorganic acids and organic acids. More specifically, examples of the inorganic acids include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and the like. Examples of the organic acids include formic acid, acetic acid, and propion. Examples include acid, phthalic acid, methanessulfonic acid, p-toluenesulfonic acid, trihalogenoacetic acid, trihalogenomethanesulfonic acid, and the like. Lewis acids include dimethyltin dichloride, dibutyltin dichloride, dibutyltin dilaurate, dibutyltin diacetate, tetrachlorotin, dibutyltin oxide, diacetoxytetrabutyldistanoxane, zinc chloride, acetylacetone zinc, aluminum chloride, aluminum fluoride , Triphenylaluminum, acetylacetonealuminum, isopropoxidealuminum, tetrachlorotitanium and its complexes, tetraiodo titanium, dichlorotitanium diisopropoxide, titanium isopropoxide, etc., titanium alkoxide, calcium acetate, boron trifluoride, three Boron fluoride diethyl ether complex, boron trifluoride piperidine complex, boron trifluoride ethylamine complex, boron trifluoride acetic acid complex, boron trifluoride phosphate complex, boron trifluoride t-butylmethyl ether complex Boron trifluoride dibutyl ether complex, boron trifluoride THF complex, boron trifluoride methylsulfide complex, boron trifluoride phenol complex, etc., boron trifluoride various complexes and boron trichloride various complexes, etc. Examples thereof include boron halide compounds and complexes thereof. Preferred among these are acidic compounds, but inorganic acids such as hydrochloric acid and sulfuric acid, organic acids such as methanessulfonic acid, p-toluenesulfonic acid, trihalogenoacetic acid, and trihalogenomethanesulfonic acid, Lewis acid is more preferred.

  The reaction temperature is preferably in the range of 0 ° C. to 120 ° C., but a lower temperature may be selected depending on the reaction rate, the stability of the raw materials used, and the reaction results. It is better to avoid crystallization and other reactions because they cause problems. Therefore, 5 to 110 ° C is preferable, and 10 to 100 ° C is more preferable. When a solvent having a boiling point in a relatively high temperature region is used, azeotropic dehydration proceeds well if the boiling point is lowered under reduced pressure conditions.

In order to produce the thietane compound of the present invention, it is preferable to use 3-mercaptothietane and a compound having one or more aldehyde groups or keto groups as raw materials. If the latter compound has two or more aldehyde groups or keto groups in total, the resulting thietane compound has more thietanyl groups, which is preferable from the viewpoint of heat resistance and the like. When the latter compound further has an aromatic ring or a heterocyclic ring, it is often preferable that the obtained resin has excellent dyeability.

Compounds having more than one aldehyde group or keto group, acetal preferably has a skeleton such Keta Le.

  In the case of the present invention, for example, when 3-mercaptothietane and a compound having an aldehyde group are used, the reaction proceeds as shown in the following formula (4).

式中、Ｒは、水素原子、または、チエタニル基を含まない場合、直鎖もしくは分岐の炭素数１〜４のチア化されていても良い炭化水素基、環状の炭素数３〜６のチア化されていても良い炭化水素基、１，４−ジチアン基、アリーレン基、アラルキレン基を表し、チエタニル基を含む場合、直鎖もしくは分岐の炭素数３〜６のチア化されていても良い炭化水素基、環状の炭素数３〜１２のチア化されていても良い炭化水素基を表す。

In the formula, when R does not include a hydrogen atom or a thietanyl group, it may be a straight chain or branched hydrocarbon group having 1 to 4 carbon atoms which may be thiated, or a cyclic group having 3 to 6 carbon atoms. Represents a hydrocarbon group, 1,4-dithian group, arylene group, aralkylene group, which may be substituted, and when it contains a thietanyl group, it may be a straight or branched hydrocarbon having 3 to 6 carbon atoms and may be thiated And a cyclic hydrocarbon group having 3 to 12 carbon atoms which may be thiated.

For this reaction, a compound having a raw material aldehyde or carbonyl group such as ketone, acetal, among the compounds such Keta Le, for compounds having an aldehyde or ketone, acetal, ketal groups, the use of 3-mercaptothietane the amount is theoretically necessary and is 2 mol per mol of the respective functional groups. However, in order to improve the production rate of the target product, it is preferable to use the number of moles of the starting 3-mercaptothietan more than necessary. Specifically, it is more preferable to use 1.1 times or more the required amount. It is more preferable to use 1.2 times or more. Considering economical efficiency and purification load, it is preferably 2 times or less.
If the stability of 3-mercaptothietane is considered and the yield of the target product is given top priority, selectivity may be improved by increasing the amount used and increasing the reaction rate. However, it is preferable to remove excess 3-mercaptothietane in consideration of the properties of the finally obtained compound and the resin obtained by polymerization and curing. In such a case, excess 3-mercaptothietan is preferably treated as an alkali salt, recovered and reused.

  Next, it describes about the polymeric composition containing the thietane compound which has a structure represented by Formula (1) of this invention. A constituent requirement of the polymerizable composition of the present invention is to contain a thietane compound having a structure represented by the formula (1), and the content thereof is 10 to the entire polymerizable composition. It is preferably contained in an amount of not less than 100% by weight. Adjustment of optical properties such as refractive index and Abbe number of resin formed by curing the polymerizable composition, hue, light resistance and weather resistance, heat resistance, impact resistance, hardness, specific gravity, linear expansion coefficient, polymerization shrinkage To adjust various physical properties such as rate, water absorption, hygroscopicity, chemical resistance, viscoelasticity, adjustment of transmittance and transparency, viscosity of polymerizable composition, and other handling and handling methods of storage, etc. For the purpose of improving the resin and improving the handling properties, methods and operations generally used when synthesizing organic compounds such as purification, washing, heat insulation, cold preservation, filtration, and reduced pressure treatment are applied. Or the like as a stabilizer or a resin modifier may be preferable for the purpose of obtaining a good resin. Examples of compounds that can be added to improve stability such as long-term storage stability, polymerization stability, and thermal stability include compounds such as polymerization retarders, polymerization inhibitors, oxygen scavengers, and antioxidants. However, the present invention is not limited to those described.

  Here, it describes about a resin modifier. Examples of the resin modifier include known thietane compounds other than the present invention, dithietane compounds, trithietane compounds, thiolane compounds, dithiolane compounds, trithiolane compounds, dithian compounds, trithiane compounds, episulfide compounds and epoxy compounds, amine compounds Thiol compounds that can be used as raw materials of the present invention, hydroxy compounds including phenolic compounds, iso (thio) cyanate compounds, mercapto organic acids, organic acids and anhydrides, amino acids and mercaptoamines, (meth) Examples include olefins including acrylates, cyclic organic compounds and inorganic compounds having sulfur atoms or selenium atoms, and simple sulfurs. Among these resin modifiers, olefins including epoxy compounds, iso (thio) cyanate compounds, and (meth) acrylates are more preferable for overcoming the brittleness of the resulting resin and improving impact resistance. Amine compounds, thiol compounds, and phenol compounds are preferred for improving the hue of the resulting resin. Among these, a compound having one or more SH groups is more preferable. A compound having two or more SH groups and having a sulfide bond is more preferable. Cyclic organic compounds and inorganic compounds having a sulfur atom or a selenium atom are preferable for improving the refractive index of the resin, and in particular, when a single sulfur is used, the operation is simple and the effect of improving the refractive index is particularly large. preferable. As a single sulfur addition amount, 3 to 30% by weight may be used with respect to the entire polymerizable composition. Considering the heat resistance and brittleness of the resulting resin, it is preferable to use 5 to 25% by weight.

Specific examples of thietane compounds other than the thietane compound of the present invention that can be used as the resin modifier of the present invention include bis (3-thietanyl) sulfide, 1,4-bis (3-thietanyl) -1,3, 4-trithiabutane, 1,6-bis (3-thietanyl) -1,3,4,6, -tetrathiahexane, 1,6-bis (3-thietanyl) -1,3,5,6, -tetrathia Hexane, 1,1-bis (3-thietanylthio) methane, 1,2-bis (3-thietanylthio) ethane, 1,2-bis (3-thietanylthio) propane, 1,3-bis (3-thietanylthio) propane, 1,3-bis (3-thietanylthio) -2-methylpropane, 1,4-bis (3-thietanylthio) butane, 1,4-bis (3-thietanylthio) -2-methylbutane, 1,3-bis 3-thietanylthio) butane, 1,5-bis (3-thietanylthio) pentane, 1,5-bis (3-thietanylthio) -2-methylpentane, 1,5-bis (3-thietanylthio) -3-thiapentane, , 6-bis (3-thietanylthio) hexane, 1,6-bis (3-thietanylthio) -2-methylhexane, 3,8-bis (3-thietanylthio) -3,6-dithiaoctane, 1,2,3- Tris (3-thietanylthio) propane, 2,2-bis (3-thietanylthio) -1,3-bis (3-thietanylthiomethyl) propane, 2,2-bis (3-thietanylthiomethyl) -1- (3-thietanylthio) butane, 1,5-bis (3-thietanylthio) -2- (3-thietanylthiomethyl) -3-thiapentane, 1,5-bis (3-thie Nylthio) -2,4-bis (3-thietanylthiomethyl) -3-thiapentane, 1- (3-thietanylthio) -2,2-bis (3-thietanylthiomethyl) -4-thiahexane, 1,5 , 6-Tris (3-thietanylthio) -4- (3-thietanylthiomethyl) -3-thiahexane, 1,8-bis (3-thietanylthio) -4- (3-thietanylthiomethyl) -3,6 -Dithiaoctane, 1,8-bis (3-thietanylthio) -4,5-bis (3-thietanylthiomethyl) -3,6-dithiaoctane, 1,8-bis (3-thietanylthio) -4,4-bis (3-thietanylthiomethyl) -3,6-dithiaoctane, 1,8-bis (3-thietanylthio) -2,5-bis (3-thietanylthiomethyl) -3,6-dithiaoctane, 1,8- Screw (3-thietanylthio) -2,4,5-tris (3-thietanylthiomethyl) -3,6-dithiaoctane, 1,1,1-tris [[2- (3-thietanylthio) ethyl] thiomethyl] -2 -(3-thietanylthio) ethane, 1,1,2,2-tetrakis [[2- (3-thietanylthio) ethyl] thiomethyl] ethane, 1,11-bis (3-thietanylthio) -4,8-bis (3 -Thietanylthiomethyl) -3,6,9-trithiaundecane, 1,11-bis (3-thietanylthio) -4,7-bis (3-thietanylthiomethyl) -3,6,9-trithia Undecane, 1,11-bis (3-thietanylthio) -5,7-bis (3-thietanylthiomethyl) -3,6,9-trithiaundecane, 1,1,3,3-tetrakis (3-thietanylthio) Tilthio) propane, 1,1,2,2-tetrakis (3-thietanylthiomethylthio) ethane, 3- (3-thietanylthiomethyl) -1,5-di (3-thietanylthio) -2,4-dithiapentane Chain aliphatic 3-thietanylthio compounds such as bis (3-thietanyl) disulfide, bis (3-thietanyl) trisulfide, bis (3-thietanyl) tetrasulfide and the like, and 1,3 -Bis (3-thietanylthio) cyclohexane, 1,4-bis (3-thietanylthio) cyclohexane, 1,3-bis (3-thietanylthiomethyl) cyclohexane, 1,4-bis (3-thietanylthiomethyl) cyclohexane 2,5-bis (3-thietanylthiomethyl) -1,4-dithiane, 4,6-bis (3 Thietanylthiomethyl) -1,3-dithiane, 4,5-bis (3-thietanylthiomethyl) -1,3-dithiolane, 2,4-bis (3-thietanylthiomethyl) -1,3- Dithietane, 2,5-bis [[2- (3-thietanylthio) ethyl] thiomethyl] -1,4-dithiane, 2,5-bis (3-thietanylthiomethyl) -2,5-dimethyl-1,4 A cycloaliphatic 3-thietanylthio compound such as dithiane, 2-bis (3-thietanylthio) methyl-1,3-dithiolane, and
1,2-bis (3-thietanylthio) benzene, 1,3-bis (3-thietanylthio) benzene, 1,4-bis (3-thietanylthio) benzene, 1,2-bis (3-thietanylthiomethyl) benzene 1,3-bis (3-thietanylthiomethyl) benzene, 1,4-bis (3-thietanylthiomethyl) benzene, bis [4- (3-thietanylthio) phenyl] methane, 2,2-bis [ 4- (3-thietanylthio) phenyl] propane, bis [4- (3-thietanylthio) phenyl] sulfide, bis [4- (3-thietanylthio) phenyl] sulfone, 4,4′-bis (3-thietanylthio) biphenyl, etc. Aromatic 3-thietanylthio compounds of 1,3-bis (3-thietanylthio) propan-1-one, Examples thereof include 3-bis (3-thietanylthio) -2-methylpropan-1-one, but are not limited to these exemplary compounds. Among the exemplified compounds, preferred compounds include bis (3-thietanyl) sulfide, 1,4-bis (3-thietanyl) -1,3,4-trithiabutane, 1,6-bis (3-thietanyl) -1, 3,4,6, -tetrathiahexane, 1,6-bis (3-thietanyl) -1,3,5,6, -tetrathiahexane, 1,1-bis (3-thietanylthio) methane and 1,2 -Bis (3-thietanylthio) ethane, 1,2,3-tris (3-thietanylthio) propane, 1,8-bis (3-thietanylthio) -4- (3-thietanylthiomethyl) -3,6-dithiaoctane 1,11-bis (3-thietanylthio) -4,8-bis (3-thietanylthiomethyl) -3,6,9-trithiaundecane, 1,11-bis (3-thietanylthio) -4,7 -Screw 3-thietanylthiomethyl) -3,6,9-trithiaundecane, 1,11-bis (3-thietanylthio) -5,7-bis (3-thietanylthiomethyl) -3,6,9-tri Thiaundecane, 2,5-bis (3-thietanylthiomethyl) -1,4-dithiane, 2,5-bis [[2- (3-thietanylthio) ethyl] thiomethyl] -1,4-dithiane, 2, 5-bis (3-thietanylthiomethyl) -2,5-dimethyl-1,4-dithiane, 4,5-bis (3-thietanylthiomethyl) -1,3-dithiolane, 2,4-bis ( 3-thietanylthiomethyl) -1,3-dithietane, 2-bis (3-thietanylthio) methyl-1,3-dithiolane, bis (3-thietanyl) disulfide, bis (3-thietanyl) trisulfide, bis (3 -Chieta And bis (3-thietanyl) sulfide, 1,4-bis (3-thietanyl) -1,3,4-trithiabutane, 1,6-bis (3-thietanyl). -1,3,4,6, -tetrathiahexane, 1,6-bis (3-thietanyl) -1,3,5,6, -tetrathiahexane, bis (3-thietanylthio) methane, bis (3- Thietanylthiomethyl) sulfide, 2-bis (3-thietanylthio) methyl-1,3-dithiolane, bis (3-thietanyl) disulfide, bis (3-thietanyl) trisulfide, bis (3-thietanyl) tetrasulfide. .

Next, specific examples of the episulfide compound as the resin modifier of the present invention include bis (1,2-epithioethyl) sulfide, bis (epithioethylthio) methane, bis (epithioethylthio) benzene, bis [ Epithioethyl compounds such as 4- (epithioethylthio) phenyl] sulfide, bis [4- (epithioethylthio) phenyl] methane, bis (1,2-epithioethyl) disulfide, bis (2,3-epithiopropyl) Sulfide, bis (2,3-epithiopropylthio) methane, 1,2-bis (2,3-epithiopropylthio) ethane, 1,2-bis (2,3-epithiopropylthio) propane, , 3-bis (2,3-epithiopropylthio) propane, 1,3-bis (2,3-epithiopropylthio) -2-methylpropane 1,4-bis (2,3-epithiopropylthio) butane, 1,4-bis (2,3-epithiopropylthio) -2-methylbutane, 1,3-bis (2,3-epithiopropyl) Thio) butane, 1,5-bis (2,3-epithiopropylthio) pentane, 1,5-bis (2,3-epithiopropylthio) -2-methylpentane, 1,5-bis (2, 3-epithiopropylthio) -3-thiapentane, 1,6-bis (2,3-epithiopropylthio) hexane, 1,6-bis (2,3-epithiopropylthio) -2-methylhexane, 3,8-bis (2,3-epithiopropylthio) -3,6-dithiaoctane, 1,2,3-tris (2,3-epithiopropylthio) propane, 2,2-bis (2,3 -Epithiopropylthio) -1,3-bis (2 3-epithiopropylthiomethyl) propane, 2,2-bis (2,3-epithiopropylthiomethyl) -1- (2,3-epithiopropylthio) butane, 1,5-bis (2,3 -Epithiopropylthio) -2- (2,3-epithiopropylthiomethyl) -3-thiapentane, 1,5-bis (2,3-epithiopropylthio) -2,4-bis (2,3 -Epithiopropylthiomethyl) -3-thiapentane, 1- (2,3-epithiopropylthio) -2,2-bis (2,3-epithiopropylthiomethyl) -4-thiahexane, 1,5, 6-Tris (2,3-epithiopropylthio) -4- (2,3-epithiopropylthiomethyl) -3-thiahexane, 1,8-bis (2,3-epithiopropylthio) -4- (2,3-epithiopropylthiome Til) -3,6-dithiaoctane, 1,8-bis (2,3-epithiopropylthio) -4,5-bis (2,3-epithiopropylthiomethyl) -3,6-dithiaoctane, 1, 8-bis (2,3-epithiopropylthio) -4,4-bis (2,3-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (2,3-epithiopropyl) Thio) -2,5-bis (2,3-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (2,3-epithiopropylthio) -2,4,5-tris ( 2,3-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,1,1-tris [[2- (2,3-epithiopropylthio) ethyl] thiomethyl] -2- (2,3- Epithiopropylthio) ethane, 1,1,2,2- Trakis [[2- (2,3-epithiopropylthio) ethyl] thiomethyl] ethane, 1,11-bis (2,3-epithiopropylthio) -4,8-bis (2,3-epithiopropyl) Thiomethyl) -3,6,9-trithiaundecane, 1,11-bis (2,3-epithiopropylthio) -4,7-bis (2,3-epithiopropylthiomethyl) -3,6 , 9-trithiaundecane, 1,11-bis (2,3-epithiopropylthio) -5,7-bis (2,3-epithiopropylthiomethyl) -3,6,9-trithiaundecane, Chain aliphatic 2,3-epithiopropylthio compounds such as bis (2,3-epithiopropyl) disulfide, and
1,3-bis (2,3-epithiopropylthio) cyclohexane, 1,4-bis (2,3-epithiopropylthio) cyclohexane, 1,3-bis (2,3-epithiopropylthiomethyl) Cyclohexane, 1,4-bis (2,3-epithiopropylthiomethyl) cyclohexane, 2,5-bis (2,3-epithiopropylthiomethyl) -1,4-dithiane, 2,5-bis [[ 2- (2,3-epithiopropylthio) ethyl] thiomethyl] -1,4-dithiane, 2,5-bis (2,3-epithiopropylthiomethyl) -2,5-dimethyl-1,4- Cycloaliphatic 2,3-epithiopropylthio compounds such as dithiane, and
1,2-bis (2,3-epithiopropylthio) benzene, 1,3-bis (2,3-epithiopropylthio) benzene, 1,4-bis (2,3-epithiopropylthio) benzene 1,2-bis (2,3-epithiopropylthiomethyl) benzene, 1,3-bis (2,3-epithiopropylthiomethyl) benzene, 1,4-bis (2,3-epithiopropyl) Thiomethyl) benzene, bis [4- (2,3-epithiopropylthio) phenyl] methane, 2,2-bis [4- (2,3-epithiopropylthio) phenyl] propane, bis [4- ( 2,3-epithiopropylthio) phenyl] sulfide, bis [4- (2,3-epithiopropylthio) phenyl] sulfone, 4,4′-bis (2,3-epithiopropylthio) biphenyl, etc. Aromatic 2, 3-epithiopropylthio compound,
Monofunctional episulfide compounds such as ethylene sulfide, propylene sulfide, 3-mercaptopropylene sulfide, 4-mercaptobutene sulfide, epithiochlorohydrin,
Bis (2,3-epithiopropyl) ether, bis (2,3-epithiopropyloxy) methane, 1,2-bis (2,3-epithiopropyloxy) ethane, 1,2-bis (2, 3-epithiopropyloxy) propane, 1,3-bis (2,3-epithiopropyloxy) propane, 1,3-bis (2,3-epithiopropyloxy) -2-methylpropane, 1,4 -Bis (2,3-epithiopropyloxy) butane, 1,4-bis (2,3-epithiopropyloxy) -2-methylbutane, 1,3-bis (2,3-epithiopropyloxy) butane 1,5-bis (2,3-epithiopropyloxy) pentane, 1,5-bis (2,3-epithiopropyloxy) -2-methylpentane, 1,5-bis (2,3-epi Thiopropyloxy) 3-thiapentane, 1,6-bis (2,3-epithiopropyloxy) hexane, 1,6-bis (2,3-epithiopropyloxy) -2-methylhexane, 3,8-bis (2, 3-epithiopropyloxy) -3,6-dithiaoctane, 1,2,3-tris (2,3-epithiopropyloxy) propane, 2,2-bis (2,3-epithiopropyloxy) -1 , 3-bis (2,3-epithiopropyloxymethyl) propane, 2,2-bis (2,3-epithiopropyloxymethyl) -1- (2,3-epithiopropyloxy) butane, 1, 5-bis (2,3-epithiopropyloxy) -2- (2,3-epithiopropyloxymethyl) -3-thiapentane, 1,5-bis (2,3-epithiopropyloxy) -2, 4-bis (2, -Epithiopropyloxymethyl) -3-thiapentane, 1- (2,3-epithiopropyloxy) -2,2-bis (2,3-epithiopropyloxymethyl) -4-thiahexane, 1,5, 6-Tris (2,3-epithiopropyloxy) -4- (2,3-epithiopropyloxymethyl) -3-thiahexane, 1,8-bis (2,3-epithiopropyloxy) -4- (2,3-epithiopropyloxymethyl) -3,6-dithiaoctane, 1,8-bis (2,3-epithiopropyloxy) -4,5-bis (2,3-epithiopropyloxymethyl) 3,6-dithiaoctane, 1,8-bis (2,3-epithiopropyloxy) -4,4-bis (2,3-epithiopropyloxymethyl) -3,6-dithiaoctane, 1,8- Screw( 2,3-epithiopropyloxy) -2,5-bis (2,3-epithiopropyloxymethyl) -3,6-dithiaoctane, 1,8-bis (2,3-epithiopropyloxy) -2 , 4,5-tris (2,3-epithiopropyloxymethyl) -3,6-dithiaoctane, 1,1,1-tris [[2- (2,3-epithiopropyloxy) ethyl] thiomethyl]- 2- (2,3-epithiopropyloxy) ethane, 1,1,2,2-tetrakis [[2- (2,3-epithiopropyloxy) ethyl] thiomethyl] ethane, 1,11-bis (2 , 3-epithiopropyloxy) -4,8-bis (2,3-epithiopropyloxymethyl) -3,6,9-trithiaundecane, 1,11-bis (2,3-epithiopropyloxy) ) -4,7-Bis 2,3-epithiopropyloxymethyl) -3,6,9-trithiaundecane, 1,11-bis (2,3-epithiopropyloxy) -5,7-bis (2,3-epithiopropyl) Chain aliphatic 2,3-epithiopropyloxy compounds such as (oxymethyl) -3,6,9-trithiaundecane, and
1,3-bis (2,3-epithiopropyloxy) cyclohexane, 1,4-bis (2,3-epithiopropyloxy) cyclohexane, 1,3-bis (2,3-epithiopropyloxymethyl) Cyclohexane, 1,4-bis (2,3-epithiopropyloxymethyl) cyclohexane, 2,5-bis (2,3-epithiopropyloxymethyl) -1,4-dithiane, 2,5-bis [[ 2- (2,3-epithiopropyloxy) ethyl] thiomethyl] -1,4-dithiane, 2,5-bis (2,3-epithiopropyloxymethyl) -2,5-dimethyl-1,4- Cycloaliphatic 2,3-epithiopropyloxy compounds such as dithiane, and
1,2-bis (2,3-epithiopropyloxy) benzene, 1,3-bis (2,3-epithiopropyloxy) benzene, 1,4-bis (2,3-epithiopropyloxy) benzene 1,2-bis (2,3-epithiopropyloxymethyl) benzene, 1,3-bis (2,3-epithiopropyloxymethyl) benzene, 1,4-bis (2,3-epithiopropyl) Oxymethyl) benzene, bis [4- (2,3-epithiopropyloxy) phenyl] methane, 2,2-bis [4- (2,3-epithiopropyloxy) phenyl] propane, bis [4- ( 2,3-epithiopropyloxy) phenyl] sulfide, bis [4- (2,3-epithiopropyloxy) phenyl] sulfone, 4,4′-bis (2,3-epithiopropyloxy) bi Examples include aromatic 2,3-epithiopropyloxy compounds such as phenyl, but are not limited to the exemplified compounds.

  Among the exemplified compounds, preferred compounds include bis (1,2-epithioethyl) sulfide, bis (2,3-epithiopropyl) sulfide, bis (2,3-epithiopropylthio) methane, and bis (1,2- Epithioethyl) disulfide and bis (2,3-epithiopropyl) disulfide, and more preferred compounds are bis (1,2-epithioethyl) disulfide and bis (2,3-epithiopropyl) disulfide.

  Specific examples of the epoxy compound as the resin modifier of the present invention include phenolic epoxy compounds obtained by condensation reaction of polyphenol compounds such as bisphenol A glycidyl ether and epihalohydrin compounds, hydrogenated bisphenol A glycidyl ether, and the like. Alcohol-based epoxy compounds obtained by condensation of polyhydric alcohol compounds and epihalohydrin compounds, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 1,2-hexahydrophthalic acid diglycidyl ester, etc. Glycidyl ester epoxy compounds obtained by condensation of polyvalent organic acid compounds and epihalohydrin compounds, amine epoxy compounds obtained by condensation of secondary amine compounds and epihalohydrin compounds, etc. And the like Le cyclohexene diepoxide and an aliphatic polyvalent epoxy compound.

Specific examples of the sulfide group-containing epoxide compound and the ether group-containing epoxide compound include bis (2,3-epoxypropyl) sulfide, bis (2,3-epoxypropylthio) methane, 1,2-bis (2, 3-epoxypropylthio) ethane, 1,2-bis (2,3-epoxypropylthio) propane, 1,3-bis (2,3-epoxypropylthio) propane, 1,3-bis (2,3- Epoxypropylthio) -2-methylpropane, 1,4-bis (2,3-epoxypropylthio) butane, 1,4-bis (2,3-epoxypropylthio) -2-methylbutane, 1,3-bis (2,3-epoxypropylthio) butane, 1,5-bis (2,3-epoxypropylthio) pentane, 1,5-bis (2,3-epoxypropylthio) ) -2-methylpentane, 1,5-bis (2,3-epoxypropylthio) -3-thiapentane, 1,6-bis (2,3-epoxypropylthio) hexane, 1,6-bis (2, 3-epoxypropylthio) -2-methylhexane, 3,8-bis (2,3-epoxypropylthio) -3,6-dithiaoctane, 1,2,3-tris (2,3-epoxypropylthio) propane 2,2-bis (2,3-epoxypropylthio) -1,3-bis (2,3-epoxypropylthiomethyl) propane, 2,2-bis (2,3-epoxypropylthiomethyl) -1 -(2,3-epoxypropylthio) butane, 1,5-bis (2,3-epoxypropylthio) -2- (2,3-epoxypropylthiomethyl) -3-thiapentane, 1,5-bis ( 2 3-epoxypropylthio) -2,4-bis (2,3-epoxypropylthiomethyl) -3-thiapentane, 1- (2,3-epoxypropylthio) -2,2-bis (2,3-epoxy Propylthiomethyl) -4-thiahexane, 1,5,6-tris (2,3-epoxypropylthio) -4- (2,3-epoxypropylthiomethyl) -3-thiahexane, 1,8-bis (2 , 3-epoxypropylthio) -4- (2,3-epoxypropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (2,3-epoxypropylthio) -4,5-bis (2, 3-epoxypropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (2,3-epoxypropylthio) -4,4-bis (2,3-epoxypropylthiomethyl) -3,6-dithi Aoctane, 1,8-bis (2,3-epoxypropylthio) -2,5-bis (2,3-epoxypropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (2,3-epoxy Propylthio) -2,4,5-tris (2,3-epoxypropylthiomethyl) -3,6-dithiaoctane, 1,1,1-tris [[2- (2,3-epoxypropylthio) ethyl] Thiomethyl] -2- (2,3-epoxypropylthio) ethane, 1,1,2,2-tetrakis [[2- (2,3-epoxypropylthio) ethyl] thiomethyl] ethane, 1,11-bis ( 2,3-epoxypropylthio) -4,8-bis (2,3-epoxypropylthiomethyl) -3,6,9-trithiaundecane, 1,11-bis (2,3-epoxypropylthio)- 4,7 Bis (2,3-epoxypropylthiomethyl) -3,6,9-trithiaundecane, 1,11-bis (2,3-epoxypropylthio) -5,7-bis (2,3-epoxypropylthio) Chain aliphatic 2,3-epoxypropylthio compounds such as methyl) -3,6,9-trithiaundecane, bis (2,3-epoxypropyl) disulfide, and the like, and
1,3-bis (2,3-epoxypropylthio) cyclohexane, 1,4-bis (2,3-epoxypropylthio) cyclohexane, 1,3-bis (2,3-epoxypropylthiomethyl) cyclohexane, 1 , 4-bis (2,3-epoxypropylthiomethyl) cyclohexane, 2,5-bis (2,3-epoxypropylthiomethyl) -1,4-dithiane, 2,5-bis [[2- (2, Cyclic epoxy such as 3-epoxypropylthio) ethyl] thiomethyl] -1,4-dithiane, 2,5-bis (2,3-epoxypropylthiomethyl) -2,5-dimethyl-1,4-dithiane A 2,3-epoxypropylthio compound, and
1,2-bis (2,3-epoxypropylthio) benzene, 1,3-bis (2,3-epoxypropylthio) benzene, 1,4-bis (2,3-epoxypropylthio) benzene, 1, 2-bis (2,3-epoxypropylthiomethyl) benzene, 1,3-bis (2,3-epoxypropylthiomethyl) benzene, 1,4-bis (2,3-epoxypropylthiomethyl) benzene, bis [4- (2,3-epoxypropylthio) phenyl] methane, 2,2-bis [4- (2,3-epoxypropylthio) phenyl] propane, bis [4- (2,3-epoxypropylthio) Aromatic 2, such as phenyl] sulfide, bis [4- (2,3-epoxypropylthio) phenyl] sulfone, 4,4′-bis (2,3-epoxypropylthio) biphenyl 3-epoxypropylthio compound,
Monofunctional epoxy compounds such as ethylene oxide, propylene oxide, glycidol, epichlorohydrin,
Bis (2,3-epoxypropyl) ether, bis (2,3-epoxypropyloxy) methane, 1,2-bis (2,3-epoxypropyloxy) ethane, 1,2-bis (2,3-epoxy) Propyloxy) propane, 1,3-bis (2,3-epoxypropyloxy) propane, 1,3-bis (2,3-epoxypropyloxy) -2-methylpropane, 1,4-bis (2,3 -Epoxypropyloxy) butane, 1,4-bis (2,3-epoxypropyloxy) -2-methylbutane, 1,3-bis (2,3-epoxypropyloxy) butane, 1,5-bis (2, 3-epoxypropyloxy) pentane, 1,5-bis (2,3-epoxypropyloxy) -2-methylpentane, 1,5-bis (2,3-epoxypropyloxy) 3-thiapentane, 1,6-bis (2,3-epoxypropyloxy) hexane, 1,6-bis (2,3-epoxypropyloxy) -2-methylhexane, 3,8-bis (2,3- Epoxypropyloxy) -3,6-dithiaoctane, 1,2,3-tris (2,3-epoxypropyloxy) propane, 2,2-bis (2,3-epoxypropyloxy) -1,3-bis ( 2,3-epoxypropyloxymethyl) propane, 2,2-bis (2,3-epoxypropyloxymethyl) -1- (2,3-epoxypropyloxy) butane, 1,5-bis (2,3- Epoxypropyloxy) -2- (2,3-epoxypropyloxymethyl) -3-thiapentane, 1,5-bis (2,3-epoxypropyloxy) -2,4-bis (2, -Epoxypropyloxymethyl) -3-thiapentane, 1- (2,3-epoxypropyloxy) -2,2-bis (2,3-epoxypropyloxymethyl) -4-thiahexane, 1,5,6-tris (2,3-epoxypropyloxy) -4- (2,3-epoxypropyloxymethyl) -3-thiahexane, 1,8-bis (2,3-epoxypropyloxy) -4- (2,3-epoxy Propyloxymethyl) -3,6-dithiaoctane, 1,8-bis (2,3-epoxypropyloxy) -4,5-bis (2,3-epoxypropyloxymethyl) -3,6-dithiaoctane, 1, 8-bis (2,3-epoxypropyloxy) -4,4-bis (2,3-epoxypropyloxymethyl) -3,6-dithiaoctane, 1,8-bis ( 2,3-epoxypropyloxy) -2,5-bis (2,3-epoxypropyloxymethyl) -3,6-dithiaoctane, 1,8-bis (2,3-epoxypropyloxy) -2,4 5-tris (2,3-epoxypropyloxymethyl) -3,6-dithiaoctane, 1,1,1-tris [[2- (2,3-epoxypropyloxy) ethyl] thiomethyl] -2- (2, 3-epoxypropyloxy) ethane, 1,1,2,2-tetrakis [[2- (2,3-epoxypropyloxy) ethyl] thiomethyl] ethane, 1,11-bis (2,3-epoxypropyloxy) -4,8-bis (2,3-epoxypropyloxymethyl) -3,6,9-trithiaundecane, 1,11-bis (2,3-epoxypropyloxy) -4,7-bis 2,3-epoxypropyloxymethyl) -3,6,9-trithiaundecane, 1,11-bis (2,3-epoxypropyloxy) -5,7-bis (2,3-epoxypropyloxymethyl) Chain aliphatic 2,3-epoxypropyloxy compounds such as -3,6,9-trithiaundecane, and
1,3-bis (2,3-epoxypropyloxy) cyclohexane, 1,4-bis (2,3-epoxypropyloxy) cyclohexane, 1,3-bis (2,3-epoxypropyloxymethyl) cyclohexane, 1 , 4-bis (2,3-epoxypropyloxymethyl) cyclohexane, 2,5-bis (2,3-epoxypropyloxymethyl) -1,4-dithiane, 2,5-bis [[2- (2, Cyclic epoxy such as 3-epoxypropyloxy) ethyl] thiomethyl] -1,4-dithiane, 2,5-bis (2,3-epoxypropyloxymethyl) -2,5-dimethyl-1,4-dithiane 2,3-epoxypropyloxy compounds, and
1,2-bis (2,3-epoxypropyloxy) benzene, 1,3-bis (2,3-epoxypropyloxy) benzene, 1,4-bis (2,3-epoxypropyloxy) benzene, 1, 2-bis (2,3-epoxypropyloxymethyl) benzene, 1,3-bis (2,3-epoxypropyloxymethyl) benzene, 1,4-bis (2,3-epoxypropyloxymethyl) benzene, bis [4- (2,3-epoxypropyloxy) phenyl] methane, 2,2-bis [4- (2,3-epoxypropyloxy) phenyl] propane, bis [4- (2,3-epoxypropyloxy) Phenyl] sulfide, bis [4- (2,3-epoxypropyloxy) phenyl] sulfone, 4,4′-bis (2,3-epoxypropyloxy) biphenyl Examples include aromatic 2,3-epoxypropyloxy compounds such as phenyl, but are not limited to the exemplified compounds.

Specific examples of amine compounds that can be added as a resin modifier include ethylamine, n-propylamine, isopropylamine, n-butylamine, sec-butylamine, ter-butylamine, pentylamine, hexylamine, heptylamine, octylamine, Decylamine, laurylamine, myristylamine, 3-pentylamine, 2-ethylhexylamine, 1,2-dimethylhexylamine, allylamine, aminomethylbicycloheptane, cyclopentylamine, cyclohexylamine, 2,3-dimethylcyclohexylamine, aminomethylcyclohexane Aniline, benzylamine, phenethylamine, 2,3-, or 4-methylbenzylamine, o-, m-, or p-methylaniline, o-, m-, or p Ethylaniline, aminomorpholine, naphthylamine, furfurylamine, α-aminodiphenylmethane, toluidine, aminopyridine, aminophenol, aminoethanol, 1-aminopropanol, 2-aminopropanol, aminobutanol, aminopentanol, aminohexanol, methoxyethylamine, 2- (2-aminoethoxy) ethanol, 3-ethoxypropylamine, 3-propoxypropylamine, 3-butoxypropylamine, 3-isopropoxypropylamine, 3-isobutoxypropylamine, 2,2-diethoxyethylamine, etc. A monofunctional primary amine compound of
Ethylenediamine, 1,2-, or 1,3-diaminopropane, 1,2-, 1,3-, or 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7 -Diaminoheptane, 1,8-diaminooctane, 1,10-diaminodecane, 1,2-, 1,3-, or 1,4-diaminocyclohexane, o-, m- or p-diaminobenzene, 3,4 -Or 4,4'-diaminobenzophenone, 3,4- or 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 3,3'-, or 4,4 '-Diaminodiphenylsulfone, 2,7-diaminofluorene, 1,5-, 1,8-, or 2,3-diaminonaphthalene, 2,3 2,6- or 3,4-diaminopyridine, 2,4- or 2,6-diaminotoluene, m- or p-xylylenediamine, isophoronediamine, diaminomethylbicycloheptane, 1,3-, Alternatively, 1,4-diaminomethylcyclohexane, 2-, or 4-aminopiperidine, 2-, or 4-aminomethylpiperidine, 2-, or 4-aminoethylpiperidine, N-aminoethylmorpholine, N-aminopropylmorpholine, etc. A primary polyamine compound of
Diethylamine, dipropylamine, di-n-butylamine, di-sec-butylamine, diisobutylamine, di-n-pentylamine, di-3-pentylamine, dihexylamine, dioctylamine, di (2-ethylhexyl) amine, methyl Hexylamine, diallylamine, N-methylallylamine, piperidine, pyrrolidine, diphenylamine, N-methylamine, N-ethylamine, dibenzylamine, N-methylbenzylamine, N-ethylbenzylamine, dicyclohexylamine, N-methylaniline, N -Monofunctional secondary amine compounds such as ethylaniline, dinaphthylamine, 1-methylpiperazine, morpholine,
N, N′-dimethylethylenediamine, N, N′-dimethyl-1,2-diaminopropane, N, N′-dimethyl-1,3-diaminopropane, N, N′-dimethyl-1,2-diaminobutane, N, N′-dimethyl-1,3-diaminobutane, N, N′-dimethyl-1,4-diaminobutane, N, N′-dimethyl-1,5-diaminopentane, N, N′-dimethyl-1 , 6-Diaminohexane, N, N′-dimethyl-1,7-diaminoheptane, N, N′-diethylethylenediamine, N, N′-diethyl-1,2-diaminopropane, N, N′-diethyl-1 , 3-diaminopropane, N, N′-diethyl-1,2-diaminobutane, N, N′-diethyl-1,3-diaminobutane, N, N′-diethyl-1,4-diaminobutane, N, N'-diethyl-1,5-di Aminopentane, N, N′-diethyl-1,6-diaminohexane, N, N′-diethyl-1,7-diaminoheptane, piperazine, 2-methylpiperazine, 2,5-dimethylpiperazine, 2,6-dimethyl Piperazine, homopiperazine, 1,1-di- (4-piperidyl) methane, 1,2-di- (4-piperidyl) ethane, 1,3-di- (4-piperidyl) propane, 1,4-di- Secondary polyamine compounds such as (4-piperidyl) butane and tetramethylguanidine can be exemplified, but are not limited to the exemplified compounds. Moreover, the said amine compound may be used individually or in mixture of 2 or more types. Of the exemplified compounds, benzylamine and piperazines are more preferred compounds.

  The thiol compound that can be added as a resin modifier includes those containing at least one sulfur atom in addition to the mercapto group. Specific examples of these compounds include monofunctional thiol compounds such as methyl mercaptan, ethyl mercaptan, propyl mercaptan, butyl mercaptan, octyl mercaptan, dodecyl mercaptan, tert-dodecyl mercaptan, hexadecyl mercaptan, octadecyl mercaptan, cyclohexyl mercaptan, benzyl mercaptan, Examples thereof include aliphatic mercaptan compounds such as ethylphenyl mercaptan, 2-mercaptomethyl-1,3-dithiolane, 2-mercaptomethyl-1,4-dithian, and aromatic mercaptan compounds such as thiophenol and mercaptotoluene. It is not limited to.

Examples of the bifunctional or higher polythiol compound include 1,1-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), diethylene glycol 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 ( - mercaptopropionate), tetrakis (mercaptomethyl) aliphatic such as methane polythiol compound,
1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,2-bis (mercaptomethyl) benzene, 1,3-bis (mercaptomethyl) benzene, 1,4- Bis (mercaptomethyl) 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, 1,3,3 5-tris (mercaptomethyl) benzene, 1,2,3-tris (mercaptoethyl) benzene, 1,2,4-tris (mer Puttoethyl) benzene, 1,3,5-tris (mercaptoethyl) benzene, 2,5-toluenedithiol, 3,4-toluenedithiol, 1,3-di (p-methoxyphenyl) propane-2,2-dithiol, Aromatic polythiols such as 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, 1,2,4-tris (mercaptoethylthio) ) Aromatic polythiol compounds containing sulfur atoms in addition to mercapto groups such as benzene, 1,3,5-tris (mercaptoethylthio) benzene, and their nuclear alkylated products,
Bis (mercaptomethyl) sulfide, bis (mercaptoethyl) sulfide, bis (mercaptopropyl) sulfide, bis (mercaptomethylthio) methane, bis (2-mercaptoethylthio) methane, bis (3-mercaptopropylthio) methane, 1, 2-bis (mercaptomethylthio) ethane, 1,2-bis (2-mercaptoethylthio) ethane, 1,2-bis (3-mercaptopropyl) ethane, 1,3-bis (mercaptomethylthio) propane, 1,3 -Bis (2-mercaptoethylthio) propane, 1,3-bis (3-mercaptopropylthio) propane, 1,2,3-tris (mercaptomethylthio) propane, 1,2,3-tris (2-mercaptoethyl) Thio) 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 (mercaptomethylthiomethyl) ) Methane, 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, , 5-dimercaptomethyl-2,5-dimethyl-1,4-dithiane, bis (mercaptomethyl) disulfide, bis (mercaptoethyl) disulfide, bis (mercaptopropyl) disulfide, and other sulfur atoms in addition to mercapto groups Aliphatic polythiol compounds, and esters of these thioglycolic and mercaptopropionic acids,
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), dithiodipropionic acid bis (2,3-dimercaptopropyl ester) and other mercapto groups, aliphatic polythiol compounds containing a sulfur atom and an ester bond, and 3,4-thiophenedithiol A heterocyclic compound containing a sulfur atom in addition to a mercapto group such as 2,5-dimercapto-1,3,4-thiadiazole,
2-mercaptoethanol, 3-mercapto-1,2-propanediol, glycerol di (mercaptoacetate), 1-hydroxy-4-mercaptocyclohexane, 2,4-dimercaptophenol, 2-mercaptohydroquinone, 4-mercaptophenol, 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 mono (3-mercaptopropionate), pentaerythritol bis (3-mercaptopropionate), pentaerythritol tris (thioglycolate), dipentaerythritol pentakis (3 Mercaptopropionate), hydroxymethyl - tris (mercaptoethylthiomethyl) methane, compounds containing 1-hydroxyethyl-thio-3-mercaptoethyl hydroxy group other than the mercapto group of thio benzene,
1,1,3,3-tetrakis (mercaptomethylthio) propane, 1,1,2,2-tetrakis (mercaptomethylthio) ethane, 4,6-bis (mercaptomethylthio) -1,3-dithiacyclohexane, 1, 1,5,5-tetrakis (mercaptomethylthio) -3-thiapentane, 1,1,6,6-tetrakis (mercaptomethylthio) -3,4-dithiahexane, 2,2-bis (mercaptomethylthio) ethanethiol, 2- (4,5-Dimercapto-2-thiapentyl) -1,3-dithiacyclopentane, 2,2-bis (mercaptomethyl) -1,3-dithiacyclopentane, 2,5-bis (4,4- Bis (mercaptomethylthio) -2-thiabutyl) -1,4-dithiane, 2,2-bis (mercaptomethylthio) -1,3-propa Dithiol, 3-mercaptomethylthio-1,7-dimercapto-2,6-dithiaheptane, 3,6-bis (mercaptomethylthio) -1,9-dimercapto-2,5,8-trithianonane, 4,6-bis (mercapto) Methylthio) -1,9-dimercapto-2,5,8-trithianonane, 3-mercaptomethylthio-1,6-dimercapto-2,5-dithiahexane, 2- (2,2-bis (mercaptomethylthio) ethyl) -1 , 3-dithietane, 1,1,9,9-tetrakis (mercaptomethylthio) -5- (3,3-bis (mercaptomethylthio) -1-thiapropyl) 3,7-dithianonane, tris (2,2-bis ( Mercaptomethylthio) ethyl) methane, tris (4,4-bis (mercaptomethylthio) -2-thiabutyl) me , Tetrakis (2,2-bis (mercaptomethylthio) ethyl) methane, tetrakis (4,4-bis (mercaptomethylthio) -2-thiabutyl) methane, 3,5,9,11-tetrakis (mercaptomethylthio) -1 , 13-dimercapto-2,6,8,12-tetrathiatridecane, 3,5,9,11,15,17-hexakis (mercaptomethylthio) -1,19-dimercapto-2,6,8,12, 14,18-hexathiononadecane, 9- (2,2-bis (mercaptomethylthio) ethyl) -3,5,13,15-tetrakis (mercaptomethylthio) -1,17-dimercapto-2,6,8, 10,12,16-hexathiaheptadecane, 3,4,8,9-tetrakis (mercaptomethylthio) -1,11-dimercapto-2 , 5,7,10-tetrathiaundecane, 3,4,8,9,13,14-hexakis (mercaptomethylthio) -1,16-dimercapto-2,5,7,10,12,15-hexathiahexadecane 8- {bis (mercaptomethylthio) methyl} -3,4,12,13-tetrakis (mercaptomethylthio) -1,15-dimercapto-2,5,7,9,11,14-hexathiapentadecane, 4, 6-bis {3,5-bis (mercaptomethylthio) -7-mercapto-2,6-dithiaheptylthio} -1,3-dithiane, 4- {3,5-bis (mercaptomethylthio) -7-mercapto -2,6-dithiaheptylthio} -6-mercaptomethylthio-1,3-dithiane, 1,1-bis {4- (6-mercaptomethylthio) -1,3-dithi Nilthio} -3,3-bis (mercaptomethylthio) propane, 1,3-bis {4- (6-mercaptomethylthio) -1,3-dithianylthio} -1,3-bis (mercaptomethylthio) propane, 1- { 4- (6-Mercaptomethylthio) -1,3-dithianylthio} -3- {2,2-bis (mercaptomethylthio) ethyl} -7,9-bis (mercaptomethylthio) -2,4,6,10-tetra Thiaundecane, 1- {4- (6-mercaptomethylthio) -1,3-dithianylthio} -3- {2- (1,3-dithietanyl)} methyl-7,9-bis (mercaptomethylthio) -2,4 , 6,10-tetrathiaundecane, 1,5-bis {4- (6-mercaptomethylthio) -1,3-dithianylthio} -3- {2- (1,3-dithieta L)} methyl-2,4-dithiapentane, 4,6-bis [3- {2- (1,3-dithietanyl)} methyl-5-mercapto-2,4-dithiapentylthio] -1,3- Dithiane, 4,6-bis {4- (6-mercaptomethylthio) -1,3-dithianylthio} -1,3-dithiane, 4- {4- (6-mercaptomethylthio) -1,3-dithianylthio} -6 -{4- (6-mercaptomethylthio) -1,3-dithianylthio} -1,3-dithiane, 3- {2- (1,3-dithietanyl)} methyl-7,9-bis (mercaptomethylthio) -1 , 11-dimercapto-2,4,6,10-tetrathiaundecane, 9- {2- (1,3-dithietanyl)} methyl-3,5,13,15-tetrakis (mercaptomethylthio) -1,17- Zimmerka Put-2,6,8,10,12,16-hexathiaheptadecane, 3- {2- (1,3-dithietanyl)} methyl-7,9,13,15-tetrakis (mercaptomethylthio) -1, 17-dimercapto-2,4,6,10,12,16-hexathiaheptadecane, 3,7-bis {2- (1,3-dithietanyl)} methyl-1,9-dimercapto-2,4,6 , 8-tetrathianonane, 4- {3,4,8,9-tetrakis (mercaptomethylthio) -11-mercapto-2,5,7,10-tetrathiaundecyl} -5-mercaptomethylthio-1,3 -Dithiolane, 4,5-bis {3,4-bis (mercaptomethylthio) -6-mercapto-2,5-dithiahexylthio} -1,3-dithiolane, 4- {3,4-bis (mercaptomethyl) H ) -6-mercapto-2,5-dithiahexylthio} -5-mercaptomethylthio-1,3-dithiolane, 4- {3-bis (mercaptomethylthio) methyl-5,6-bis (mercaptomethylthio) -8 -Mercapto-2,4,7-trithiaoctyl} -5-mercaptomethylthio-1,3-dithiolane, 2- [bis {3,4-bis (mercaptomethylthio) -6-mercapto-2,5-dithia Hexylthio} methyl] -1,3-dithietane, 2- {3,4-bis (mercaptomethylthio) -6-mercapto-2,5-dithiahexylthio} mercaptomethylthiomethyl-1,3-dithietane, 2- {3,4,8,9-tetrakis (mercaptomethylthio) -11-mercapto-2,5,7,10-tetrathiaundecylthio} mercapto Tylthiomethyl-1,3-dithietane, 2- {3-bis (mercaptomethylthio) methyl-5,6-bis (mercaptomethylthio) -8-mercapto-2,4,7-trithiaoctyl} mercaptomethylthiomethyl-1, 3-dithietane, 4,5-bis [1- {2- (1,3-dithietanyl)}-3-mercapto-2-thiapropylthio] -1,3-dithiolane, 4- [1- {2- ( 1,3-dithietanyl)}-3-mercapto-2-thiapropylthio] -5- {1,2-bis (mercaptomethylthio) -4-mercapto-3-thiabutylthio} -1,3-dithiolane, 2- [ Bis {4- (5-mercaptomethylthio-1,3-dithiolanyl) thio}] methyl-1,3-dithietane, 4- {4- (5-mercaptomethylthio-1,3-dithio Ranyl) thio} -5- [1- {2- (1,3-dithietanyl)}-3-mercapto-2-thiapropylthio] -1,3-dithiolane and dithioacetal or dithioketal skeletons such as oligomers thereof A compound having
Tris (mercaptomethylthio) methane, tris (mercaptoethylthio) methane, 1,1,5,5-tetrakis (mercaptomethylthio) -2,4-dithiapentane, bis [4,4-bis (mercaptomethylthio) -1,3 -Dithiabutyl] (mercaptomethylthio) methane, tris [4,4-bis (mercaptomethylthio) -1,3-dithiabutyl] methane, 2,4,6-tris (mercaptomethylthio) -1,3,5-trithiacyclohexane 2,4-bis (mercaptomethylthio) -1,3,5-trithiacyclohexane, 1,1,3,3-tetrakis (mercaptomethylthio) -2-thiapropane, bis (mercaptomethyl) methylthio-1,3 5-trithiacyclohexane, tris [(4-mercaptomethyl-2,5-dithi Cyclohexyl-1-yl) methylthio] methane, 2,4-bis (mercaptomethylthio) -1,3-dithiacyclopentane, 2-mercaptoethylthio-4-mercaptomethyl-1,3-dithiacyclopentane, 2 -(2,3-dimercaptopropylthio) -1,3-dithiacyclopentane, 4-mercaptomethyl-2- (2,3-dimercaptopropylthio) -1,3-dithiacyclopentane, 4- Mercaptomethyl-2- (1,3-dimercapto-2-propylthio) -1,3-dithiacyclopentane, tris [2,2-bis (mercaptomethylthio) -1-thiaethyl] methane, tris [3,3- Bis (mercaptomethylthio) -2-thiapropyl] methane, tris [4,4-bis (mercaptomethylthio) -3-thiabutyl] me 2,4,6-tris [3,3-bis (mercaptomethylthio) -2-thiapropyl] -1,3,5-trithiacyclohexane, tetrakis [3,3-bis (mercaptomethylthio) -2-thiapropyl ] Compounds having an orthocarboxylic acid trithioester skeleton, such as methane and further oligomers thereof,
3,3′-di (mercaptomethylthio) -1,5-dimercapto-2,4-dithiapentane, 2,2′-di (mercaptomethylthio) -1,3-dithiacyclopentane, 2,7-di (mercapto) Methyl) -1,4,5,9-tetrathiaspiro [4,4] nonane, 3,9-dimercapto-1,5,7,11-tetrathiaspiro [5,5] undecane, and oligomers thereof. Examples include compounds having an ortho-carbonic acid tetrathioester skeleton, but are not limited to these exemplified compounds. These exemplary compounds may be used alone or in combination of two or more.

  Among these compounds, more preferable compounds are compounds having a mercaptomethylthio group, and examples thereof include compounds having the aforementioned dithioacetal or dithioketal skeleton, orthocarboxylic acid trithioesters, compounds having an orthocarbonic acid tetrathioester skeleton, and the like. it can. These exemplified compounds may be used alone or in combination of two or more. Of these compounds, it is preferable to select an aliphatic polythiol compound rather than an aromatic one in consideration of the optical properties of the resulting resin, particularly the Abbe number. Further, in view of optical properties, particularly refractive index requirements, it is more preferable to select a compound having a sulfur atom in addition to a thiol group such as a sulfide bond and / or a disulfide bond. It is more preferable to select a compound having a thioester skeleton and an orthocarbonic acid tetrathioester skeleton. In order to increase the three-dimensional crosslinkability in consideration of the heat resistance of the resulting resin, it is particularly preferable to select one or more polythiol compounds having three or more functions. As the most preferred polythiol in the above points, 2,5-bis (mercaptomethyl) -1,4-dithiane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8-dimercaptomethyl -1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 5,7-dimercaptomethyl-1 , 11-dimercapto-3,6,9-trithiaundecane, 1,1,1,1-tetrakis (mercaptomethyl) methane, 1,1,3,3-tetrakis (mercaptomethylthio) propane, 1,1,2 , 2-tetrakis (mercaptomethylthio) ethane, 4,6-bis (mercaptomethylthio) -1,3-dithiane, 2- (2,2-bis (me Captomethylthio) ethyl) -1,3-dithietane is a compound selected from at least one compound in the case of three or more functional groups and at least one compound selected from at least one compound and three or more functional compounds in the case of two or more functional groups. It is done.

Specific examples of hydroxy compounds containing phenol compounds as the resin modifier of the present invention are monofunctional or higher mono- or polyols and also include phenolic hydroxyl groups. Those containing a sulfur atom in the molecule are also included. Specific examples of monofunctional compounds include methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, pentanol, isoamyl alcohol, hexanol, heptanol, octanol, nonyl alcohol, decanol, Dodecyl alcohol, cetyl alcohol, isotridecyl alcohol, stearyl alcohol, 2-ethyl-1-hexanol, allyl alcohol, methoxyethanol, ethoxyethanol, phenoxyethanol, cyclopropanol, cyclobutanol, cyclopentanol, cyclohexanol, cyclooctanol, benzyl Alcohol, phenylethyl alcohol, methylcyclohexanol, furfuryl alcohol, tetrahydrofur Furfuryl alcohol, methyl lactate, ethyl lactate, aliphatic, such as butyl lactate monofunctional alcohol compounds,
Aromatic monofunctional phenolic compounds such as phenol, cresol, ethylphenol, methoxyphenol, ethoxyphenol, methoxyethylphenol, cumylphenol, phenoxyphenol, tert-butylphenol, naphthol,
Examples of the bifunctional or higher polyol compound include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, neopentyl glycol, glycerin, trimethylol ethane, trimethylol propane, butane triol, and 1,2-methyl glycoside. , Pentaerythritol, dipentaerythritol, tripentaerythritol, sorbitol, erythritol, threitol, mannitol, ribitol, arabinitol, xylitol, allitol, dolcitol, glycol, inositol, hexanetriol, triglycerol, triethylene glycol, polyethylene glycol, tris ( 2-hydroxyethyl) isocyanurate, cyclobutanediol, cyclope Tandiol, cyclohexanediol, cycloheptanediol, cyclooctanediol, cyclohexanedimethanol, hydroxypropylcyclohexanol, bicyclo [4,3,0] -nonanediol, dicyclohexanediol, tricyclo [5,3,1,1] dodecanediol , Bicyclo [4,3,0] -nonanedimethanol, dicyclohexanediol, tricyclo [5,3,1,1] dodecanediethanol, spiro [3,4] octanediol, butylcyclohexanediol, 1,1-bicyclohexene Silidenediol, cyclohexanetriol, maltitol, lactitol, dihydroxynaphthalene, trihydroxynaphthalene, tetrahydroxynaphthalene, dihydroxybenzene, benzenetriol, bif Nyltetraol, trihydroxyphenanthrene, bisphenol A, bisphenol F, xylylene glycol, bis (2-hydroxyethoxy) benzene, bisphenol A-bis (2-hydroxyethyl ether), tetrabromobisphenol A, tetrabromobisphenol A-bis (2-hydroxyethyl ether), polyols such as dibromoneopentyl glycol,
In addition, oxalic acid, glutamic acid, adipic acid, acetic acid, propionic acid, phthalic acid, isophthalic acid, salicylic acid, pyromellitic acid, 3-bromopropionic acid, 2-bromoglycolic acid, dicarboxycyclohexane, butanetetracarboxylic acid, bromophthalate Examples include condensation reaction products of an organic polybasic acid such as an acid and the polyol, and addition reaction products of the polyol and an alkylene oxide such as ethylene oxide and propylene oxide, but are not limited to the exemplified compounds. Furthermore, you may use halogen substituted bodies, such as these chlorine substituted bodies and bromine substituted bodies.

  Examples of the mono- or polyol compound containing a sulfur atom include bis [4- (hydroxyethoxy) phenyl] sulfide, bis [4- (2-hydroxypropoxy) phenyl] sulfide, and bis [4- (2,3- Dihydroxypropoxy) phenyl] sulfide, bis [4- (4-hydroxycyclohexyloxy) phenyl] sulfide, bis [2-methyl-4- (hydroxyethoxy) -6-butylphenyl] sulfide and these compounds on average 3 per hydroxyl group Compounds having an ethylene oxide and / or propylene oxide added thereto, bis (2-hydroxyethyl) sulfide, 1,2-bis (2-hydroxyethylmercapto) ethane, bis (2-hydroxyethyl) disulfide, 1,4 -Dithian-2, -Diol, bis (2,3-dihydroxypropyl) sulfide, tetrakis (4-hydroxy-2-thiabutyl) methane, bis (4-hydroxyphenyl) sulfone (bisphenol S), tetrabromobisphenol S, tetramethylbisphenol S, 4 , 4-thiobis (6-tert-butyl-3-methylphenol), 1,3-bis (2-hydroxyethylthioethyl) cyclohexane and the like, but are not limited to the exemplified compounds. Furthermore, you may use halogen substituted bodies, such as these chlorine substituted bodies and bromine substituted bodies.

Specific examples of the iso (thio) cyanate compounds as the resin modifier of the present invention include methyl isocyanate, ethyl isocyanate, n-propyl isocyanate, isopropyl isocyanate, n-butyl isocyanate, sec-butyl isocyanate. Nert, tert-butyl isocyanate, pentyl isocyanate, hexyl isocyanate, heptyl isocyanate, octyl isocyanate, decyl isocyanate, lauryl isocyanate, myristyl isocyanate, octadecyl isocyanate, 3-pentyl isocyanate, 2-ethylhexyl isocyanate Narate, 2,3-dimethylcyclohexyl isocyanate, 2-methoxyphenyl isocyanate, 4-methoxyphenyl isocyanate, α-methylbenzyl isocyanate DOO, phenylethyl isocyanate, phenyl isocyanate, o-, m-, or p- tolyl isocyanate, cyclohexyl isocyanate, benzyl isocyanate, monofunctional isocyanate compounds such as isocyanate methyl bicycloheptane,
Hexamethylene diisocyanate, 2,2-dimethylpentane diisocyanate, 2,2,4-trimethylhexane diisocyanate, butene diisocyanate, 1,3-butadiene-1,4-diisocyanate, 2,4 , 4-trimethylhexamethylene diisocyanate, 1,6,11-undecatriisocyanate, 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanato-4-isocyanatomethyloctane, bis (isocyanato Ethyl) carbonate, bis (isocyanatoethyl) ether, lysine diisocyanate methyl ester, lysine triisocyanate, xylylene diisocyanate, bis (isocyanatoethyl) benzene, bis (isocyanatopropyl) benzene, α, α, α ', Α'-tetramethylxylylene Diisocyanate, bis (isocyanatobutyl) benzene, bis (isocyanatomethyl) naphthalene, bis (isocyanatomethyl) diphenyl ether, bis (isocyanatoethyl) phthalate, mesityrylene triisocyanate, 2,6-di (isocyanate) Aliphatic polyisocyanate compounds such as natomethyl) furan,
Isophorone diisocyanate, bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, dicyclohexyldimethylmethane diisocyanate, 2,2-dimethyldicyclohexylmethane diisocyanate, 2, 5-bis (isocyanatomethyl) bicyclo- [2,2,1] -heptane, 2,6-bis (isocyanatomethyl) bicyclo- [2,2,1] -heptane, 3,8-bis (isocyanato Fats such as methyl) tricyclodecane, 3,9-bis (isocyanatomethyl) tricyclodecane, 4,8-bis (isocyanatomethyl) tricyclodecane, 4,9-bis (isocyanatomethyl) tricyclodecane Cyclic polyisocyanate compounds,
Phenylene diisocyanate, tolylene diisocyanate, ethylphenylene diisocyanate, isopropylphenylene diisocyanate, dimethylphenylene diisocyanate, diethylphenylene diisocyanate, diisopropylphenylene diisocyanate, trimethylbenzene triisocyanate, benzene triisocyanate , Biphenyl diisocyanate, toluidine diisocyanate, 4,4-diphenylmethane diisocyanate, 3,3-dimethyldiphenylmethane-4,4-diisocyanate, bibenzyl-4,4-diisocyanate, bis (isocyanatophenyl ) Ethylene, 3,3-dimethoxybiphenyl-4,4-diisocyanate, phenylisocyanatoethyl isocyanate, hexahydrobenzene diiso Annatto, aromatic polyisocyanate compound such as hexahydroterephthalic diphenylmethane-4,4-diisocyanate,
Bis (isocyanatomethyl) sulfide, bis (isocyanatoethyl) sulfide, bis (isocyanatopropyl) sulfide, bis (isocyanatohexyl) sulfide, bis (isocyanatomethyl) sulfone, bis (isocyanatomethyl) disulfide, bis ( Isocyanatoethyl) disulfide, bis (isocyanatopropyl) disulfide, bis (isocyanatomethylthio) methane, bis (isocyanatoethylthio) methane, bis (isocyanatoethylthio) ethane, bis (isocyanatomethylthio) ethane, 1, Sulfur-containing aliphatic isocyanate compounds such as 5-diisocyanato-2-isocyanatomethyl-3-thiapentane,
Diphenyl sulfide-2,4-diisocyanate, diphenyl sulfide-4,4-diisocyanate, 3,3-dimethoxy-4,4-diisocyanatodibenzylthioether, bis (4-isocyanatomethylbenzene) sulfide, Aromatic sulfide isocyanate compounds such as 4,4-methoxybenzenethioethylene glycol-3,3-diisocyanate,
Diphenyl disulfide-4,4-diisocyanate, 2,2-dimethyldiphenyl disulfide-5,5-diisocyanate, 3,3-dimethyldiphenyl disulfide-5,5-diisocyanate, 3,3-dimethyldiphenyl disulfide 6,6-diisocyanate, 4,4-dimethyldiphenyl disulfide-5,5-diisocyanate, 3,3-dimethoxydiphenyl disulfide-4,4-diisocyanate, 4,4-dimethoxydiphenyl disulfide-3 Aromatic disulfide-based isocyanate compounds such as 1,3-diisocyanate, sulfur-containing heterocyclic compounds such as 2,5-diisocyanatothiophene, 2,5-bis (isocyanatomethyl) thiophene,
In addition, 2,5-diisocyanatotetrahydrothiophene, 2,5-bis (isocyanatomethyl) tetrahydrothiophene, 3,4-bis (isocyanatomethyl) tetrahydrothiophene, 2,5-diisocyanato-1,4- Dithiane, 2,5-bis (isocyanatomethyl) -1,4-dithiane, 4,5-diisocyanato-1,3-dithiolane, 4,5-bis (isocyanatomethyl) -1,3-dithiolane, 4, Examples thereof include 5-bis (isocyanatomethyl) -2-methyl-1,3-dithiolane, but are not limited to the exemplified compounds. In addition, halogen-substituted products such as chlorine-substituted products, bromine-substituted products, alkyl-substituted products, alkoxy-substituted products, nitro-substituted products, prepolymer-modified products with polyhydric alcohols, carbodiimide-modified products, urea-modified products, and burette-modified products. Bodies, dimerization or trimerization reaction products can also be used.

Further, specific examples of the isothiocyanate compound include methyl isothiocyanate, ethyl isothiocyanate, n-propyl thioisocyanate, isopropyl isothiocyanate, n-butyl isothiocyanate, sec-butyl isothiocyanate, tert- Butyl isothiocyanate, pentyl isothiocyanate, hexyl isothiocyanate, heptyl isothiocyanate, octyl isothiocyanate, decyl isothiocyanate, lauryl isothiocyanate, myristyl isothiocyanate, octadecyl isothiocyanate, 3-pentyl isothiocyanate Narate, 2-ethylhexyl isothiocyanate, 2,3-dimethylcyclohexyl isothiocyanate, 2-methoxyphenyl isothiocyanate, 4-methoxyphenyl Nyl isothiocyanate, α-methylbenzyl isothiocyanate, phenylethyl isothiocyanate, phenyl isothiocyanate, o-, m-, or p-tolyl isothiocyanate, cyclohexyl isothiocyanate, benzyl isothiocyanate, isothiocyanate Monofunctional isothiocyanate compounds such as natomethylbicycloheptane,
Aliphatic polyisothiocyanate compounds such as 1,6-diisothiocyanatohexane, p-phenyleneisopropylidenediisothiocyanate,
Cycloaliphatic diisothiocyanate, alicyclic polyisothiocyanate compounds such as diisothiocyanatomethylbicycloheptane,
1,2-diisothiocyanatobenzene, 1,3-diisothiocyanatobenzene, 1,4-diisothiocyanatobenzene, 2,4-diisothiocyanatotoluene, 2,5-diisothiocyanato-m Xylene, 4,4-diisothiocyanato-1,1-biphenyl, 1,1-methylenebis (4-isothiocyanatobenzene), 1,1-methylenebis (4-isothiocyanato-2-methylbenzene), 1, 1-methylenebis (4-isothiocyanato-3-methylbenzene), 1,1- (1,2-ethanediyl) bis (isothiocyanatobenzene), 4,4-diisothiocyanatobenzophenone, 4,4-diisothiocyana -3,3-dimethylbenzophenone, diphenyl ether-4,4-diisothiocyanate, diphenylamine-4,4-di Aromatic isothiocyanate compounds such as soothiocyanate, further 1,3-benzenedicarbonyldiisothiocyanate, 1,4-benzenedicarbonyldiisothiocyanate, (2,2-pyridine) -4,4-di Examples include carbonyl isothiocyanate compounds such as carbonyl diisothiocyanate, but are not limited to the exemplified compounds.

  Specific examples of the isothiocyanate compound containing one or more sulfur atoms in addition to the isothiocyanato group include thiobis (3-isothiocyanatopropane), thiobis (2-isothiocyanatoethane), dithiobis (2- Sulfur-containing aliphatic isothiocyanate compounds such as isothiocyanatoethane), 1-isothiocyanato-4-[(2-isothiocyanato) sulfonyl] benzene, thiobis (4-isothiocyanatobenzene), sulfonylbis (4-isothiocyanato) Benzene), sulfur-containing aromatic isothiocyanate compounds such as dithiobis (4-isothiocyanatobenzene), 2,5-diisothiocyanatothiophene, 2,5-diisothiocyanato-1,4-dithiane, etc. Although sulfur heterocyclic compounds etc. are mentioned, it is not limited to an exemplary compound. Furthermore, halogen substituted products such as chlorine-substituted products, bromine-substituted products, alkyl-substituted products, alkoxy-substituted products, nitro-substituted products, prepolymer-modified products with polyhydric alcohols, carbodiimide-modified products, urea-modified products, and burette-modified products. Bodies, dimerization or trimerization reaction products, and the like can also be used.

  Furthermore, the isothiocyanate compound which has an isocyanato group is also mentioned. Aliphatic and alicyclic compounds such as 1-isocyanato-6-isothiocyanatohexane, 1-isocyanato-4-isothiocyanatocyclohexane, 1-isocyanato-4-isothiocyanatobenzene, 4-methyl-3-isocyanato- Aromatic compounds such as 1-isothiocyanatobenzene, heterocyclic compounds such as 2-isocyanato-4,6-diisothiocyanato-1,3,5-triazine, and 4-isocyanato-4′-isothi In addition to isothiocyanato groups such as isocyanatodiphenyl sulfide and 2-isocyanato-2′-isothiocyanatodiethyl disulfide, compounds containing sulfur atoms are not limited to the exemplified compounds. Furthermore, halogen substituted products such as chlorine-substituted products, bromine-substituted products, alkyl-substituted products, alkoxy-substituted products, nitro-substituted products, prepolymer-modified products with polyhydric alcohols, carbodiimide-modified products, urea-modified products, and burette-modified products. Bodies, dimerization or trimerization reaction products, and the like can also be used.

  Specific examples of preferred mercapto organic acid compounds as the resin modifier of the present invention include thioglycolic acid, 3-mercaptopropionic acid, thioacetic acid, thiolactic acid, thiomalic acid, thiosalicylic acid, and the like, but exemplary compounds It is not limited to only. Moreover, the said mercapto organic acid compound may be used individually or in mixture of 2 or more types.

  Specific examples of preferred organic acids and their anhydrides include hydrocarbon-based organic acids such as formic acid, acetic acid, propionic acid, butyric acid, benzoic acid, p-toluenesulfonic acid, methanesulfonic acid, and their halogens, nitro, cyanation Monofunctional organic acids such as trifluoroacetic anhydride, chloroacetic anhydride, dichloroacetic anhydride, trichloroacetic anhydride, phthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride Acid, methylnorbornenoic anhydride, methylnorbornanoic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, etc., bifunctional organic acids such as phthalic acid, succinic acid, thiodiglycolic acid, Examples include sulfur-containing organic acids such as thiodipropionic acid and dithiodipropionic acid. The present invention is not limited to.

Specific examples of preferred olefins include benzyl acrylate, benzyl methacrylate, butoxyethyl acrylate, butoxymethyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxymethyl methacrylate, glycidyl acrylate, glycidyl methacrylate, phenoxy. Ethyl acrylate, phenoxyethyl methacrylate, phenyl methacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate , Tetraethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, ethylene glycol bisglycidyl acrylate, ethylene glycol bisglycidyl methacrylate, bisphenol A diacrylate, bisphenol A Dimethacrylate, 2,2-bis (4-acryloxyethoxyphenyl) propane, 2,2-bis (4-methacryloxyethoxyphenyl) propane, 2,2-bis (4-acryloxyethoxyphenyl) propane, 2 , 2-bis (4-methacryloxydiethoxyphenyl) propane, bisphenol F diacrylate, bisphenol F dimethacrylate, 1 1-bis (4-acryloxyethoxyphenyl) methane, 1,1-bis (4-methacryloxyethoxyphenyl) methane, 1,1-bis (4-acryloxyethoxyphenyl) methane, 1,1-bis ( 4-methacryloxydiethoxyphenyl) methane, dimethyloltricyclodecane diacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, glycerol diacrylate, glycerol dimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol Tetramethacrylate, methylthioacrylate, methylthiomethacrylate, phenylthioacrylate, benzylthiomethacrylate, xylylenedithiol diacrylate, key (Meth) acrylate compounds such as silylenedithiol dimethacrylate, mercaptoethyl sulfide diacrylate, mercaptoethyl sulfide dimethacrylate,
Allyl compounds such as allyl glycidyl ether, diallyl phthalate, diallyl terephthalate, diallyl isophthalate, diallyl carbonate, diethylene glycol bisallyl carbonate, styrene, chlorostyrene, methylstyrene, bromostyrene, dibromostyrene, divinylbenzene, 3,9-divinylspirobi (m -Dioxane), vinyl compounds such as divinyl sulfide, divinyl disulfide, and the like, and diisopropenylbenzene are exemplified, but are not limited to the exemplified compounds.

  Furthermore, the above-mentioned several types of resin modifiers may be used alone or in combination of two or more. The amount of the resin modifier added varies depending on the structure of the compound constituting the polymerizable composition and cannot be generally limited, but is usually 0.001 wt% to 50 wt% with respect to the polymerizable composition. It is possible to add in a range. Considering optical properties of the obtained resin, it is preferable that the addition amount is 0.005 wt% to 25 wt%. If it is 0.01 wt%-15 wt%, it is more preferable.

  The polymerizable composition containing the thietane compound having the structure represented by the formula (1) of the present invention can be usually cured using a method for polymerizing a known thietane compound, and is a cured resin. The type and amount of the curing catalyst and the like, and the type and ratio of the monomer differ depending on the structure of the compound constituting the polymerizable composition and cannot be generally limited. Other than the above resin modifiers, amines, phosphines, organic acids and salts thereof, esters, anhydrides, inorganic acids, quaternary ammonium salts, quaternary phosphonium salts, tertiary sulfonium salts, secondary iodonium salts, Lewis acids , Radical polymerization catalysts, cationic polymerization catalysts and the like are usually used.

Specific examples of the curing catalyst include triethylamine, tri-n-butylamine, tri-n-hexylamine, N, N-diisopropylethylamine, triethylenediamine, triphenylamine, N, N-dimethylethanolamine, N, N-diethylethanolamine. N, N-dibutylethanolamine, triethanolamine, N-ethyldiethanolamine, N, N-dimethylbenzylamine, N, N-diethylbenzylamine, tribenzylamine, N-methyldibenzylamine, N, N-dimethyl Cyclohexylamine, N, N-diethylcyclohexylamine, N, N-dimethylbutylamine, N-methyldicyclohexylamine, N-methylmorpholine, N-isopropylmorpholine, pyridine, quinoline, N, N-dimethylanily N, N-diethylaniline, α-, β-, or γ-picoline, 2,2′-bipyridyl, 1,4-dimethylpiperazine, dicyandiamide, tetramethylethylenediamine, hexamethylenetetramine, 1,8-diazabicyclo (5 , 4,0) -7-undecene, aliphatic and aromatic tertiary amines such as 2,4,6-tris (N, N-dimethylaminomethyl) phenol,
Trimethylphosphine, triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tribenzylphosphine, 1,2-bis (diphenylphosphino) ethane, 1,2-bis (dimethylphosphine) Fino) phosphines such as ethane,
Trifluoroacetic acid, trichloroacetic acid, trifluoroacetic anhydride, ethyl trifluoroacetate, sodium trifluoroacetate, trihalogenoacetic acid and its esters, anhydrides, salts, p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, trifluoro Trihalogenomethanesulfonic acid and its esters, anhydrides, salts, hydrochloric acid, sulfuric acid, nitric acid such as lomethanesulfonic anhydride, ethyl trifluoromethanesulfonate, sodium trifluoromethanesulfonate,
Quaternary ammonium salts such as tetramethylammonium chloride, tetrabutylammonium chloride, tetrabutylammonium bromide,
Quaternary phosphonium salts such as tetramethylphosphonium chloride, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide,
Tertiary sulfonium salts such as trimethylsulfonium bromide and tributylsulfonium bromide, secondary iodium salts such as diphenyliodonium bromide, dimethyltin dichloride, dibutyltin dichloride, dibutyltin dilaurate, dibutyltin diacetate, tetrachlorotin, dibutyltin oxide , Diacetoxytetrabutyl distanoxane, zinc chloride, acetylacetone zinc, aluminum chloride, aluminum fluoride, triphenylaluminum, acetylacetone aluminum, isopropoxide aluminum, tetrachlorotitanium and its complex, tetraiodotitanium, dichlorotitanium diisopropoxy , Titanium alkoxides such as titanium isopropoxide, calcium acetate, boron trifluoride, boron trifluoride diethyl ether complex, boron trifluoride Lysine complex, boron trifluoride ethylamine complex, boron trifluoride acetic acid complex, boron trifluoride phosphate complex, boron trifluoride t-butylmethyl ether complex, boron trifluoride dibutyl ether complex, boron trifluoride THF complex Lewis acids such as boron trifluoride methyl sulfide complex, boron trifluoride phenol complex and other boron trifluoride complexes and boron trichloride complex such as boron trifluoride compounds and complexes thereof,
2,2′-azobis (2-cyclopropylpropionitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile) ), Radical polymerization catalysts such as t-butylperoxy-2-ethylhexanoate, n-butyl-4,4′-bis (t-butylperoxy) valerate, t-butylperoxybenzoate,
Diphenyliodonium hexafluorophosphoric acid, diphenyliodonium hexafluoroarsenic acid, diphenyliodonium hexafluoroantimony, triphenylsulfonium tetrafluoroboric acid, triphenylsulfonium hexafluorophosphoric acid, triphenylsulfonium hexafluoroarsenic acid, (tricumyl) iodonium tetrakis (pentafluoro) Examples thereof include cationic polymerization catalysts such as phenyl) borate, but are not limited to the exemplified compounds.

  The above curing catalysts may be used alone or in admixture of two or more. When two or more of these curing catalysts having different reactivity are used in combination, the handling property of the monomer, the optical properties of the resulting resin, the hue It is preferable because transparency and optical distortion (pulse separation) may be improved.

  Among the above compounds, preferred are tertiary amine compounds and phosphine compounds, quaternary ammonium salts, quaternary phosphonium salts, dimethyltin dichloride, dibutyltin dichloride, dibutyltin dilaurate, dibutyltin diacetate, tetrachlorotin, dibutyl. Organotin compounds such as tin oxide, diacetoxytetrabutyl distanoxane, diphenyliodonium hexafluorophosphoric acid, diphenyliodonium hexafluoroarsenic acid, diphenyliodonium hexafluoroantimony, triphenylsulfonium tetrafluoroboric acid, triphenylsulfonium hexafluorophosphoric acid Cation heavy, such as triphenylsulfonium hexafluoroarsenate, (tolylcumyl) iodonium tetrakis (pentafluorophenyl) borate Is the catalysts.

  The addition amount of the curing catalyst is used in the range of 0.001 to 10 wt% with respect to the total weight of the polymerizable composition, but is preferably used in the range of 0.005 to 5 wt%. It is more preferable to use in the range of 0.01 to 1 wt%. If the addition amount of the curing catalyst is within this range, it is possible to produce a resin that is cured well, the pot life is maintained, and the resin obtained has good transparency and optical properties. There is. The curing catalyst may be added directly to the thietane compound of the present invention, or may be added after being dissolved or dispersed in another compound constituting the polymerizable composition, but after being dissolved or dispersed in another compound. The addition may give a preferable result. Furthermore, when a curing catalyst is added, a preferable result may be obtained if it is carried out in a nitrogen atmosphere or a dry gas atmosphere. Furthermore, in order to further draw out the performance of the obtained resin, it is preferable that the amount of unreacted functional groups remaining in the resin is 0.5 wt% or less with respect to the total weight of the resin. More preferably, it is 0.3 wt% or less.

  When a polymerizable composition containing a thietane compound having a structure represented by the formula (1) of the present invention is cured and a resin is molded, other than the above, as in a known molding method, depending on the purpose Stabilizers, resin modifiers, chain extenders, crosslinking agents, light stabilizers typified by HALS, UV absorbers typified by benzotriazole, antioxidants typified by hindered phenols, anti-coloring Various substances such as an agent, a dye represented by an anthraquinone-based disperse dye, a filler, an external mold release agent represented by a silicone series or an internal mold release agent, and an adhesion improver may be added.

  Examples of the internal release agent used in the present invention may be any as long as they have a release effect and do not impair physical properties such as transparency of the resin, but preferably a surfactant. Is used. Surfactants that are preferably used as mold release agents are broadly classified into ionic surfactants and nonionic surfactants, and ionic surfactants are classified into anionic surfactants and cationic surfactants. The Examples of the anionic surfactant include sulfate ester, sulfonate ester, and phosphate ester. Among these, phosphate ester surfactants are preferable, and acidic phosphate ester anionic surfactants are particularly preferable. Is preferred. Some of the compounds described as the above-mentioned catalysts such as quaternary ammonium salts and quaternary phosphonium salts can also be used as internal mold release agents as long as they exhibit a mold release effect. These internal release agents may be used alone or in combination of two or more. These are appropriately selected from the monomer combination, polymerization conditions, economy, and ease of handling. The amount of the internal mold release agent used is usually in the range of 1 to 10,000 ppm based on the total weight of the gun composition, either alone or as a mixture of two or more. When the addition amount is 1 ppm or more, the release ability is good, and when it is 10000 ppm or less, release from the mold during the casting polymerization is suppressed, and deterioration of surface accuracy of the lens surface and white turbidity of the obtained lens are prevented. Can do.

  The addition amount of various additives other than the internal mold release agent that enables the above addition varies depending on the type, structure, and effect of each additive and cannot be generally limited. It is used in the range of 0.001 to 10 wt% with respect to the weight, but is preferably used in the range of 0.01 to 5 wt%. The dye is preferably used in the range of 1 ppb to 100 ppm instead of this range. Within these ranges, a well cured resin can be produced, and a resin having good transparency and optical properties may be obtained.

  A typical polymerization method for obtaining a resin (for example, a plastic lens) obtained by curing the composition of the present invention is cast polymerization. That is, the polymerizable composition of the present invention is injected between molding molds held by a gasket or a tape. The injection operation is preferably performed in a normal atmosphere as long as there is no particular problem, but better results may be obtained if it is performed in a nitrogen atmosphere or a dry gas atmosphere. The inside of the mold may be replaced with nitrogen gas or dry gas in advance. Here, if necessary, the polymerizable composition may be mixed with a curing catalyst and a resin modifier, or may be preliminarily subjected to operations such as depressurization at 10 kPa or less such as a defoaming operation, filter filtration and the like. Then, it can be cured by heating in a heatable apparatus such as an oven or water, and the resin can be taken out.

  The polymerization method and polymerization conditions for obtaining a resin obtained by curing the composition of the present invention cannot be generally limited by the type and amount of the curing catalyst used and the type and ratio of the monomer.

  The heating polymerization conditions of the polymerizable composition of the present invention injected into the molding mold differ depending on the composition and structure of the polymerizable composition containing the compound having the structure represented by the formula (1) of the present invention and are generally limited. The polymerization temperature is about −50 to 200 ° C., but the temperature is about −50 to 200 ° C., but the conditions are largely different depending on the type of resin modifier, the type of curing catalyst, the shape of the molding mold, etc. 150 ° C. is preferred. It is more preferable in the temperature range of 0 ° C to 130 ° C. The polymerization time is 0.01 to 100 hours, preferably 0.05 to 50 hours. More preferably, it is performed for 0.1 to 25 hours. In some cases, it is possible to perform polymerization by combining the temperature conditions with programs such as low temperature, temperature increase, and temperature decrease.

  Furthermore, the polymerizable composition of the present invention can shorten the polymerization time by irradiating an energy beam such as an electron beam or an ultraviolet ray. In this case, a curing catalyst such as a radical polymerization catalyst or a cationic polymerization catalyst described as the above-described curing catalyst may be added. Moreover, about the cured resin taken out, you may perform processes, such as annealing, as needed. The annealing condition varies depending on the structure of the compound constituting the polymerizable composition to be cured, the structure of the resin to be obtained, and the like, and cannot be generally limited, but is usually performed at 30 ° C to 200 ° C, but at 50 ° C to 150 ° C. Preferably it is done. More preferably, it is carried out at 70 ° C to 130 ° C.

  Furthermore, the resin of the present invention can be obtained as a molded product of various forms by changing the molding mold during casting polymerization, and has a high refractive index and transparency such as a spectacle lens, a camera lens, and a light emitting diode (LED). It can be used for various applications that require a resin that takes advantage of In particular, it is suitable as an optical material such as a spectacle lens and a camera lens. The refractive index of the optical material of the present invention is usually 1.70 or more, and is preferably 1.74 or more, more preferably 1.76 or more, particularly from the viewpoint of fashionability or the like of an eyeglass lens produced using the optical material. Preferably it is 1.77 or more.

In the lens using the optical material of the present invention thus obtained, if necessary, antireflection, imparting high hardness, improving abrasion resistance, improving chemical resistance, imparting antifogging, imparting fashion, etc. Therefore, physical or chemical treatments such as surface polishing, antistatic treatment, hard coat treatment, non-reflective coating treatment, and dyeing treatment can be performed.
[Example]
Hereinafter, the present invention will be specifically described by way of examples. The present invention is not limited to the following examples. In addition, the performance test of the obtained cured resin was implemented with the following test methods.
Refractive index (ne) Abbe number (νe): Measured at 20 ° C. using a Purfrich refractometer.
Heat resistance: Tg in the TMA penetration method (50 g load, pin tip 0.5 mmφ) was regarded as heat resistance.
-Resin transparency: Observed visually under a high-pressure mercury lamp. Cloudy ones were marked with x, and ones with excellent transparency were marked with ◯.
-Dyeing property: As a dyeing bath, to 1 L of pure water, 1.5 g of dispersed dye “MLP-Blue” manufactured by Mitsui BASF Dye Co., Ltd., 2.0 g of “MLP-Yellow”, 1.5 g of ML P-Blue Then, 3.0 g of benzyl alcohol was dissolved as a carrier, and a solution maintained at 90 ° C. was prepared. Using this dyeing solution, the above immersion process was performed, and then the dyeing process was confirmed visually. Those that were dyed well were marked with ○, and those that had problems with dyeing were marked with ×.
-Strength test: A sample width of about 10 mm and a thickness of 3 mm were prepared, and the tensile strength was measured by performing a test with a tester IN STRON 5582, using a test speed of 1 mm / min.

[Example 1]
234 g of 3-mercaptothietane, 112 g of 2-thiophene aldehyde and 500 g of toluene were charged into a reactor equipped with a stirrer, a thermometer and a Dane Stark equipped with a condenser, and 2 g of p-toluenesulfonic acid was added as a catalyst. Then, an azeotropic dehydration reaction was performed at a reaction temperature of 45 ° C. under reduced pressure. After completion of the reaction for 1 hour, the reaction was stopped when about 36 g of water was recovered. After completion of the reaction, the toluene layer was washed with 100 g of a 15% aqueous sodium hydroxide solution. Furthermore, after the toluene layer was washed three times with water, the toluene layer was taken out and concentrated under reduced pressure. The obtained residue had a purity of about 90% by HPLC analysis. Subsequently, purification was performed with a silica gel column using chloroform and hexane as developing solvents to obtain a main component. The main component obtained was almost colorless. As a result of analysis to confirm the structure of the compound obtained by purification, it was 2- [1,1-bis (3-thietanylthio) methyl] thiophene (hereinafter abbreviated as compound (a)).

  Here, the identification data of the obtained compound is shown below.

［実施例２］
２−チオフェンアルデヒドの代わりに３−チオフェンアルデヒドを用いたこと以外は実施例１と同様にして反応、洗浄、取り出し、精製を行った。精製により得られた化合物の構造を確認する為に分析を行った結果、３−［１，１−ビス（３−チエタニルチオ）メチル］チオフェン、（以下、化合物（ｂ）と略す）であった。

[Example 2]
The reaction, washing, removal and purification were carried out in the same manner as in Example 1 except that 3-thiophenaldehyde was used instead of 2-thiophenaldehyde. As a result of analysis to confirm the structure of the compound obtained by purification, it was 3- [1,1-bis (3-thietanylthio) methyl] thiophene (hereinafter abbreviated as compound (b)).

  Here, the identification data of the obtained compound is shown below.

［実施例３］
２−チオフェンアルデヒド１１２ｇの代わりにベンズアルデヒド１０６ｇを用いたこと以外は実施例１と同様にして反応、洗浄、取り出し、精製を行った。精製により得られた化合物の構造を確認する為に分析を行った結果、１−［１，１−ビス（３−チエタニルチオ）メチル］ベンゼン（以下、化合物（ｃ）と略す）であった。

[Example 3]
The reaction, washing, removal and purification were carried out in the same manner as in Example 1 except that 106 g of benzaldehyde was used instead of 112 g of 2-thiophenaldehyde. As a result of analysis to confirm the structure of the compound obtained by purification, it was 1- [1,1-bis (3-thietanylthio) methyl] benzene (hereinafter abbreviated as compound (c)).

  Here, the identification data of the obtained compound is shown below.

［実施例４］
２−チオフェンアルデヒド１１２ｇの代わりにテレフタルアルデヒド１３４ｇを用いたこと以外は実施例１と同様にして反応、洗浄、取り出し、精製を行った。精製により得られた化合物の構造を確認する為に分析を行った結果、１，４−ビス［１，１−ビス（３−チエタニルチオ）メチル］ベンゼン（以下、化合物（ｄ）と略す）であった。

[Example 4]
The reaction, washing, removal and purification were performed in the same manner as in Example 1 except that 134 g of terephthalaldehyde was used instead of 112 g of 2-thiophenaldehyde. As a result of analysis to confirm the structure of the compound obtained by purification, it was 1,4-bis [1,1-bis (3-thietanylthio) methyl] benzene (hereinafter abbreviated as compound (d)). It was.

  Here, the identification data of the obtained compound is shown below.

［実施例５］
室温２０℃にてビーカーに化合物（ａ）３０ｇと紫外線吸収剤としてバイオソーブ５８３（共同薬品社製）０．０３ｇを混合し溶解した後、窒素雰囲気下で硬化触媒としてＢＦ３・ジブチルエーテル錯体０．１５ｇを添加後混合したものを減圧下で０．４時間脱泡した後、ガラスモールドとガスケットよりなるモールド型に注入した。このモールドを３０℃から１２０℃まで徐々に昇温し、２４時間で重合を行った。重合終了後、徐々に冷却し、樹脂をモールドから取り出した。得られた樹脂は、透明性に優れ、歪みのない外観良好なものであった。

[Example 5]
30 g of compound (a) and 0.03 g of Biosorb 583 (manufactured by Kyodo Yakuhin Co., Ltd.) were mixed and dissolved in a beaker at room temperature of 20 ° C., and then 0.15 g of BF3 / dibutyl ether complex as a curing catalyst in a nitrogen atmosphere. After mixing, the mixture was degassed for 0.4 hours under reduced pressure, and then poured into a mold comprising a glass mold and a gasket. The mold was gradually heated from 30 ° C. to 120 ° C. and polymerized in 24 hours. After the polymerization was completed, the mixture was gradually cooled and the resin was taken out from the mold. The obtained resin was excellent in transparency and good in appearance without distortion.

When the optical properties of the obtained resin were measured, the refractive index was ne = 1.739 and νe = 29. The results are summarized in Table 5.
[Example 6]
A resin was obtained in the same manner as in Example 5 except that 30 g of compound (b) was used instead of compound (a). The obtained resin eventually had excellent transparency and good appearance without distortion. When the optical properties of the obtained resin were measured, the refractive index was ne = 1.739 and νe = 29. The physical properties obtained are summarized in Table 5.
[Example 7]
A resin was obtained in the same manner as in Example 6 except that 30 g of compound (d) was used instead of compound (a). The obtained resin eventually had excellent transparency and good appearance without distortion. When the optical properties of the obtained resin were measured, the refractive index was ne = 1.734 and νe = 30. The physical properties obtained are summarized in Table 5.
[Examples 8 to 10]
Resin in the same manner as in Example 6 except that 30 g of each of compounds (a) to (d) was used and 3.0 g of 1,1,2,2-tetrakis (mercaptomethylthio) ethane was added as a resin modifier. Got. The obtained resin eventually had excellent transparency and good appearance without distortion. The physical properties obtained are summarized in Table 5.
[Examples 11 to 13]
Resin in the same manner as in Example 6 except that 30 g of compound (d) was used and 3.0 g of 1,1,2,2-tetrakis (mercaptomethylthio) ethane and 3.0 g of sulfur were added as a resin modifier. Got. The obtained resin eventually had excellent transparency and good appearance without distortion. The physical properties obtained are summarized in Table 5.
[Comparative Example 1]
Bis (3-thietanyl) disulfide was synthesized as a thietane compound, and a resin was obtained in the same manner as in Example 6.

When the optical properties and heat resistance of the obtained resin were measured, it was found that the refractive index was ne = 1.736 and νe = 33. The physical properties obtained are summarized in Table 5.

Claims (12)

A thietane compound having one or more skeleton and two or more thietanyl groups selected from dithio acetal skeleton and dithioketal bone skeleton or Ranaru group in the molecule,
The thietane compound which has a structure represented by following formula (1).

(In the formula, R 1 and R 2 each independently represent a hydrogen atom, a phenyl group, a thienyl group or a group represented by the following formula (*). However, R 1 and R 2 are not both hydrogen atoms.)

  The thietane compound according to claim 1, wherein R1 and / or R2 has a structure having an aromatic ring and / or a heterocyclic ring.   The thietane compound is 2- [1,1-bis (3-thietanylthio) methyl] thiophene, 3- [1,1-bis (3-thietanylthio) methyl] thiophene, 1- [1,1-bis (3-thietanylthio) The thietane compound according to any one of claims 1 and 2, which is any one of) methyl] benzene and 1,4-bis [1,1-bis (3-thietanylthio) methyl] benzene.   A polymerizable composition comprising the thietane compound according to any one of claims 1 to 3.   Furthermore, the polymeric composition of Claim 4 containing a single-piece | unit sulfur.   A resin obtained by curing the polymerizable composition according to claim 4 or 5.   An optical material comprising the resin according to claim 6.   A method for producing a resin, comprising a step of cast polymerization of the polymerizable composition according to claim 4. The method for producing a thietane compound according to any one of claims 1 to 3, wherein 3-mercaptothietane and a compound having one or more aldehyde groups or keto groups are used as raw materials. The method according to claim 9 compounds having one or more of the above aldehyde group or keto group is one having at least two aldehyde or keto group in total. The method according to claim 9 or 10, wherein the compound having at least one aldehyde group or keto group further has an aromatic ring and / or a heterocyclic ring.   The method according to any one of claims 9 to 11, wherein the azeotropic dehydration reaction is performed using a proton acid and / or a Lewis acid as a catalyst at a temperature in the range of 0 to 120 ° C. .