JP4299726B2 - Polymerizable composition for optical resin - Google Patents

Description

  The present invention relates to an application of a polythietane compound that can be suitably used in the field of resins such as optical materials that require a high refractive index and high transparency. The present invention also relates to a polymerizable composition containing the polythietane compound and sulfur, a resin and an optical material obtained by polymerizing and curing the composition, and a method for producing a resin for curing the composition.

  In recent years, plastic lenses are rapidly becoming popular in optical materials such as eyeglass 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, but physical and chemical properties are good in impact resistance, easy dyeing, and heat resistance. That is, there is no problem, and the specific gravity is low. In other words, the lens manufacturing method and the monomer compound are safe for the human body and easy to handle.

For the purpose of achieving a high refractive index, a polythiourethane resin in which a sulfur atom is introduced into the molecule is known. The polythiourethane resin is a resin having an excellent balance such as high refractive index, good impact resistance and dyeability. In addition, a method using a polyepisulfide compound has been proposed as having a high refractive index and a high Abbe number. (For example, see Patent Document 1)
In addition, as a method for pursuing a higher refractive index than a method using a polyepisulfide compound, a method of adding a known sulfur-containing compound to a polyepisulfide compound has been proposed. In the method of adding a sulfur-containing compound, there are cases where the crosslinkability of the resin is lowered and the heat resistance is lowered, or the resin strength is lowered. (For example, see Patent Document 2 and Patent Document 3)

On the other hand, the inventors of the present application have previously found a resin obtained by polymerizing and curing a polythietane compound and a general compound as a high-strength resin that can achieve a high refractive index other than the polyepisulfide compound, I am making a proposal. (For example, see Patent Document 4)
Japanese Patent Laid-Open No. 9-110979 JP 2001-002783 A Japanese Patent Laid-Open No. 2004-002712 JP 2003-327583 A

  The object of the present invention is to have a higher refractive index of a plastic lens and at the same time to have a resin having a higher strength. It is to provide a transparent resin.

  As a result of searching for a polymerizable composition having a higher refractive index and higher strength using the polythietane compound, the present inventors have found that the polymerizability contains a specific polythietane compound and sulfur at a specific blending ratio. The composition has been found and the present invention has been achieved.

That is, the present invention
[1] A polymerizable composition containing a polythietane compound having a structure represented by the following formula (1) and sulfur, and when the total of the polythietane compound and sulfur is 100 parts by weight, the sulfur The polymerizable composition whose content is 5-25 weight part.

  Wherein R ′ and R ″ are a substituted or unsubstituted hydrocarbon group having 1 to 2 carbon atoms which may be thiated, U is a substituted or unsubstituted straight chain which may be thiated, Represents a branched or cyclic C1-C8 alkylene group, arylene group or aralkylene group, l represents an integer of 0-2, o represents an integer of 1 or 2, m, n represents an integer of 0-3, p , Q represents an integer of 0 or 1.).

Hereinafter, [2] to [7] are each a preferred embodiment of the present invention.
[2] The compound having the structure represented by formula (1) is bis (3-thietanyl) disulfide, bis (3-thietanyl) sulfide, bis (3-thietanylthio) methane, or bis (3-thietanylthiomethyl). The polymerizable composition according to [1], which is any of sulfides.
[3] A resin obtained by curing the polymerizable composition according to [1] or [2].
[4] An optical material containing the resin according to [3].
[5] A method for producing a resin comprising a step of cast polymerization of the polymerizable composition according to [1] or [2].
[6] As described in [1] or [2], a boron trihalide compound and a complex thereof, and one or more compounds selected from trihalogenomethanesulfonic acid, an ester thereof, and an anhydride are used as a curing catalyst. A method for producing a resin, comprising a step of curing the polymerizable composition.
[7] A resin comprising a step of curing one obtained by adding one or more compounds having one or more SH groups as a resin modifier to the polymerizable composition according to [1] or [2] Manufacturing method.

  According to the present invention, it is possible to produce a polymerization composition useful for increasing the refractive index as an alternative to an optical material in the high refractive index field, particularly a resin using a polyepisulfide compound as a raw material. The resin obtained from the polymerized composition has high optical properties, and contributes to high refractive index and thinning, particularly in the field of eyeglass lenses.

Hereinafter, the present invention will be described in detail.
First, a specific polythietane compound which is one of the constituent features of the present invention will be described.

  The specific polythietane compound used in the present invention has a structure represented by the following formula (1). In addition, the “carbon number” in the description of the following formula (1) indicates the carbon number after thialation when it is thialated.

(In the formula, R ′ and R ″ are a substituted or unsubstituted divalent hydrocarbon group having 1 to 2 carbon atoms which may be thiated, a linear, branched or cyclic alkylene group, or a linear chain. Represents a branched or cyclic alkenylene group, and U represents a substituted or unsubstituted linear, branched or cyclic alkylene group having 1 to 8 carbon atoms, an arylene group or an aralkylene group which may be thiated. l represents an integer of 0-2, o represents an integer of 1 or 2, m, n represents an integer of 0-3, p, q represents an integer of 0-2.)

  The substituted or unsubstituted divalent hydrocarbon group having 1 to 2 carbon atoms represented by R ′ and R ″ is a linear, branched or cyclic alkylene group, or a linear, branched or cyclic alkenylene group. U is preferably a linear, branched or cyclic alkylene group having 1 to 8 carbon atoms, an arylene group having 6 to 8 carbon atoms, or an aralkylene group having 7 to 8 carbon atoms, and an alkyl in the alkylene group and the aralkylene group. A part of the methylene group in the component may be thiated by replacing with sulfur, for example, a divalent group derived from a linear alkane such as methane, ethane, propane, butane, isopropane, sec-butane, etc. , Divalent groups derived from branched alkanes such as tert-butane, sec-pentane and neo-pentane, and cyclic alkanes such as cyclopentane and cyclohexane Divalent groups derived from linear or branched thiaalkanes such as 3-thiapentane, 4-thiahexane, 3,6-dithiaoctane, 3,6,9-trithiaundecane, 1,4 A divalent group derived from a cyclic thiaalkane such as dithiane, 1,3-dithiane, 1,3-dithiolane, 1,3-dithietane, or an unsubstituted or alkyl-substituted benzene such as benzene, toluene or xylene. Examples thereof include a divalent group and a divalent group derived from an aromatic heterocycle such as thiophene.

  U may be substituted with an alkylene sulfide (thio) group containing a reactive functional group such as an episulfide group, and may have 1 to 3 thietanyl groups or thietanylthio groups as substituents. . That is, trifunctional or higher functional polythietane compounds are also included.

  Specific examples of the compound having the structure represented by the formula (1) include bis (3-thietanyl) sulfide, bis (3-thietanyl) disulfide, bis (3-thietanyl) trisulfide, and bis (3-thietanyl) tetra. Sulfide, 1,4-bis (3-thietanyl) -1,3,4-trithiabutane, 1,5-bis (3-thietanyl) -1,2,4,5-tetrathiapentane, 1,6-bis ( 3-thietanyl) -1,3,4,6, -tetrathiahexane, 1,6-bis (3-thietanyl) -1,3,5,6, -tetrathiahexane, 1,7-bis (3- Thietanyl) -1,2,4,5,7-pentathiaheptane, 1,7-bis (3-thietanylthio) -1,2,4,6,7-pentathiaheptane, 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, 1,6-bis (3-thietanylthio) hexane, 1,6-bis (3- Thietanylthio) -2-methylhexane, 3,8-bis (3-thietanylthio) -3,6-dithiaoctane, 1,2,3-tris (3-thietanyl) E) 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-thietanylthio) -2,4-bis (3-thiethani) Luthiomethyl) -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) E) -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-bis (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-to Thiaundecane, 1,11-bis (3-thietanylthio) -4,7-bis (3-thietanylthiomethyl) -3,6,9-trithiaundecane, 1,11-bis (3-thietanylthio) -5 , 7-bis (3-thietanylthiomethyl) -3,6,9-trithiaundecane, 1,1,3,3-tetrakis (3-thietanylthiomethylthio) propane, 1,1,2,2- Chain aliphatic 3-thietanylthio compounds such as tetrakis (3-thietanylthiomethylthio) ethane, 3- (3-thietanylthiomethyl) -1,5-di (3-thietanylthio) -2,4-dithiapentane, as well as,

1,3-bis (3-thietanylthio) cyclohexane, 1,4-bis (3-thietanylthio) cyclohexane, 1,3-bis (3-thietanylthiomethyl) cyclohexane, 1,4-bis (3-thietanylthio) Methyl) 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-dithiane, 2-bis (3-thietanylthio) methyl-1,3-dithi Orchids and cyclic aliphatic 3-thietanylthio compounds, 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. An aromatic 3-thietanylthio compound of 1,3-bis (3-thietanylthio) propan-1-one, , 1,3-bis (3-thietanylthio) -2-methyl-1-but-one and the like, but is not limited to only these exemplified compounds. Among the exemplified compounds, preferred compounds include bis (3-thietanyl) disulfide, bis (3-thietanyl) sulfide, bis (3-thietanyl) trisulfide, bis (3-thietanyl) tetrasulfide, 1,4-bis ( 3-thietanyl) -1,3,4-trithiabutane, 1,5-bis (3-thietanyl) -1,2,4,5-tetrathiapentane, 1,6-bis (3-thietanyl) -1,3 , 4,6, -tetrathiahexane, 1,6-bis (3-thietanyl) -1,3,5,6, -tetrathiahexane, 1,7-bis (3-thietanyl) -1,2,4 , 5,7-pentathiaheptane, 1,7-bis (3-thietanylthio) -1,2,4,6,7-pentathiaheptane, 1,1-bis (3-thietanylthio) methane and 1,2- Screw (3- Ethaneylthio) 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-bis (3- Thietanylthiomethyl) -3,6,9-trithiaundecane, 1,11-bis (3-thietanylthio) -5,7-bis (3-thietanylthiomethyl) -3,6,9-trithiaundecane 2,5-bis (3-thietanylthiomethyl) -1,4-dithiane, 2,5-bis [[2- (3-thietanylthio) ethyl] thiomethyl] -1,4-dithiane, 2,5- Screw (3-Chi Tanylthiomethyl) -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-dithiola, and more preferable compounds include bis (3-thietanyl) disulfide, bis (3-thietanyl) sulfide, bis (3 -Thietanyl) trisulfide, bis (3-thietanyl) tetrasulfide, 1,4-bis (3-thietanyl) -1,3,4-trithiabutane, 1,5-bis (3-thietanyl) -1,2, 4,5-tetrathiapentane, 1,6-bis (3-thietanyl) -1,3,4,6, -tetrathiahexane, 1,6-bis (3-thietanyl) -1,3,5,6 , -Tetrathiahexane, 1,7-bis (3-thietanyl) -1,2,4,5,7-pentathiaheptane, 1,7-bis (3-thietanylthio) -1,2,4,6,7 -Pentathiaheptane, bis (3-thietanylthio) methane, bis (3-thietanylthiomethyl) sulfide, 2-bis (3-thietanylthio) methyl-1,3-dithiolane.

  Next, sulfur, which is another constituent element of the present invention, will be described.

  Sulfur used in the present invention is inorganic sulfur (sulphur alone), and the purity used in the transparent resin of the present invention is preferably 98% or more, more preferably 99% or more, More preferably, it is 99.5% or more. In order to increase purity, a method of removing volatile components may be preferable.

  In addition, the sulfur property is not a problem as long as it is a form that can be dissolved in the polythietane compound, which is another constituent of the present invention, but is preferably a powder, and more preferably a fine powder.

  In the present invention, the polythietane compound represented by the formula (1) and inorganic sulfur (sulphur simple substance) are mixed and dissolved, and the sulfur addition amount in the composition is the formula (from the viewpoint of a high refractive index. When the total of the polythietane compound represented by 1) and sulfur is 100 parts by weight, the effect of improving the refractive index is small when the amount of sulfur added is less than 5 parts by weight. Further, when the total amount of the polythietane compound represented by formula (1) and sulfur is 100 parts by weight, if the amount of sulfur added is more than 25 parts by weight, it is not preferable from the viewpoints of heat resistance, strength and turbidity. Therefore, the addition amount of sulfur is preferably 5 to 25 parts by weight when the total of the polythietane compound represented by formula (1) and sulfur is 100 parts by weight. More preferably, the addition amount of sulfur is 8 to 25 parts by weight when the total of the polythietane compound represented by formula (1) and sulfur is 100 parts by weight. More preferably, the addition amount of sulfur is 10 to 20 parts by weight when the total of the polythietane compound represented by formula (1) and sulfur is 100 parts by weight.

  As a method for mixing the polythietane compound and sulfur according to the present invention, it is sufficient to add sulfur to the polythietane compound and then dissolve it by stirring. In this case, it is preferable to increase the temperature as necessary. . In addition, it may be added and dissolved in the resin modifiers and curing catalysts described later, all of which are mixed separately in the same container, even if they are mixed at the same time under stirring or added stepwise. Later, it may be remixed in the same container.

  The constituent requirements of the polymerizable composition according to the present invention are a polymerizable composition containing a polythietane compound having a structure represented by (1) and sulfur. Further 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, To adjust the physical properties such as polymerization shrinkage, water absorption, hygroscopicity, chemical resistance, viscoelasticity, adjustment of transmittance and transparency, viscosity of polymerizable composition, and other handling and transportation methods For the purpose of improving resin and handling, etc., methods and operations generally used when synthesizing organic compounds such as purification, washing, heat retention, cold insulation, filtration, reduced pressure treatment, etc. It may be preferable to add a known compound or the like as a stabilizer or a resin modifier for the purpose of obtaining a good resin. Examples of compounds 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.

  Purification of the polymerizable composition is a technique used to improve the transparency of the resin obtained by curing, to improve the hue, or to increase the purity. The formula (1) according to the present invention is used. A method for purifying a polymerizable composition containing a polythietane compound having a structure represented by the following is a known method such as distillation, recrystallization, column chromatography (silica gel method, activated carbon method, ion exchange resin method, etc.), Any method may be used at any timing as long as the extraction is performed, and it is only necessary that the transparency and hue of the resin obtained by curing a composition generally obtained by purification are improved.

  The method of washing the polymerizable composition is a technique used to improve the transparency of the resin obtained by curing or to improve the hue, but when the polymerizable composition is synthesized and taken out or after the synthesis A substance that is washed with a polar and / or non-polar solvent at a timing such as after removal of the resin and inhibits the transparency of the resin, for example, an inorganic salt used in synthesizing a polymerizable composition, or a by-product, For example, a method of removing or reducing the amount of ammonium salt or thiourea can be mentioned. The solvent to be used can not be generally limited by the polymerizable composition itself to be washed or the polarity of the solution containing the polymerizable composition, but the component to be removed can be dissolved and the polymerizable composition to be washed Those which are hardly compatible with itself or a solution containing a polymerizable composition are preferable, and not only one type but also two or more types may be mixed and used. The components to be removed here vary depending on the purpose and application, but are preferably as small as possible. Usually, good results may be obtained when the content is 5000 ppm or less, more preferably 1000 ppm or less.

  The method of keeping, cooling, and filtering the polymerizable composition is a technique used to improve the transparency of the resin obtained by curing or to improve the hue, but it is synthesized and taken out. In general, it is performed at a timing such as at the time of extraction or after removal after synthesis. For example, in the case where the polymerizable composition is crystallized during storage and handling becomes worse, the heat retention is a method in which the polymerizable composition and the resin obtained by curing the polymerizable composition are heated and dissolved within a range in which the performance of the resin does not deteriorate. Is mentioned. The temperature range to be heated and the method of heating and dissolving cannot be generally limited depending on the structure of the compound constituting the polymerizable composition to be handled, but are usually performed within the freezing point + 50 ° C., preferably within + 20 ° C., and can be stirred. Examples thereof include a method in which the internal solution is moved and dissolved by mechanical stirring with an apparatus or bubbling with an inert gas in the composition. The cold insulation is usually performed for the purpose of enhancing the storage stability of the polymerizable composition, but when the melting point is high and there is a problem in handling after crystallization, it is necessary to consider the storage temperature. Although the cold temperature cannot be generally limited by the structure of the compound constituting the polymerizable composition to be handled and the storage stability, in the case of the polymerizable composition containing the compound having the structure represented by the formula (1), 20 ° C. It is good to store at the following low temperature, Preferably it is 10 degrees C or less. However, when the melting point is high, handling at a temperature higher than the freezing point is usually good in use. If dissolution by heating is possible easily, there is no problem even if it is stored below the freezing point.

  In the case of a polymerizable composition used for optical applications, since its very high transparency is required, it is usually preferable to filter the polymerizable composition with a filter having a small pore size. The pore size of the filter used here is usually 0.05 to 10 μm, but in view of operability and performance, it is preferably 0.05 to 5 μm, more preferably 0.1 to 5 μm. When the polymerizable composition containing the thietane compound of the present invention is filtered without exception, good results are often obtained. As for the temperature at which filtration is performed, a more preferable result may be obtained if it is performed at a low temperature near the freezing point. However, if solidification proceeds during filtration, it may be performed at a temperature that does not hinder the filtration operation. There is.

  The reduced pressure treatment is a technique generally used to remove a solvent, dissolved gas, and odor that lower the performance of a resin obtained by curing a polymerizable composition. The dissolved solvent generally causes a decrease in the refractive index and heat resistance of the resin obtained, so it is necessary to remove it as much as possible. The permissible value of the dissolved solvent cannot be generally limited depending on the structure of the compound constituting the polymerizable composition to be handled and the structure of the dissolved solvent, but it is usually preferably 1% or less, more preferably 5000 ppm or less. It is preferable to remove the dissolved gas because it has a detrimental effect on the polymerization of the dissolved gas and bubbles mixed into the resulting resin. In particular, it is preferable to remove a gas such as water vapor by bubbling with a dry gas. About a dissolved amount, it cannot unconditionally limit by the structure of the compound which comprises a polymeric composition, the physical property and structure of dissolved gas, and a kind.

  Examples of the resin modifier include known thietane compounds other than those contained in the polymerizable composition according to the present invention, dithietane compounds, trithiethane compounds, thiolane compounds, dithiolane compounds, trithiolane compounds, dithian compounds, trithian compounds, episulfide compounds, and the like. Epoxy compounds, amine compounds, thiol compounds, hydroxy compounds including phenolic compounds, iso (thio) cyanate compounds, mercapto organic acids, organic acids and anhydrides, amino acids and mercaptoamines, (meth) acrylates Examples include olefins including thiols, cyclic organic compounds and inorganic compounds having sulfur atoms or selenium atoms. 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. Of these, iso (thio) cyanate compounds are particularly preferred. 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.

  Specific examples of the episulfide compound as the resin modifier according to the present invention include bis (1,2-epithioethyl) sulfide, bis (1,2-epithioethyl) disulfide, bis (epithioethylthio) methane, and bis (epi Thioethylthio) benzene, bis [4- (epithioethylthio) phenyl] sulfide, epithioethyl compounds such as bis [4- (epithioethylthio) phenyl] methane, bis (2,3-epithiopropyl) sulfide, Bis (2,3-epithiopropyl) disulfide, bis (2,3-epithiopropylthio) methane, 1,2-bis (2,3-epithiopropylthio) ethane, 1,2-bis (2, 3-epithiopropylthio) propane, 1,3-bis (2,3-epithiopropylthio) propane, 1,3-bis (2, -Epithiopropylthio) -2-methylpropane, 1,4-bis (2,3-epithiopropylthio) butane, 1,4-bis (2,3-epithiopropylthio) -2-methylbutane, , 3-bis (2,3-epithiopropylthio) butane, 1,5-bis (2,3-epithiopropylthio) pentane, 1,5-bis (2,3-epithiopropylthio) -2 -Methylpentane, 1,5-bis (2,3-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-epithiopropipropyl Ruthio) -4- (2,3-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (2,3-epithiopropylthio) -4,5-bis (2,3-epi Thiopropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (2,3-epithiopropylthio) -4,4-bis (2,3-epithiopropylthiomethyl) -3,6-dithiaoctane 1,8-bis (2,3-epithiopropylthio) -2,5-bis (2,3-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (2,3- Epithiopropylthio) -2,4,5-tris (2,3-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,1,1-tris [[2- (2,3-epithiopropyl Thio) ethyl] thiomethyl] -2- (2,3- Pithiopropylthio) ethane, 1,1,2,2-tetrakis [[2- (2,3-epithiopropylthio) ethyl] thiomethyl] ethane, 1,11-bis (2,3-epithiopropylthio) ) -4,8-bis (2,3-epithiopropylthiomethyl) -3,6,9-trithiaundecane, 1,11-bis (2,3-epithiopropylthio) -4,7-bis (2,3-epithiopropylthiomethyl) -3,6,9-trithiaundecane, 1,11-bis (2,3-epithiopropylthio) -5,7-bis (2,3-epithio) Chain aliphatic 2,3-epithiopropylthio compounds such as propylthiomethyl) -3,6,9-trithiaundecane, and

1,3-bis (2,3-epithiopropylthio) cyclohexane, 1,4-bis (2,3-epithiopropylthio) cyclohexane, 1,3-bis (2,3-epithiopropylthiomethyl) Cyclohexane, 1,4-bis (2,3-epithiopropylthiomethyl) cyclohexane, 2,5-bis (2,3-epithiopropylthiomethyl) -1,4-dithiane, 2,5-bis [[ 2- (2,3-epithiopropylthio) ethyl] thiomethyl] -1,4-dithiane, 2,5-bis (2,3-epithiopropylthiomethyl) -2,5-dimethyl-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 , 3-epithiopropylthio compound,

Monofunctional episulfide compounds such as ethylene sulfide, propylene sulfide, mercaptopropylene sulfide, mercaptobutene sulfide, epithiochlorohydrin,

Bis (2,3-epithiopropyl) ether, bis (2,3-epithiopropyloxy) methane, 1,2-bis (2,3-epithiopropyloxy) ethane, 1,2-bis (2, 3-epithiopropyloxy) propane, 1,3-bis (2,3-epithiopropyloxy) propane, 1,3-bis (2,3-epithiopropyloxy) -2-methylpropane, 1,4 -Bis (2,3-epithiopropyloxy) butane, 1,4-bis (2,3-epithiopropyloxy) -2-methylbutane, 1,3-bis (2,3-epithiopropyloxy) butane 1,5-bis (2,3-epithiopropyloxy) pentane, 1,5-bis (2,3-epithiopropyloxy) -2-methylpentane, 1,5-bis (2,3-epi Thiopropyloxy) 3-thiapentane, 1,6-bis (2,3-epithiopropyloxy) hexane, 1,6-bis (2,3-epithiopropyloxy) -2-methylhexane, 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) It can be exemplified aromatic 2,3-epithiopropyl oxy compounds such biphenyl, but is not limited only to the exemplified compounds.

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

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

  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-epoxypropyl) disulfide, 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) pen 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-epoxy Propylchi Methyl) -3-thiapentane, 1,5-bis (2,3-epoxypropylthio) -2,4-bis (2,3-epoxypropylthiomethyl) -3-thiapentane, 1- (2,3-epoxy Propylthio) -2,2-bis (2,3-epoxypropylthiomethyl) -4-thiahexane, 1,5,6-tris (2,3-epoxypropylthio) -4- (2,3-epoxypropyl) Thiomethyl) -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-dithiaoctane, 1,8-bis (2,3-epoxypropylthio) -2,5-bis (2,3-epoxypropylthiomethyl) -3,6-dithiaoctane 1,8-bis (2,3-epoxypropylthio) -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-epoxypropylthiomethyl) -3,6,9-trithiaundecane and the like chain aliphatic 2,3-epoxypropylthio compounds, 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) Aromatics such as phenyl] sulfide, bis [4- (2,3-epoxypropylthio) phenyl] sulfone, 4,4′-bis (2,3-epoxypropylthio) biphenyl , 3-epoxypropyl-thio compounds,

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) It can be exemplified aromatic 2,3-epoxypropyloxy compounds such biphenyl, but is not limited only 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- or 1,4-diaminomethylcyclohexane, 2- or 4-aminopiperidine, 2- or 4-aminomethylpiperidine, 2- or 4-aminoethylpiperidine, N-aminoethylmorpholine, N- Primary polyamine compounds such as aminopropylmorpholine,

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-diaminopentane, N, N′-diethyl-1,6-diaminohexane, N, N′-diethyl-1,7-diaminoheptane, piperazine, 2-methylpiperazine, 2,5-dimethylpiperazine 2,6-dimethylpiperazine, homopiperazine, 1,1-di- (4-piperidyl) methane, 1,2-di- (4-piperidyl) ethane, 1,3-di- (4-piperidyl) propane, Secondary polyamine compounds such as 1,4-di- (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, more preferred are benzylamine and piperazines.

  Further, examples of the thiol compound that can be added as a resin modifier include 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, Aliphatic mercaptan compounds such as ethylphenyl mercaptan, 2-mercaptomethyl-1,3-dithiolane, 2-mercaptomethyl-1,4-dithiane, aromatic mercaptan compounds such as thiophenol and mercaptotoluene,

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 ( 3-mercaptopropionate), aliphatic polythiol compounds such as tetrakis (mercaptomethyl) methane,

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,

Polythiol containing a heterocyclic ring such as 2-methylamino-4,6-dithiol-sym-triazine, 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, Mercapto such as 2,3-tris (mercaptoethylthio) benzene, 1,2,4-tris (mercaptoethylthio) benzene, 1,3,5-tris (mercaptoethylthio) benzene, and their nuclear alkylated products An aromatic polythiol compound containing a sulfur atom in addition to the group,

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, 1,1,2,2-tetrakis (mercaptomethylthio) ethane, 1,1,3,3-tetrakis ( Mercaptomethylthio) propane, bis (2,3-dimercaptopropyl) sulfide, bis (1,3-di) Lucaptopropyl) sulfide, 2,5-dimercapto-1,4-dithiane, 2,5-dimercaptomethyl-1,4-dithiane, 2,5-dimercaptomethyl-2,5-dimethyl-1,4- Dithiane, 4,6-bis (mercaptomethylthio) -1,3-dithiane, bis (mercaptomethyl) disulfide, bis (mercaptoethyl) disulfide, bis (mercaptopropyl) disulfide, and the like, and thioglycolic acid and mercaptopropionic acid Ester of

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), an aliphatic polythiol compound containing a sulfur atom in addition to a mercapto group such as bis (2,3-dimercaptopropyl ester) dithiodipropionate

Heterocyclic compounds containing sulfur atoms in addition to mercapto groups such as 3,4-thiophenedithiol, 2,5-dimercapto-1,3,4-thiadiazole, bismuthiol,

Examples of the mercapto compound having a hydroxy group include 2-mercaptoethanol, 3-mercapto-1,2-propanediol, glycerin di (mercaptoacetate), 1-hydroxy-4-mercaptocyclohexane, 2,4-di Mercaptophenol, 2-mercaptohydroquinone, 4-mercaptophenol, 1,3-dimercapto-2-propanol, 2,3-dimercapto-1-propanol, 1,2-dimercapto-1,3-butanediol, pentaerythritol tris ( 3-mercaptopropionate), pentaerythritol mono (3-mercaptopropionate), pentaerythritol bis (3-mercaptopropionate), pentaerythritol tris (thioglycolate), dipentaerythritol Examples include tall pentakis (3-mercaptopropionate), hydroxymethyl-tris (mercaptoethylthiomethyl) methane, 1-hydroxyethylthio-3-mercaptoethylthiobenzene, etc. Absent. Furthermore, you may use the chlorine substituted body of these polythiol compounds, and the halogen substituted body of a bromine substituted body. These can be used alone or in combination of two or more. Among these thiol compounds, in view of the refractive index of the resin obtained, preferred are polysulfide-based polythiol compounds, and more preferred are polythiol compounds composed only of carbon, hydrogen, and sulfur atoms. Considering the heat resistance of the resulting resin, it is preferably bifunctional or higher, more preferably tetrafunctional or higher, rather than simple. Specific examples of preferred ones include bis (mercaptomethyl) sulfide, 1,1,2,2-tetrakis (mercaptomethylthio) ethane, 1,1,3,3-tetrakis (mercaptomethylthio) propane, 4,8-dimercapto Methyl-1,11-mercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-mercapto-3,6,9-trithiaundecane, and 5,7-dimercaptomethyl -1,11-mercapto-3,6,9-trithiaundecane.

  Specific examples of hydroxy compounds containing phenolic compounds as resin modifiers according to 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, tetrahydrofurfuryl 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 In addition to polyols such as (2-hydroxyethyl ether) and dibromoneopentyl glycol, oxalic acid, glutamic acid, adipic acid, acetic acid, propionic acid, phthalic acid, isophthalic acid, salicylic acid, pyromellitic acid, 3-bromopropionic acid, 2 -Condensation reaction product of an organic polybasic acid such as bromoglycolic acid, dicarboxycyclohexane, butanetetracarboxylic acid, bromophthalic acid and the polyol and the polyol and ethylene oxide or propylene. Examples include addition reaction products with alkylene oxides such as lenoxide, 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'-tetramethylxylyl 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 and the like can also be used.

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, isothiocyan Monofunctional isothiocyanate compounds such as natomethylbicycloheptane,

Aliphatic polyisothiocyanate compounds such as 1,6-diisothiocyanatohexane, p-phenyleneisopropylidenediisothiocyanate,
Alicyclic polyisothiocyanate compounds such as cyclohexane diisothiocyanate, 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 isothiocyanate group include thiobis (3-isothiocyanatopropane), thiobis (2-isothiocyanatoethane), dithiobis ( Sulfur-containing aliphatic isothiocyanate compounds such as 2-isothiocyanatoethane), 1-isothiocyanato-4-[(2-isothiocyanato) sulfonyl] benzene, thiobis (4-isothiocyanatobenzene), sulfonyl bis (4-isothi Ouocyanatobenzene), sulfur-containing aromatic isothiocyanate compounds such as dithiobis (4-isothiocyanatobenzene), 2,5-diisothiocyanatothiophene, 2,5-diisothiocyanato-1,4-dithiane, etc. However, it is not limited to the exemplified compounds.Furthermore, halogen-substituted products such as chlorine-substituted products and 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.

  Furthermore, the isothiocyanate compound which has an isocyanate 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 isothiocyanate 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 and 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.

  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 and divinyl disulfide, and diisopropenylbenzene are exemplified, but the compound is 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 0.01 wt% to 50 wt% with respect to the polymerizable composition. It is possible to add in a range, preferably 0.01 wt% to 25 wt%, more preferably 0.01 wt% to 15 wt%.

  The composition of the present invention can usually be cured using a known method for polymerizing a polythietane compound, and the type and amount of a curing catalyst for obtaining a cured resin, the type and ratio of monomers. Varies depending on the structure of the compound constituting the polymerizable composition and cannot be generally limited, but as the type of curing catalyst, amines other than the resin modifier of the present invention, 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,
Cationic polymerization catalysts such as diphenyliodonium hexafluorophosphoric acid, diphenyliodonium hexafluoroarsenic acid, diphenyliodonium hexafluoroantimony, triphenylsulfonium tetrafluoroboric acid, triphenylsulfonium hexafluorophosphoric acid, and triphenylsulfonium hexafluoroarsenic acid can be mentioned. However, it is 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 In some cases, transparency and optical distortion (pulse separation) may be improved.

  Among the above compounds, preferred are dimethyltin dichloride, dibutyltin dichloride, dibutyltin dilaurate, dibutyltin diacetate, tetrachlorotin, dibutyltin oxide, organotin compounds such as diacetoxytetrabutyldistanoxane, and trifluoroacetic acid. , Trichloroacetic acid, trifluoroacetic anhydride, ethyl trifluoroacetate, sodium trifluoroacetate, trihalogenoacetic acid and its esters, anhydrides, salts, p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, trifluoromethanesulfonic acid Anhydrides, trihalogenomethanesulfonic acid such as ethyl trifluoromethanesulfonate, sodium trifluoromethanesulfonate and its esters, anhydrides, salts, boron trifluoride, boron trifluoride diethyl ether complex, three Boron fluoride 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, trifluoride Lewis acids such as boron trifluoride compounds such as boron THF complex, boron trifluoride methyl sulfide complex, boron trifluoride phenol complex, etc. More preferred are dimethyltin dichloride, trifluoromethanesulfonic acid and its anhydrides, esters, salts and various complexes of boron trifluoride.

  The addition amount of the curing catalyst of the polymerizable composition in the present invention is used in the range of 0.001 to 10 wt%, preferably 0.01 to 5 wt%, more preferably 0, based on the total weight of the polymerizable composition. Used in the range of 0.01 to 1 wt%. When 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 compound described in the present application, or may be added after being dissolved or dispersed in another compound, but it is preferable that the curing catalyst is added after being dissolved or dispersed in another compound. There is a case. Furthermore, when a curing catalyst is added, a favorable result may be obtained if it is carried out in a nitrogen atmosphere or a dry gas atmosphere. In order to further draw out the performance of the resin obtained, a preferable result may be obtained when 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. Is preferably 0.4 wt% or less.

  When curing and molding the composition of the present invention, as in the known molding method depending on the purpose, other stabilizers, resin modifiers, chain extenders, cross-linking agents, HALS systems are representative. Light stabilizers, UV absorbers typified by benzotriazoles, antioxidants typified by hindered phenols, anti-coloring agents, dyes typified by anthraquinone disperse dyes, bluing agents, fillers, silicones Add various substances such as external mold release agents typified by the system or internal mold release agents typified by surfactants such as acidic phosphates, quaternary ammonium salts or quaternary phosphonium salts, and adhesion improvers. (Herein, the internal mold release agent includes those which exhibit a mold release effect among the above-mentioned various catalysts). The amount of the various additives that can be added differs depending on the type, structure, and effect of each additive and cannot be generally limited, but is usually 0.001 with respect to the total weight of the polymerizable composition. It is used in the range of -10 wt%, preferably in the range of 0.01-5 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. Moreover, about the cured resin taken out, you may perform processes, such as annealing, as needed. The annealing conditions vary depending on the structure of the compound constituting the polymerizable composition to be cured, the structure of the resin to be obtained, etc., and cannot be generally limited, but are usually 30 ° C to 200 ° C, preferably 50 ° C to 150 ° C, more preferably Is performed at 70 ° C to 130 ° C.

  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 are appropriately selected from known methods and conditions depending on the type and amount of the curing catalyst used and the type and ratio of the monomer. be able to.

  The polymerization condition of the polymerizable composition of the present invention injected into the molding mold is a polymerizable composition containing a polythietane compound having a structure represented by the formula (1) of the present invention and usually sulfur with a purity of 98% or more. Depending on the composition and structure of the product, it cannot be generally limited, and it cannot be limited because the conditions vary greatly depending on the type of resin modifier, the type of curing catalyst, the shape of the molding mold, etc., but approximately -50 to 200 ° C, preferably Is carried out at a temperature of -20 ° C to 150 ° C, more preferably 0 ° C to 130 ° C for 0.01 to 100 hours, preferably 0.05 to 50 hours, more preferably 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 composition of the present invention can shorten the polymerization time by irradiation with ultraviolet rays or the like. At this time, a curing catalyst such as a radical polymerization catalyst may be added.

  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 in 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.

  Furthermore, in the lens using the optical material of the present invention, in order to improve antireflection, imparting high hardness, improving wear resistance, improving chemical resistance, imparting antifogging properties, or imparting fashionability, etc., as necessary. Further, physical or chemical treatment such as surface polishing, antistatic treatment, hard coat treatment, non-reflective coating treatment, and dyeing treatment can be performed.

  Hereinafter, the present invention will be specifically described by way of examples. The present invention is not limited to the following examples. Among the performance tests of the obtained cured resin, the optical properties, specific gravity, heat resistance, and transparency were evaluated by the following test methods.

Refractive index (ne) Abbe number (νe): Measured at 20 ° C. using a Purfrich refractometer.
-Heat resistance: Tg was measured by the TMA penetration method. Tg of 80 ° C. or more was rated as “◯”, and Tg less than 80 ° C. was marked as “x”.
-Transparency: Observed visually under a high-pressure mercury lamp for a slide projector.
-Strength: A drop ball test (an iron ball having a weight of 16 g was dropped from a height of 127 cm) was performed on a lens having a center thickness of 1.5 mm, and the resin was not broken. The thing was set as x.

[Example 1]
Add 5 parts by weight of sulfur to 95 parts by weight of bis (3-thietanyl) disulfide in a beaker at room temperature of 20 ° C. to obtain a mixture of 100 parts by weight in total. To this mixture, 0.01 part by weight of Biosorb 583 (manufactured by Kyodo Yakuhin Co., Ltd.) as an ultraviolet absorber and 0.4 part by weight of BF ₃ / butyl ether complex as a catalyst were charged, and stirred for 30 minutes to sufficiently dissolve the powder. After filtering the obtained mixed liquid, defoaming was sufficiently performed under a reduced pressure of 1.3 kPa or less. The defoamed liquid was poured into a mold molded with a glass mold and a tape, placed in a polymerization furnace capable of temperature programming, gradually heated from 30 ° C. to 120 ° C., and polymerized in 20 hours. After cooling to near room temperature, the glass mold was released to obtain a resin. The obtained resin was colorless with excellent transparency and good appearance without distortion. Table 1 shows the refractive index, heat resistance, transparency, and strength of the obtained resin.

[Examples 2 to 6]
The experiment was repeated under the same conditions as in Example 1 except that the compounds and compositions shown in Table 1 were used. Table 1 shows the evaluation results of the refractive index, heat resistance, transparency and strength of the obtained resin.

[Example 7]
5 parts by weight of sulfur is added to 95 parts by weight of bis (3-thietanyl) disulfide in a beaker at room temperature of 20 ° C. to obtain a mixture of 100 parts by weight in total. Further, 3 parts by weight of 4,8or4,7or5,7-bis (mercaptomethyl) -3,6,9-trithia-undecanedithiol (hereinafter referred to as “modifier 1”) as a modifier for this mixture, UV absorption 0.01 parts by weight of Biosorb 583 (manufactured by Kyodo Yakuhin Co., Ltd.) as an agent and 0.4 parts by weight of BF ₃ / butyl ether complex as a catalyst were added and stirred for 30 minutes to sufficiently dissolve the powder. After filtering the obtained mixed liquid, defoaming was sufficiently performed under a reduced pressure of 1.3 kPa or less. The defoamed liquid was poured into a mold molded with a glass mold and a tape, placed in a temperature-programmable polymerization furnace, gradually heated from 30 ° C. to 120 ° C., and polymerized in 20 hours. After cooling to near room temperature, the glass mold was released to obtain a resin. The obtained resin was colorless with excellent transparency and good appearance without distortion. Table 2 shows the refractive index, heat resistance, transparency, and strength of the obtained resin.

[Example 8]
The experiment was performed under the same conditions as in Example 7 except that the compounds and compositions shown in Table 2 were used. Table 2 shows the evaluation results of the refractive index, heat resistance, transparency and strength of the obtained resin.

[Comparative Example 1]
30 parts by weight of sulfur is added to 70 parts by weight of bis (3-thietanyl) disulfide in a beaker at room temperature of 20 ° C. to obtain a mixture of a total of 100 parts by weight. To this mixture, 0.01 part by weight of Biosorb 583 (manufactured by Kyodo Yakuhin Co., Ltd.) as an ultraviolet absorber and 0.4 part by weight of BF ₃ / butyl ether complex as a catalyst were charged, and stirred for 30 minutes to sufficiently dissolve the powder. After filtering the obtained mixed liquid, defoaming was sufficiently performed under a reduced pressure of 1.3 kPa or less. The defoamed liquid was poured into a mold molded with a glass mold and a tape, placed in a temperature-programmable polymerization furnace, gradually heated from 30 ° C. to 120 ° C., and polymerized in 20 hours. After cooling to near room temperature, the glass mold was released to obtain a resin. Table 3 shows the evaluation results of the obtained resin for refractive index, heat resistance, transparency, and strength. Although the refractive index ne of the obtained resin was as high as 1.78, turbidity was observed, and the heat resistance and strength test results were x.

[Comparative Example 2]
The experiment was performed under the same conditions as in Example 1 except that the compounds and compositions shown in Table 3 were used. Table 2 shows the evaluation results of the refractive index, heat resistance, transparency and strength of the obtained resin. The obtained resin was transparent, and the heat resistance and strength test results were good, but the refractive index ne = 1.73 was low.

[Comparative Examples 3 to 4]
The experiment was repeated under the same conditions as in Comparative Example 1 except that the compounds and compositions shown in Table 4 were used. Table 4 shows the evaluation results of the refractive index, heat resistance, transparency and strength of the obtained resin. In Comparative Example 3, the refractive index of the obtained resin was ne = 1.75, but the heat resistance and strength test results were x. In Comparative Example 4, the obtained resin had a refractive index ne = 1.76, and the transparency, heat resistance, and strength test results were x.

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Claims (7)

A polymerizable composition comprising a polythietane compound having a structure represented by the following formula (1) and sulfur, wherein the total content of the polythietane compound and sulfur is 100 parts by weight, and the sulfur content Is a polymerizable composition of 5 to 25 parts by weight.

Wherein R ′ and R ″ are a substituted or unsubstituted hydrocarbon group having 1 to 2 carbon atoms which may be thiated, and U is a substituted or unsubstituted straight chain which may be thiated. Represents a branched or cyclic alkylene group having 1 to 8 carbon atoms, an arylene group or an aralkylene group, l represents an integer of 0 to 2, o represents an integer of 1 or 2, m, n represents an integer of 0 to 3, p and q represent an integer of 0 to 2.) The polythietane compound having the structure represented by the formula (1) is bis (3-thietanyl) disulfide, bis (3-thietanyl) sulfide, bis (3-thietanylthio) methane, or bis (3-thietanylthiomethyl) sulfide. The polymerizable composition according to claim 1, which is any one of them. A resin obtained by curing the polymerizable composition according to claim 1. An optical material containing the resin according to claim 3. A method for producing a resin comprising a step of cast polymerization of the polymerizable composition according to claim 1. The polymerization property according to claim 1 or 2, wherein a boron trihalide compound and a complex thereof, and one or more compounds selected from trihalogenomethanesulfonic acid, an ester thereof and an anhydride thereof are used as a curing catalyst. A method for producing a resin, comprising a step of curing the composition. A method for producing a resin, comprising the step of curing the polymerizable composition according to claim 1 or 2 further added with at least one compound having one or more SH groups as a resin modifier.