WO2007086449A1

WO2007086449A1 - Polythiocarbonate polythiol poly(meth)acrylate

Info

Publication number: WO2007086449A1
Application number: PCT/JP2007/051144
Authority: WO
Inventors: Takafumi Hirakawa; Atsushi Morikami; Yasuhiro Kawachi; Mizuho Oda
Original assignee: Ube Industries, Ltd.
Priority date: 2006-01-26
Filing date: 2007-01-25
Publication date: 2007-08-02
Also published as: JP5320744B2; TW200745213A; JPWO2007086449A1

Abstract

Disclosed is a polythiocarbonate polythiol poly(meth)acrylate having a structure wherein a hydrogen atom in a mercapto group of a polythiocarbonate polythiol is substituted by a (meth)acryloyl group represented by the following general formula (1). (1) (In the formula, X represents a hydrogen atom or a methyl group.) This compound can be polymerized and molded within a short time, and is thus suitable as an optical plastic material for optical lenses or the like.

Description

Specification

Polythiocarbonate polythiol poly (meth) acrylate

Technical field

[0001] The present invention relates to a plastic useful as an optical plastic raw material used in plastic lenses, prisms, optical fibers, information recording substrates, colored filters, infrared absorption filters, optical adhesives, optical films and the like. Carbonate polythiol Poly (meth) acrylate.

Background art

[0002] Plastic materials are lightweight, tough and easy to dye, and have recently been used in various optical applications such as lenses. However, when plastic materials are used for eyeglass lenses, etc., it is necessary to increase the thickness of the lens with a low refractive index. There is a problem of becoming. In addition, plastics generally tend to have a higher Abbe number and lower chromatic aberration as the refractive index of the material increases. This large chromatic aberration also causes the problem that the object to be watched will be blurred and blurred. . For these reasons, a material having a high refractive index and a high Abbe number is required as an optical plastic material.

As such an optical plastic material, Patent Document 1 proposes a polythiourethane obtained by reacting a polythiol and a polyisocyanate, and Patent Document 2 increases the content of sulfur atoms as the polythiol. Things have been further proposed. As materials having a higher refractive index are demanded, polythioethers, which are ring-opening polymers of polysulfide, described in Patent Document 3 and Patent Document 4 have been proposed. It was. Since these polythiourethanes and polythioethers generally have a refractive index of 1.6 or higher and an Abbe number of 30 or higher, they are often used as thin and light spectacle lenses in recent years.

[0004] Furthermore, Patent Document 5 proposes a polythiourethane obtained by reacting polythiocarbonate polythiol with polyisocyanate Z polyisothiocyanate.

[0005] However, polythiourethanes and polythioethers are used to produce optical lenses. However, it took a long time for thermal polymerization molding, and depending on the material, it might take about 1 to 3 days, leaving room for improvement in terms of productivity.

[0006] For the purpose of solving the problem of productivity, a method for obtaining an optical plastic lens by polymerizing and molding a radically polymerizable compound in a short time by photopolymerization has been proposed. Patent Document 6, Patent Document 7 and Patent Document 8 propose a method for obtaining an optical plastic lens using acrylic acid esters or thioacrylic acid esters containing a bromine atom or a sulfur atom. Patent Document 10 proposes a method for obtaining an optical plastic lens using a (meth) acrylic acid ester having a sulfur-containing alicyclic structure.

[0007] However, these methods enable polymerization in a short time, and the obtained resin has good optical performance (high refractive index and high Abbe number), but mechanical performance. (Bending strength, bending fracture strain, etc.) were not satisfactory.

[0008] Patent Document 1: Japanese Patent Publication No. 4 58489

Patent Document 2: Japanese Patent Laid-Open No. 5-148340

Patent Document 3: Japanese Patent Laid-Open No. 9-71580

Patent Document 4: Japanese Patent Laid-Open No. 9-110979

Patent Document 5: Japanese Unexamined Patent Publication No. 2005-336476

Patent Document 6: Japanese Patent Laid-Open No. 63-248811

Patent Document 7: JP-A-1-26613

Patent Document 8: Japanese Patent Laid-Open No. 3-217412

Patent Document 9: Japanese Patent Laid-Open No. 3-215801

Patent Document 10: JP-A-4 161410

Disclosure of the invention

Problems to be solved by the invention

[0009] The present invention can be polymerized and molded in a short time, and in addition to the excellent optical performance (high refractive index, high Abbe number) required for optical plastic materials such as optical lenses, The purpose is to provide a raw material for producing a plastic material having high mechanical performance (high bending strength, high bending fracture strain). Means for solving the problem

As a result of intensive studies, the present inventors have found that an optical plastic material having the above-mentioned performance can be produced by using a novel polythiocarbonate polythiol poly (meth) atelate described below. As a result, the present invention has been completed.

[0011] That is, the present invention relates to the following matters.

1. A polythiocarbonate polythiol poly (meth) acrylate having a structure in which a hydrogen atom of a mercapto group of a polythiocarbonate polythiol is substituted with a (meth) atalyloyl group represented by the general formula (1).

[0013] [Chemical 1]

(In the formula, X represents a hydrogen atom or a methyl group.)

2. The polythiocarbonate polythiol poly (meth) acrylate according to the above 1, wherein the polythiocarbonate polythiol has a repeating unit represented by the general formula (2).

[0014] [Chemical 2]

(In the formula, R represents a divalent hydrocarbon group, which may have a substituent not involved in the reaction, and may contain a heteroatom or a ring structure in the carbon chain.)

3. The polythiocarbonate polythiol poly (meth) phthalate as described in 1 above, wherein the polythiocarbonate polythiol has at least two types of repeating units represented by the general formula (2).

[0015] 4. The polythiocarbonate polythiol poly (meth) acrylate represented by the general formula (3) and having a number average molecular weight of 300 to 3000.

[0016] [Chemical 3]

(In the formula, R is as defined above, n represents a number of 1 or more, and X and Y each independently represent a hydrogen atom or a methyl group.)

5. The polythiocarbonate polythiol poly (meth) acrylate according to any one of the above 14 which is liquid at room temperature.

[0017] 6. The polythiocarbonate polythiol poly (meth) attaly according to any one of the above 1 to 4, wherein the degree of substitution of the hydrogen atom of the mercapto group by the (meth) atalyloyl group of the general formula (1) is ¾0% or more. rate.

[0018] 7. The polythiocarbonate polythiol poly (meth) acrylate according to any one of the above 14 wherein APHA is 150 or less.

[0019] 8. The polythiocarbonate polythiol poly (meth) acrylate according to any one of claims 14 to 14, wherein the viscosity at 35 ° C is lOOOOmPa'sec or less.

[0020] 9. Reacting polythiocarbonate polythiol with 3-logeno (l-methyl) propio-nornolide represented by the general formula (4), followed by a vinyl bond formation reaction with dehalogenated hydrogen. 14. The method for producing a polythiocarbonate polythiol poly (meth) acrylate according to any one of the above 14 characterized by the above.

[0021] [Chemical 4]

(In the formula, X represents a hydrogen atom or a methyl group, and A and B each independently represent a halogen atom.)

10. Polythiocarbonate in which the hydrogen atom of the mercapto group of polythiocarbonate polythiol is substituted with a 3-logeno (2-methyl) propionyl group represented by the general formula (5) Topolythiolpoly 3 logeno (1-methyl) propionate,

[0022] [Chemical 5]

(Wherein X and A are as defined above.)

11. The polythiocarbonate polythionorepoly 3 logeno (1-2-methinole) propionate represented by the general formula (6) and having a number average molecular weight of 350 3200.

[Chemical 6]

(In the formula, A and C each independently represent a halogen atom, and R XY and n are as defined above.)

12. A polymerizable composition comprising 3 100% of the polythiocarbonate polythiol poly (meth) atarylate according to any one of 18 above on a weight basis.

[0024] 13. A polymer cured product obtained by subjecting the polymerizable composition as described in 12 above to a radical polymerization reaction.

[0025] 14. An optical material using the polymerized and cured product as described in 13 above.

The invention's effect

The polymerizable composition containing the polythiocarbonate polythiol poly (meth) acrylate of the present invention can be polymerized and molded in a short time, and the cured product is an optical plastic material such as an optical lens. In addition to the performance required for the above-mentioned, that is, excellent optical performance (high refractive index, high Abbe number), a plastic material having excellent mechanical performance (high bending strength, high bending fracture strain) is provided. Therefore, for example, plastic lenses, prisms, optical fibers, information recording substrates, colored filters, infrared absorption filters, optical adhesives It is expected to be used for optical materials such as optical films. In addition, since the cured product has not only excellent optical performance but also excellent mechanical performance, it is expected to contribute to increasing the strength of various optical materials.

Furthermore, according to a different aspect of the present invention, it is possible to provide a novel polythiocarbonate polythiolpoly (meth) acrylate, a method for producing the same, and an intermediate suitable for the production.

BEST MODE FOR CARRYING OUT THE INVENTION

In the present application, the term “polythiocarbonate polythiol poly (meth) acrylate” refers to, in addition to the compound itself, for example, a mixture mainly composed of compounds having different degrees of polymerization produced by the production method of the present invention. means.

Hereinafter, the present invention will be described in detail.

[0029] The polythiocarbonate polythiol poly (meth) acrylate of the present invention has a structure in which a hydrogen atom of a mercapto group (thiol group) of a polythiocarbonate polythiol is substituted with a (meth) attalyloyl group. That is, it is a polythiocarbonate having a thiocarbonate structure as a repeating unit, and has a (meth) atalyloylthio group at the terminal. As will be described later, polythiocarbonate polythiol poly (meth) acrylate is obtained by reacting polythiocarbonate polythiol with 3logeno (2-methyl) propio-halide to produce polythiocarbonate polythionorepoly-3logeno (1-2-methinole). Propionate can be produced by the subsequent formation of a bulle bond with dehalogenated hydrogen.

[0030] In the present application, the notation of "(meth) attalylate" and "(meth) attaroyl" is both commonly used for both "metatalate" and "attalylate". It means both “Royle” and “Atari Royl”. Furthermore, notations such as “3-halogeno (2-methyl) propionyl” and “3-logeno (2-methyl) propionate” are both “3-halogeno-2-methylpropionol” and “3-logenopropiol”, respectively. And both “3 halogeno-2-methylpropionate” and “3 logenopropionate”.

[0031] [Polythiocarbonate Polythionole]

The polythiocarbonate polythiol used as a raw material is a carbonate compound (carbohydrate). Nate component) and polythiol compound (thiol component) are preferably produced by transesterification in the presence of a transesterification catalyst. Examples of the carbonate compound include dialkyl carbonates such as dimethyl carbonate, jetyl carbonate, di-n-butyl carbonate, and diisobutyl carbonate; diallyl carbonates such as diphenyl carbonate; alkylene powers such as ethylene carbonate and propylene carbonate; And alkyl aryl carbonates such as methyl phenol carbonate. Among these carbonate compounds, diphenyl carbonate is particularly preferable among diaryl carbonates.

[0032] As the polythiol compound, polythiol compounds corresponding to the polythiol compound used in the production of polycarbonate polyol can be used singly or in plural, specifically, And a compound in which a mercapto group is bonded to the free end of a polyvalent (at least divalent) hydrocarbon group (preferably having 2 to 14 carbon atoms). As this hydrocarbon group, an aliphatic (including alicyclic) hydrocarbon group (preferably having 2 to 14 carbon atoms), an aromatic (including araliphatic) hydrocarbon group (preferably having 6 to 14 carbon atoms). In the carbon chain, which may have substituents that do not participate in the reaction (alkyl groups, alkoxy groups, etc.), heteroatoms (oxygen atoms, sulfur atoms, nitrogen atoms) and ring structures ( An alicyclic structure, an aromatic ring structure, a heterocyclic structure, etc.) may also be included as atoms or atomic groups that are not involved in the reaction. In this case, “does not participate in the reaction” means polythiocarbonate polythiol synthesis reaction, polycarbonate polythionorepoly 3-halogeno (1-methinole) propionate synthesis reaction, polythiocarbonate polythiol poly (meta) This means that it does not participate in the acrylate synthesis reaction and the radical polymerization reaction of the polymerizable composition containing this (meth) acrylate.

[0033] Among the polyvalent hydrocarbon groups constituting the thiol compound, polyvalent hydrocarbons having a valence of 2 or more, preferably 8 or less, and more preferably 5 or less. A thiol compound based on the above may be used in combination. In particular, in all of the specific embodiments in which it is preferred to use mainly divalent compounds (eg, 80 mol% or more), thiol compounds in which a mercapto group is bonded to a divalent hydrocarbon are used. Among these, a divalent aliphatic hydrocarbon group is particularly preferable among aliphatic ones. In addition, the heteroatom In the ring structure in which a sulfur atom or an oxygen atom is preferred, an alicyclic structure or a saturated heterocyclic structure is preferable. If the polyvalent hydrocarbon group is a divalent hydrocarbon group, the thiol compound is represented by R (SH). Polythiocarbonate polythiol produced using this is

2

It has the repeating unit of the general formula (2), and the “R” force in the general formula (2) corresponds to this hydrocarbon group. For example, polythiocarbonate dithiol having the following structure is produced only from a thiol compound having a divalent hydrocarbon group.

[0034] [Chemical 7]

[0035] Here, n is a number of 1 or more. When a single compound is represented, it is an integer indicating the degree of polymerization. Since it is usually obtained from a mixture having different degrees of polymerization, it satisfies a predetermined average molecular weight. It represents the average number chosen.

In this case, the repeating unit of the general formula (2) also becomes a repeating unit as it is in the polythiocarbonate polythiol poly (meth) acrylate using the raw material as a raw material.

[0037] Furthermore, when used in combination with Chiorui匕合having a trivalent carbon hydrogen group R ² to a thiol compound having a carbon-hydrogen group R ¹ of the divalent poly Chio polythiol, as follows For example, It has a structure branched at R ² .

[0038] [Chemical 8]

[0039] Increasing the content of trivalent or higher valent hydrocarbon groups increases the branching and Z or crosslinking structure in the polymer. Since the structure increases, it is preferable to select and use it appropriately in consideration of the physical properties of the obtained optical material.

[0040] Examples of the polythiol compound in which the hydrocarbon group is an aliphatic hydrocarbon group include 1,2 ethanedithiol, 1,3 propanedithiol, 1,4 butanedithiol, 1,5 pentanedithiol, 1 , 6 Hexanedithiol, 1,7 Heptanedithiol, 1,8 Octanedithiol, 1,9-Nonandithiol, 1,10 Decandithiol, 1,12 Dodecanedithiol, 2,2 Dimethyl-1,3 Propanedithiol, 3 -Alkanedithiols such as methyl-1,5 pentanedithiol, 2-methyl-1,8 octanedithiol; Cycloalkanedithiols such as 1,4-cyclohexanedithiol;

[0041] Bis (2 mercaptoethyl) ether, bis (2 mercaptoethyl) sulfide, bis (

Alkanedithiols containing heteroatoms in carbon chains such as 2-mercaptoethyl) disulfide and 2,2,1- (ethylenedithio) jetanethiol; 1,4 in carbon chains such as bis (mercaptomethyl) cyclohexane Alkanedithiols containing alicyclic structures; 2, 5 bis (mercaptomethyl) -1,4 dioxane, 2,5 bis (mercaptomethyl) -1,4 dithiane, etc. heteroatoms and alicyclic structures Containing alkanedithiols;

[0042] Alkanetrithiols such as 1, 1, 1-tris (mercaptomethyl) ethane, 2 ethyl-2-mercaptomethyl-1, 3 propanedithiol; tetrakis (mercaptomethyl) methane, 3, 3, -thiobis (propane 1 , 2 dithio-inole), 2, 2, -thiobis (propane 1,

And alkanetetrathiols such as 3-dithiol).

[0043] The polythiol compound in which the hydrocarbon group is an aromatic hydrocarbon group includes, for example, 1,2 benzenedithionore, 1,3 benzenedithionole, 1,4 benzenedithionole, toluene 3, 4 Aromatic dithiols such as dithiols; 1,2 bis (mercaptomethyl) benzene, 1,3 bis (mercaptomethyl) benzene, araliphatic dithiols such as 1,4 bis (mercaptomethyl) benzene; 1, 3, 5 benzene Examples include trithiol and aromatic trithiol such as 1,3,5-tris (mercaptomethyl) benzene.

In the present invention, the polythiol compound may be used alone, but may be used in plural (at least two). Polyvalent hydrocarbon in polythiol compound is divalent hydrocarbon If the latter, in the latter case, the resulting polythiocarbonate polythiol has the general formula

In (2), a copolymer having plural (at least two) repeating units having different Rs is obtained. At this time, for example, if a polythiol compound having the following combination is used, the melting point and the crystallization temperature are low, and it is room temperature (40 ° C. or lower, preferably 30 ° C. or lower, depending on the specific embodiment. A liquid polythiocarbonate polythiol can be obtained at a temperature not higher than ° C, more preferably not higher than 10 ° C. The use ratio of the plurality of polythiol compounds is not particularly limited as long as a liquid polythiocarbonate polythiol can be obtained at room temperature! When using liquid polythiocarbonate polythiol as a raw material, the resulting polythiocarbonate polythiol poly (meth) acrylate is of low melting point, making it possible to perform cast polymerization at room temperature. Useful.

[0045] (a) Combination of linear alkanedithiols having different chain lengths: 1,5 pentanedithiol and 1,6 hexanedithiol, bis (mercaptoalkyl) sulfide (for example, bis (2 mercapto) (Chill) sulfide) and 1,6 hexanedithiol.

[0046] (b) Combination of straight-chain alkanedithiol and branched alkanedithiol: Combination of 1,6-hexanedithiol and 3-methyl-1,5-pentanedithiol, etc.

[0047] (c) Combination of linear alkanedithiol or branched alkanedithiol with alkanedithiol containing alicyclic structure: Combination of 1,6 hexanedithiol and 1,4 bis (mercaptomethyl) cyclohexane.

[0048] (d) Combination of linear alkanedithiol or branched alkanedithiol with alkanedithiol containing heteroatom and alicyclic structure: 1, 6 hexanedithiol and 2, 5 bis (mercaptomethyl) -1,4 dithiane Combination with.

[0049] Polythiocarbonate polythiol is produced by continuously reacting a carbonate compound (especially diaryl carbonate) and an alcohol (especially allyl alcohol) by-produced in the presence of a transesterification catalyst in the presence of a transesterification catalyst. It is preferable to carry out the transesterification reaction while extracting. At this time, the polythiol compound is used in an amount of 0.8 to 3.0 times mol of the carbonate compound so that all or almost all of the terminal ends of the resulting polyoxycarbonate polythiol molecular chain are mercapto groups. Is 0.85-2.5 times It is preferable that it is a mole, especially 0.9-2.5 times mole. Further, the amount of the transesterification catalyst used is preferably 1 to 5000 ppm, more preferably 10 to LOOOp pm on a molar basis with respect to the polythiol compound. In order to extract the by-product alcohol, it is preferable to provide a distillation apparatus in the reactor, and the reaction may be performed under a flow of inert gas (nitrogen, helium, argon, etc.).

[0050] In the transesterification reaction, it is preferable to use diphenol carbonate as diaryl carbonate. In that case, a polyvalent hydrocarbon group is a divalent hydrocarbon group as a polythiol compound. If it is used, the hydrocarbon group R preferably has 4 to 14 carbon atoms. At this time, the amount of polythiol compound (especially dithiol compound) having a carbon number power of 14 of the divalent hydrocarbon group R is 1.05 to 3.0 times as much as that of diphenyl carbonate, and further 1. A power of 1 to 2.5 times monolith S is preferable, and the coloration is low (that is, APHA is 60 or less, further 40 or less, especially 20 or less), and all or almost all of the molecular chain ends are mercapto. It is possible to obtain a polythiocarbonate polythiol that is a group (that is, the ratio of the aryloxy group (particularly phenoxy group) in the terminal group is 5% or less, more preferably 2% or less, particularly 1% or less). By controlling the ratio of aryloxy groups in the terminal groups in this way, it is possible to obtain a polythiocarbonate polythiol poly (meth) acrylate having a high content of terminal (meth) atalyloyl groups, resulting in improved optical performance. In addition, an optical material excellent in mechanical performance can be obtained. APHA represents the hue when heated and melted, and the proportion of aryloxy group is on a molar basis (the same applies hereinafter).

[0051] Conditions for the transesterification reaction (temperature, pressure, time) are not particularly limited as long as the target product can be efficiently produced. For example, a carbonate compound and a polythiol compound are converted into the presence of a transesterification catalyst. Under normal pressure or reduced pressure, react at 110 to 200 ° C for about 1 to 24 hours, then under reduced pressure at 110 to 240 ° C (especially 140 to 240 ° C) for about 0.1 to 20 hours. What is necessary is just to react for about 0.1 to 20 hours under the reduced pressure which finally becomes 20 mmHg (2.7 kPa) or less while gradually increasing the degree of vacuum at the same temperature.

[0052] When a plurality of polythiol compounds are used, a plurality of polythiol compounds may be reacted at the same time, but the carbonate compound and one polythiol compound are subjected to the same conditions. Alternatively, the corresponding polythiocarbonate polythiol may be produced by a sulfur exchange reaction, and this may be reacted with another polythiol compound. In the case of the latter, if the carbonate compound is diphenyl carbonate, a dithiol carbonate and a polythiol compound (particularly a dithiol compound) having a carbon number power of R-14 of 14 are transesterified, and then It is preferable to produce the desired product by reacting the resulting polythiocarbonate polythiol with a polythiol compound (particularly a dithiol compound) having 2 to 4 carbon atoms in R.

The transesterification catalyst is not particularly limited as long as it is a compound that catalyzes the transesterification reaction. For example, potassium carbonate, sodium alkoxide (sodium methoxide, sodium ethoxide, etc.), organic quaternary ammonium salt (tetra Basic compounds such as tetraalkyl ammonium hydroxide such as ptyl ammonium hydroxide, titanium compounds such as titanium tetrachloride, tetraalkoxy titanium (tetra- _n -butoxy titanium, tetraisopropoxy titanium, etc.), metals Examples include tin compounds such as tin, tin hydroxide, tin chloride, dibutyltin dilaurate, dibutyltyloxide, and butyltin tris (2-ethylhexanoate).

[0054] Among the transesterification catalysts, potassium carbonate, sodium alkoxide (sodium methoxide, sodium ethoxide, etc.), organic quaternary ammonium salt (tetraalkylammonium hydroxide, such as tetraptyl ammonium hydroxide) Preferred are basic compounds such as tetraalkoxytitanium (tetra- _n -butoxytitanium, tetraisopropoxytitanium, etc.). Among them, basic compounds should give polythiocarbonate polythiols with APHA of 60 or less and low coloration. Is particularly preferable.

[0055] The number average molecular weight (M) of the polythiocarbonate polythiol is preferably in the range of 200 to 2500, more preferably 400 to 2000. When the molecular weight is out of the range, the properties of polythiocarbonate polythiol poly (meth) acrylate are optically or mechanically obtained from a polymerized cured product (optical material) obtained by radical polymerization of a polymerizable composition containing the compound. Performance tends to be unsatisfactory. For example, when the number average molecular weight is less than 200, radical polymerization of a polymerizable composition containing a polythiocarbonate polythiol poly (meth) acrylate is often low in flexural fracture strain of the cured product, and if greater than 2500, the polythiocar Bonate polythiol poly (meth) atalate with high melting point and crystallization temperature Cast polymerization at low temperatures (below 40 ° C) tends to be difficult. For this reason, the amount of carbonate compound and polythiol compound used is adjusted so as to achieve the target molecular weight, but if the number average molecular weight of the reaction product deviates from the target value, for example, if the molecular weight is small, the pressure is reduced. In addition, it is preferable to adjust the molecular weight by conducting a transesterification reaction while distilling the polythiol hydride compound, and if the molecular weight is large, adding a polythiol hydride compound and further performing a transesterification reaction.

[0056] After the molecular weight adjustment, the transesterification catalyst remaining in the polythiocarbonate polythiol is preferably deactivated if necessary. When tetraalkoxytitanium is used, the transesterification catalyst can be inactivated by a known method of adding a phosphorus compound (phosphoric acid, butyl phosphate, dibutyl phosphate, etc.). Can be added by adding an equimolar amount of an inorganic or organic acid (sulfuric acid, paratoluenesulfonic acid, etc.) to the catalyst at 40 150 ° C. When an insoluble salt is precipitated by this acid addition, it is preferably removed by washing with water.

[0057] The resulting polythiocarbonate polythiol can be further reduced in coloration degree (APHA) by washing with water. For example, when the catalyst is a tetraalkylammonium hydroxide, the APHA of the resulting polythiocarbonate polythiol can be lowered by washing with water to a force of 40 or less, further 20 or less (10 or less). If the catalyst is a titanium compound, the APHA (over 100) of the polythiocarbonate polythiol can be similarly reduced. Washing with water can be performed by dissolving polythiocarbonate polythiol in a good solvent such as methylene chloride, adding an appropriate amount of water, and mixing or stirring uniformly, and the washing operation is performed multiple times as necessary. May be. When the polythiocarbonate polythiol of the present invention is produced using the polythiocarbonate polythiol that has been washed with water, the APHA is 150 or less (more preferably 100 or less, particularly 60 or less) and the coloration degree is low. You can get quality ones.

[Polythiocarbonate Polythionorepoly 3 Logeno (1-2-methinole) propionate] Polythiocarbonate Polythiol Poly 3-logeno (1-2-methyl) propionate is a polythiocarbonate polythiol represented by the general formula (4). It is produced by reacting with the 3-halogeno (1-2-methyl) propio-halide represented. Polythiocarbonate An example using dithiol as a raw material is represented by the following reaction formula.

[0059] [Chemical 9]

In the formula, X represents a hydrogen atom or a methyl group, and A and B each independently represent a halogen atom. R represents a divalent hydrocarbon group. Examples of the hydrogen atom and the rogen atom include a fluorine atom, a chlorine atom and a bromine atom, and a chlorine atom and a bromine atom are particularly preferred among the chlorine and bromine atoms. n is a number of 1 or more, and is an integer indicating the degree of polymerization when representing a single compound, but is usually a mixture having a different degree of polymerization, so that an average selected to satisfy a predetermined average molecular weight. Represents a number.

[0061] Here, since 3-halogeno (-2 methyl) propiol halide can be used by mixing different kinds, polythiocarbonate dithiol bis 3-halogeno (-2-2-) is produced. Methyl) propionate is represented by general formula (6).

[0062] [Chemical 10]

[0063] in which A and C represent a halogen atom as defined for A above, A and C may be the same or different. X and Y each independently represent a hydrogen atom or a methyl group. R represents a divalent hydrocarbon group, and n is as defined above.

[0064] Specific examples of 3-halogeno (1-2-methyl) propio-halide include 3-chloropropionyl chloride, 3-clothiol 2-methinorepropioninochloride, 3 bromopropio ninolechloride, 3 bromo-2-methinorepropiino ninole chloride. 3 Chloropropynyl Ninolev Mouth, 3 Chloro-2-Methylenopropioninolev Membrane, 3 Bromopropioninolev Mouth, 3 Bromo 2 Methylpropiol Bromide, etc. Among them, 3 Chloropropionyl Chloride, 3 Chloro 2 Methylpropiochloride is particularly preferred.

[0065] At this time, 3 logeno (l-methyl) propio-halide is 0.83.0 times monole, and 0.9.9 times monole to the menorecapto group of polythiocarbonate positive In particular, the reaction temperature at which it is preferable to use 1.0 2.0 mol is preferably in the range of 10 80 ° C, more preferably 20 70 ° C, particularly 30 60 ° C. The reaction pressure is not particularly limited, and the reaction atmosphere that is usually normal pressure is not particularly limited.

[0066] The reaction may be carried out in the presence of a solvent if necessary! The solvent should be one that can dissolve the polythiocarbonate polythiol and 3-logeno (2-methyl) propio-halide and does not inhibit the reaction. For example, methylene chloride, black mouth form, 1,2-dichloro mouth ethane, Halogenated hydrocarbons such as black benzene, aromatic hydrocarbons such as benzene, toluene and xylene, ethers such as jetyl ether, isopropyl ether and tetrahydrofuran can be used. The amount of the solvent used is not particularly limited as long as the progress of the reaction is not affected.

[0067] After the reaction is complete, the hydrogen halide gas (HB) is sufficiently discharged out of the reaction system, and then it is possible to proceed directly to the next dehalogenation-hydrogen reaction (vinyl bond formation reaction). It is preferable to proceed to the next dehydrohalogenation reaction after decomposing, neutralizing and removing the remaining propionic acid derivative and hydrogen halide with an aqueous alkali solution in the presence of a medium or solvent. Examples of the alkali used include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, and potassium hydrogen carbonate.

[0068] The thus obtained polythiocarbonate polythiol poly 3-halogeno The number average molecular weight of (til) propionate is preferably 350 3200, in particular 550 2700.

[0069] [Polythiocarbonate polythiol poly (meth) acrylate]

Polythiocarbonate polythiol poly (meth) acrylate is produced by subjecting polythiocarbonate polythiol poly 3 logeno (l-methyl) propionate to a vinyl bond formation reaction by dehalogenation in the presence of a base.

[0070] At this time, if the polythiol compound serving as the thiol component of the polythiocarbonate polythiol is a dithiol compound, when the degree of substitution of the mercapto group is 100%, as shown in the following reaction formula, Polythiocarbonate dithiol di (meth) acrylate represented by (3) can be obtained.

[0071] [Chemical 11]

[0072] Here, n represents the degree of polymerization, and when it represents a single compound, it is an integer of 1 or more (preferably 120), and is usually obtained from a mixture having a different degree of polymerization. Number) Indicates the average number selected to satisfy the average molecular weight. Other symbols in the formula are as described above.

[0073] Specific examples of the base used in the reaction include inorganic bases such as potassium hydroxide and sodium hydroxide and aqueous solutions thereof, and tertiary amines such as triethylamine and triptylamin, among which tertiary amines are preferred. .

[0074] At this time, the base is polythiocarbonate polythiol poly 3-halogeno (-2-methyl ) 1.0 to 10 times mol, more preferably 1.0 to 5.0 times mol, especially 1.2 to 4.0 times mol, relative to the 3-halogeno (l-2-methyl) propiool group of propionate. The reaction temperature preferably used is preferably in the range of 10 to 60 ° C, more preferably 0 to 50 ° C, particularly preferably 0 to 40 ° C. The reaction pressure is not particularly limited, and the reaction atmosphere that is usually normal pressure is not particularly limited.

[0075] The reaction may be carried out in the presence of a solvent if necessary! The solvent should be one that can dissolve the polythiocarbonate polythiol poly 3-halogeno (2-methyl) propionate and the base and does not inhibit the reaction. For example, methylene chloride, black mouth form, 1,2-dichloro mouth Halogenated hydrocarbons such as ethane and black benzene, aromatic hydrocarbons such as benzene, toluene and xylene, ethers such as jetyl ether, isopropyl ether and tetrahydrofuran, ketones such as acetone and methyl ethyl ketone, N, N Aprotic solvents such as dimethylformamide and dimethylsulfoxide can be used. The amount of solvent used is not particularly limited as long as it does not affect the progress of the reaction.

[0076] The polythiocarbonate polythiol poly (meth) acrylate is used after the reaction in the above-described method, after known operations and treatment methods (for example, neutralization, solvent extraction, water washing, liquid separation, solvent distillation, etc. ) To be isolated by post-treatment.

[0077] In this way, a polythiocarbonate polythiol poly (meth) acrylate in which the hydrogen atom of the mercapto group of the polythiocarbonate polythiol is substituted with a (meth) taroloyl group can be obtained. The number average molecular weight of the polythiocarbonate polythiol poly (meth) acrylate is preferably in the range of 300 to 3000, more preferably 500 to 2500.

[0078] Further, the polythiocarbonate polythiol poly (meth) acrylate is in a liquid state at room temperature (usually 40 ° C or lower, preferably 30 ° C or lower, and in some specific embodiments 20 ° C or lower). It is preferable. This can be achieved by using a liquid polythiocarbonate polythiol as a starting material at room temperature. Liquid polythiocarbonate polythiol poly (meth) acrylate is capable of cast polymerization at room temperature and is very useful in practice.

[0079] In the resulting polythiocarbonate polythiol poly (meth) acrylate, the degree of substitution of the mercapto group is adjusted to the molar ratio of the raw materials, but is preferably 80% or more, more preferably 90% or more, Particularly preferred is 95% or more. 80% substitution degree of mercapto group If it is less than 1, the mercapto group reacts with the (meth) atalyloyl group during storage to increase the viscosity, resulting in lack of storage stability.

[0080] Further, the polythiocarbonate polythiol poly (meth) acrylate obtained by the above method preferably has APHA of 150 or less (more preferably 100 or less, particularly 60 or less), and has a high quality with a low degree of coloring. In addition, since the viscosity is 35 ° C or less, lOOOOmPa'sec or less, preferably 500mPa'sec or less, it is very suitable for optical materials.

The inventor of the present invention, for the purpose of obtaining polythiocarbonate polythiol poly (meth) acrylate, directly reacts polythiocarbonate dithiol with methacrylic acid or methacrylic acid chloride, and polythiocarbonate dithiol with methyl methacrylate. An ester exchange reaction was attempted. However, the reaction between the vinyl group and the SH group resulted in polymerization (en-thiol reaction), and the target compound could not be isolated. In particular, the higher the degree of substitution of mercapto groups, the higher the viscosity of the reaction product (viscosity at 35 ° C exceeds lOOOOOOmPa'sec), which is unsuitable for cast polymerization for molding optical materials. there were. On the other hand, according to the production method of the present invention, it is possible to produce a polythiocarbonate polythiol poly (meth) acrylate which can be actually used, particularly suitable for polymerization and molding.

[Polymerizable composition, polymerization cured product (optical material)]

In addition to excellent optical performance (high refractive index and high Abbe number), the polymerized cured product (optical material) of the present invention having excellent mechanical performance (high bending strength and high bending fracture strain) is a polycarbonate. It can be obtained from a radical polymerization reaction of a polymerizable composition containing polythiol poly (meth) acrylate.

[0082] The polymerizable composition contains, as a polymerizable component, polythiocarbonate polythiol poly (meth) acrylate and, if necessary, other polymerizable compounds having at least one radical polymerizable substituent. Polythiocarbonate polythiol poly (meth) acrylate is contained in 100% by weight of the polymerizable component in 3 to: LOO% by weight, preferably 5 to: LOO% by weight, especially 10 to: LOO% by weight. . Other polymerizable compounds which are components used in combination may not be present, but can be used alone or in combination when used in combination.

[0083] Other polymerizable compounds having at least one radical polymerizable substituent include, for example, methyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) ) Atarylate, ethyl carbitol (meth) acrylate, lauryl (meth) acrylate, disiclopentale (meth) acrylate, isobol (meth) acrylate, N— n-butyl O (meth) ate Aliphatic mono (meth) acrylates such as royoxetyl carbamate, attaroyl morpholine, trifluoroethyl (meth) acrylate, perfluorooctyl cetyl (meth) acrylate;

Aromatic mono (meth) attalylate such as rate;

[0085] Aliphatic or aromatic mono (meth) acrylates containing sulfur atoms such as methylthio (meth) acrylate, ethyl thio (meth) acrylate, phenol thio (meth) acrylate, benzylthio (meth) acrylate ;

[0086] Ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1, 6 hexanediol di (meth) acrylate, triethylene glycol di (meta ) Aliphatic di (eg, acrylate, tripropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, hydrogenated bisphenol A di (meth) acrylate Meta) acrylate;

[0087] 1, 2 Ethanedithioldi (meth) acrylate, 1, 3 Propanedithioldi (meth) acrylate, 1, 4 Butanedithioldi (meth) acrylate, 1, 5 Pentanedithiodidi (meth) acrylate , 1, 6 Hexanedithioldi (meth) atarylate, 3 Methyl —1, 5 Pentanedithioldi (meth) atalylate, Bis (2— (meth) Athaloylthioethyl) sulfide, Bis (3 Ataliloylthiopropyl) sulfide, bis (2 (meth) atalyloylthiopropyl) sulfide, 1,8 bis (meth) atalyloylthio 3,6 dithiaoctane, 1,11-bis (meth) atalyloylthio-1,3 6, 9 Trithiaundecane, Bis (2 (meth) attaroyloxychetyl) sulfide, Bis (3 (Meth) attaroyloxypropyl) sulfide, Bis (2- (Meth) Athalyloxypropyl) sulfide, 1,8-Bis (meth) Athalyloxy-3, 6 Dithiaoctane, 1,11-Bis (meth) Athalyloxy-3, 6, 9-Tri Aliphatic di (meth) atareales containing sulfur atoms such as thiaundecane h

[0088] Aromatic di (meth) acrylates such as bisphenol F di (meth) acrylate, bisphenol A di (meth) acrylate, bisphenol S di (meth) acrylate;

[0089] 1,2-Bis (meth) atalyloylthiobenzene, 1,3-Bis (meth) Atalyloylthiobenzene, 1,4-Bis (meth) Ataroloylthiobenzene, 1,2-Bis (meta ) Atalyloylthiomethylbenzene, 1,3-bis (meth) atalyloylthiomethylbenzene, 1,4-bis (meth) acryloylthiomethylbenzene, 1,2-bis (2- (meth) atalyloylthio) Ethylthio) methylbenzene, 1,3-bis (2- (meth) atalyloylthioethylthio) methylbenzene, 1,4-bis (2- (meth) atalyloylthioethylthio) methylbenzene, etc. Aromatic di (meth) atarylates containing sulfur atoms;

[0090] such as trimethylolpropane tri (meth) acrylate, dipentaerythritol pentaacrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa acrylate Aliphatic or aromatic polyfunctional (trifunctional or higher) (meth) atallylate;

[0091] Ethylene glycol diglycidyl ether di (meth) acrylate, propylene glycol diglycidyl ether di (meth) acrylate, phenol glycidyl ether (meth) acrylate, resorcin diglycidyl ether (meth) acrylate, bisphenol A diglycidyl ether di Epoxy (meth) acrylate, such as (meth) acrylate, 4,4, -bishydroxyphenylsulfide diglycidyl ether di (meth) acrylate;

[0092] Bulle compounds such as bullbenzene, dibutenebenzene, N-butyrpyrrolidone, N-biylcaprolactam, ethylene glycol diallyl carbonate, trimellitic acid triallyl ester, triallyl isocyanurate, etc. ;

[0093] (Meth) acrylate oligomers such as polyurethane (meth) acrylate, polyester (meth) acrylate, polyether (meth) acrylate, polycarbonate (meth) acrylate, etc. In order to maintain the refractive index, aliphatic or aromatic (meth) acrylates containing sulfur atoms are preferred, and aliphatic ones are particularly preferred.

[0094] Furthermore, the polymerizable composition of the present invention contains a radical as an essential component in addition to the polymerizable component. Contains a polymerization initiator. The content of the radical polymerization initiator is 0.0 01-5 a weight ^_0/0 of the polymerizable component, preferably from 0.005 to 3 wt ^_0/0, more preferably from 0.01 to 2 weight ⁰ / ₀ .

[0095] Examples of the radical polymerization initiator include benzophenone, 4-methylbenzophenone, 4,4'-diclonal benzophenone, 2, 4, 6 trimethylbenzophenone, o benzoylbenzoic acid methyl ester, 4 Phenolpenzophenone, 4 Methylphenol thiobenzophenone, 3, 3 Dimethyl 4-methylbenzophenone, 4— (1,3—Atarylloyl 1,4,7,10,13 Pentaoxatridecyl) benzophenone, 3, 3 ', 4, 4, 1-tetra (tert-butylperoxycarbol) benzophenone, 4-1-benzoyl, N, N, N-methylbenzenemethanamine chloride, 2-hydroxy-1-3- (4-benzoylphenoxy) 1 N, N, N-trimethyl-1-propanum chloride, 4 benzoyl N, N dimethyl-N— [2— (1-oxo-2-propenoxy) ethyl] benzenemethanamide Carbon compounds such as Mubuguchimid, 2-Isopropylthixanthone, 4 Isopropylthixanthone, 2,4 Dimethinorexanthone, 2,4 Jetylthioxanthone, 2,4 Diisopropylthixanthone, 2,4-Dicyclothiaxanthone;

[0096] Benzyl-1,7,7 Trimethylbicyclo [2,2,1] heptane-1,3 dione, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1 chloroanthraquinone , 2 aminoleanthraquinone, 9, 10 phenanthrenequinone, at-year-old dibenzene compounds such as methyl benzenebenzene acetate;

[0097] Acetophenone, 2-hydroxy-1-2-methyl-1-phenolpropane-1-one, 1- (4-isopropylphenol) 2-hydroxy-1-2-methylpropane-1-one, 1- [4- (2 —Hydroxyethoxy) phenyl] — 2-hydroxy-2-methylpropane 1-one, 1-hydroxycyclohexyl phenyl ketone, dimethoxyacetophenone, methoxyacetophenone, 2, 2-dimethoxy-1,2-diphenylethane 1-on, 2 , 2-Diethoxy-1, 2-Diphenylethane 1-one, 1, 1-dichloroacetophenone, N, N dimethylaminoacetophenone, 2-methyl 1- (4-methylthiophene) 2 1-one morpholinol propane, 1-one, 2-benzyl-1, 2-dimethylamino 1- (4-morpholinophenol) butane 1-one, 1-ferro-1, 2, 2-propanedi Down one 2- (o-ethoxy Carbol) oxime, 3, 6 bis (2-methyl-2-morpholinopropanoyl) -9acetophenone compounds such as butylcarbazole;

[0098] Benzoin ether compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether;

[0099] Aryl phosphine oxide compounds such as 2, 4, 6 trimethylbenzoyl diphosphine phosphoxide, bis (2, 6 dichloro benzoyl) mono (4-n-propylphenyl) phosphine oxide;

[0100] 4 Dimethylaminobenzoic acid methyl ester, 4 Dimethylaminobenzoic acid ethyl ester, 4-Dimethylaminobenzoic acid-n-butoxetyl ester, 4-Dimethylaminobenzoic acid isoamyl ester, Benzoic acid 2 dimethylaminoethyl ester, 4, 4'-dimethylaminobe Aminocarbol compounds such as Nzophenone, 4,4'-Jetylaminobenzophenone, 2,5'-bis (4-dimethylaminobenzal) cyclopentanone;

[0101] 2, 2, 2 Tricyclo 1- (4, 1 tert-Butylphenol) ethane 1-one, 2, 2 Dichloromethane 1- (4-Phenoxyphenyl) 1-one, α, α, α-Tribromomethylenole F-Nolesnorephone, 2, 4, 6 Tris (trichloromethinole) triazine, 2, 4 Bis (trichloromethyl) 6- (4-methoxyphenol) triazine, 2, 4 Bis (trichloromethyl) 6- (4 -methoxystyryl) triazine, 2, 4 Bis (trichloromethyl) 6 Pipet-rutriazine, 2, 4 Bis (trichloromethyl) 6- (3,4-Methylenedioxy Phenoltriazine, 2, 4 Bis (trichloromethyl) 6- (4-Methoxynaphthyl) triazine, 2, 4 Bis (trichloromethyl) -6- [2- (5-Methylfuryl) ethyl] triazine, 2, 4 Bis (Trichrome Methyl) -6— (2 Free Ethyl) triazine, 2,2azobis (2aminopropane) dihydrochloride, 2,2-azobis [2- (imidazoline-2-yl) propane] dihydrochloride, 2,2,1bis ) Photopolymerization initiators such as halogen compounds such as 1, 4, 4, 5, 5, and 1 tetraphenyl 1,2 biimidazole.

[0102] These polymerization initiators may be used alone or in combination. The following polymerization initiators may be used in combination. The amount of the thermal polymerization initiator used is preferably in the range of 0 to 20 times the weight, more preferably 0 to 10 times the weight, especially 0 to 5 times the weight of the photopolymerization initiator. Yes.

[0103] Examples of the thermal polymerization initiator include ketones such as methyl ethyl ketone peroxide, cyclohexanone peroxide, methyl cyclohexanone peroxide, methyl acetoacetate peroxide, and acetyl acetone acetone peroxide. A baroxide compound;

[0104] 1,1-Bis (tert-hexyloxy) -1,3,3,5 Trimethylcyclohexane, 1,1-bis (tert-hexyloxy) cyclohexane, 1,1-bis (tert-butyloxy) ) -3, 3, 5 Peroxyketal compounds such as trimethylcyclohexane, di tertbutylperoxy 2-methylcyclohexane;

[0105] Hyde mouths such as P-menthane hydride, diisopropylbenzene hydride, 1, 1, 3, 3-tetramethylbutyl hydride, cumene hydride peroxide, tert-hexyl hydride peroxide, tert butyl hydride peroxide Peroxide compound;

[0106] a, α, monobis (tert-butylperoxy) diisopropylbenzene, dicumyl baroxide, 2,5 dimethyl-2,5-bis (tert-butylperoxy) hexane, tert-butylcumyl peroxide, di-tert-butylperoxide, Dialkyl peroxide compounds such as 2,5 dimethyl-2,5-bis (tert-butylperoxy) hexyne;

[0107] Disilver such as isobutyryl peroxide, 3, 3, 5 trimethylhexanoyl peroxide, otatanyl peroxide, lauroyl peroxide, stearoyl peroxide, succinic acid peroxide, benzoyl peroxide Oxide compounds;

[0108] G-propinolever oxydicarbonate, diisopropylperoxydicarbonate, bis (4-tert-butylcyclohexyl) peroxydicarbonate, bis (2 ethoxystiltyl) peroxydicarbonate, Peroxydicarbonate compounds such as bis (2-ethylhexyl) peroxydicarbonate, bis (3-methoxybutyl) peroxydicarbonate, bis (3-methyl-3-methoxybutyl) peroxydicarbonate;

[0109] a, a '~ bis (neodecanol baroxy) diisopropylbenzene, tamil peroxyside decanoate, 1, 1, 3, 3-tetramethylbutyl peroxyneodecanoate, 1-cyclohexylone 1 methyl ester Tilperoxyneodecanoate, tert-hexylperoxyneodecanoate, tret butylperoxyneodecanoate, tert-hexyl Peroxybivalate, tert butyl peroxybivalate, 1, 1, 3, 3—tetramethylbutylperoxy 2 ethylhexanoate, 2,5 dimethyl 2,5 bis (2 ethylhexanoyl peroxide) Xy) hexane, 1-cyclohexylene 1 methinoreethinoreperoxy 2-ethenorehexanoate, tert hexenoleperoxy 2-ethenorehexanoate, tert butylperoxy 2-ethylhexanoate, tert-butinoreperoxyisobutyrate Tert xylperoxyisopropyl monocarbonate, tert-butylperoxymaleic acid, tert-butylperoxy-3,3,5-trimethylhexanoate, tert-butylperoxylaurate, 2,5 dimethyl-2,5 bis (m Ruperoxy) hexane, tert-butylperoxyisopropyl monocarbonate tert-butylperoxy 2-ethylenohexenole monocarbonate, tert-kisyloxybenzoate, 2,5 dimethyl-2,5-bis (benzoylperoxy) hexane, tret-butinoleperoxyacetate, tert-butylenolepa Peroxyester compounds such as xy m-tonoleyl benzoate, tert butyl peroxybenzoate, bis (tert butyl peroxy) isophthalate;

[0110] tert butyl peroxyl monocarbonate, tert-butyl trimethylsilyl peroxide, 3, 3 ', 4, 4'-tetra (tert butyl peroxycarbol) benzophenone, 2, 3 dimethyl 2, 3 Examples thereof include organic peroxides such as diphenylbutane and azo compounds such as azobisisobutyryl-tolyl. These thermal polymerization initiators may be used alone or in combination.

[0111] The polymerizable composition of the present invention includes an antioxidant, a light absorbing material, a photosensitizer, and a filler (talc, silica, alumina, It is also possible to add various known additives such as barium sulfate and magnesium oxide), pigments, dyes, coupling agents, and release agents.

[0112] The polymerized cured product (optical material) of the present invention, after degassing the polymerizable composition as necessary under reduced pressure, is poured into a mold such as glass or plastic, and then a chemical lamp or xenon lamp. A light source such as a low-pressure mercury lamp, high-pressure mercury lamp, metal halide lamp, etc., having an intensity of 50 200 mm, preferably 100 1500 W, more preferably 200 1000 W, several seconds to 10 hours, preferably several seconds to 5 hours, more preferably several seconds to 2 By irradiation for hours, Built. The polymerization temperature is not particularly limited, but is usually in the range of −10 to 60 ° C., preferably 0 to 40 ° C. The polymerization temperature when the thermal polymerization initiator is contained in the polymerizable composition is usually 25 to 200 ° C, preferably 50 to 170 ° C.

Example

[0113] The present invention will be specifically described below with reference to Examples and Comparative Examples. The physical properties of polythiocarbonate dithiol, polythiocarbonate dithiol di (meth) acrylate and polymerized cured product (optical material) were measured by the following methods.

[0114] [Physical properties of polythiocarbonate dithiol]

1. Mercapto group value (SH value; mgKOH / g): Weigh the sample in a 100mL (milliliter) sample bottle (Weighs accurately in gram units to the fourth decimal place) and acetic anhydride-tetrahydrofuran solution ( 5mL of acetic anhydride in solution lOOmL) and 4-dimethylaminopyridine-tetrahydrofuran solution (incl. 4-dimethylaminopyridine lg in solution lOOmL) were accurately added to completely dissolve the sample. After that, it was allowed to stand at room temperature for 1 hour, and then accurately added lmL of ultrapure water, allowed to stand at room temperature for 30 minutes with occasional stirring, and titrated with 0.25M potassium hydroxide-ethanol solution (indicator: phenol). Phthalein). The SH value was calculated by the following formula.

[0115] SH value (mgKOHZg) = 14. 025 X (B—A) X f / S

(However, in the formula, S is the amount of sample collected (g), A is the amount required for titration of the sample 0.25M aqueous solution of potassium hydroxide and ethanol (mL), B is required for the blank test 0.25M Amount of potassium hydroxide-ethanol solution (mL), f represents the factor of 0.25M potassium hydroxide ethanol solution.)

[0116] 2. Number average molecular weight (M): Calculated by the following formula.

[0117] M = 112200ZSH value

[0118] 3. Melting point (° C) and crystallization temperature (° C): Using a differential scanning calorimeter (manufactured by Shimadzu Corporation; DSC-50), in the range of 100-100 ° C in a nitrogen gas atmosphere Measured at 10 ° CZ min for temperature rise and 10 ° CZ min for temperature drop.

4. Viscosity (mPa · sec): Measured at 35 ° C. using an E-type rotational viscometer (manufactured by Brookfield; Programmable Digital Viscometer DV—Π +). [0120] 5. Hue (APHA): Measured according to JIS-K1557.

[0121] 6. Ratio of aryloxy group in terminal group (%): — The integrated force of NMR was also determined for the ratio (molar basis) of aryloxy group to all terminal groups.

[0122] [Physical properties of polythiocarbonate dithiol di (meth) acrylate]

1. Number average molecular weight (M): Calculated by the following formula.

[0123] M = 1122007 (SH value of polythiocarbonate dithiol) + 108. 1 + E

(However, in the formula, 0 is substituted for polythiocarbonate dithiol ditalarate and 28.1 is substituted for polycarbonate dithiol dimethacrylate.)

2. Melting point (° C) and crystallization temperature (° C): Using a differential scanning calorimeter (manufactured by Shimadzu Corporation; DSC-50), the temperature rises in the range of 100 to 60 ° C in a nitrogen gas atmosphere. Measurements were taken at a temperature rate of 10 ° CZ and a temperature decrease rate of 10 ° CZ.

[0124] 3. Viscosity (mPa 'sec): Measured at 35 ° C using an E-type rotational viscometer (Brookfield; Programmable Digital Viscometer DV—Π +).

[0125] 4. Hue (APHA): Measured according to JIS K1557.

[0126] 5. Proportion of (meth) atalyloyl group in terminal group (%) The integrated force of NMR was also determined for the proportion of (meth) atalyloyl group with respect to all terminal groups (molar basis).

[Physical properties of polymerized cured product (optical material)]

1. Refractive index (n): Using a refractometer (Atago Abbe refractometer; MR-04), 6 wires (e

The refractive index when irradiated with X = 546 nm was measured.

[0128] 2. Abbe number (V): using the above refractometer, e line (λ = 546nm), F, line (λ = 480n e

m), C, and the refractive index (n, n, n) when irradiated with the line (λ = 644nm), respectively, and e F 'C'

Calculated by the following formula.

[0129] V = (n-l) / (n n)

e e F 'C'

[0130] 3. Flexural modulus: Measured at 23 ° C and 50% RH using a three-point bending tester (Orientec; Tensilon UCT-5T) according to JIS—K7171. The bending strength and bending fracture strain were determined. The size of the test piece was 25 mm in width, 40 mm in length, and lm m in thickness, the distance between support bases was 32 mm, and the radius of the indenter and support base was 5. Omm and 2. Omm, respectively. [0131] [Reference Example 1]

[Production of polythiocarbonate dithiol]

Into a 500 mL glass reactor equipped with a stirrer, thermometer, and distillation column (with a fractionation tube, reflux head, and condenser at the top of the column), 1,6-hexanedithiol 90.lg (0.599 mol) ), bis (2-Merukaputechiru) sulfides 77. 2 g (0. 500 mol), Jifue - Le carbonate 155 g (0. 725 mol), and 10 weight ^_0/0 tetra heptyl ammonium - Umuhidoro Kishido - methanol solution (catalyst 0. 861 g (0.332 mmol) was charged and held at 200 mmHg (27 kPa) at 160 ° C for 1 hour. Then, while distilling off the phenol, the pressure was gradually reduced to 50 mmHg over 8 hours, and when the phenol stopped distilling, the pressure was gradually reduced to 15 mmHg (2. OkPa) over 3 hours. The mixture was reacted while distilling a mixture of 1,6-hexanedithiol to obtain the desired polythiocarbonate dithiol.

[0132] The measurement results of ¹ H-NMR of the obtained polythiocarbonate dithiol are shown below.

[0133] NMR (300 MHz ゝ CDC1) δ (ppm): 1. 33 (t, J = 7.3 Hz ゝ SH) ゝ 1. 39 (m

Three

, CH), 1.62 (m, CH), 1.74 (m, SH), 2.52 (m, CH SH), 2. 74— 2.84 (

2 2 2

m, CH SCH and CH SH), 2.97 (m, CH SCO), 3.19 (m, CH SCO)

2 2 2 2 2

[0134] To this polythiocarbonate dithiol, equimolar amount of p-toluenesulfonic acid monohydrate was added to the catalyst, and the mixture was stirred at 130 ° C for 2 hours to deactivate the catalyst. Next, 430 g of methyl chloride was added to dissolve the polythiocarbonate dithiol, and the solution was washed three times with the same amount of water, and then dried over anhydrous magnesium sulfate. Dimethylene was distilled off. The physical properties of the finally obtained polythiocarbonate dithiol (A) are shown below. The SH value was consistent with the ¹ H-NMR measurement result.

[0135] SH value: 211. 4 mg KOH / g, number average molecular weight: 531, melting point: 9.7 ° C, crystallization temperature: 19.8 ° C, viscosity (35 ° C): 248mPa'sec, hue (APHA ): 10, ratio of aryloxy group in terminal group: <1%

[Example 1]

[Manufacture of polythiocarbonate dithiolbis 3-black propionate] In a 200 mL glass reactor equipped with a stirrer, thermometer, and dropping funnel, Inject 23.3 g (184 mmol) of lolopropiol chloride under nitrogen flow at 40 ° C. 47.3 g (89. 1 mmol) of polythiocarbonate dithiol (A) injected into the dropping funnel and 19 mL of 1,2 dichloroethane The mixed solution was added dropwise over 3 hours. After the reaction mixture was stirred with heating at the same temperature for 12 hours, 11.7 g (92.1 mmol) of 3 × n-propioyl chloride was added. The reaction mixture was stirred at the same temperature until the reaction was completed, then cooled to room temperature, transferred to a 2 L reactor, and 470 mL of 1,2 dichloroethane and 520 g of saturated aqueous sodium hydrogen carbonate solution were added. Stir for hours. The reaction mixture was allowed to stand, the organic layer and the aqueous layer were separated, and the organic layer was washed twice with 140 mL of water and then dried over anhydrous magnesium sulfate. The solid product was filtered, and the solvent was distilled off under reduced pressure to obtain 65. Og of colorless liquid polythiocarbonate dithiol bis 3 black propionate (B).

[0137] Yeah! The NMR measurement results are shown below.

[0138] NMR (300 MHz CDC1) δ (ppm): 1.38 (m, CH), 1.62 (m, CH), 2

3 2 2

74- 2. 84 (m, CH SCH), 2. 89— 3. 05 (m, CH SCO and C1CH CH)

2 2 2 2 2

3.12-3.23 (m, CH SCO), 3.75—3.80 (m, CH CI)

twenty two

[Example 2]

[Production of polythiocarbonate dithiol ditalylate]

Polycarbonate dithiol bis 3 black propionate (B) 65.0 g (89.2 mmol) and toluene 200 mL were poured into a glass reactor with an internal volume of 500 mL equipped with a stirrer, thermometer and dropping funnel. 36. lg (357 mmol) of triethylamine injected into the funnel was added dropwise at 25 ° C. over 30 minutes. The reaction mixture was stirred at the same temperature for 6 hours, and the solid was filtered and washed with 400 mL of toluene. The filtrate was washed with 268 mL of 1M hydrochloric acid, washed twice with 4 OOmL of water, dried over anhydrous magnesium sulfate, and the solid was filtered. After dissolving 28 mg of 4-methoxyphenol in the filtrate, the filtrate was concentrated under reduced pressure to obtain 56.2 g of polythiocarbonate dithiol dichlore HC). The yield was 98.7% based on polythiocarbonate dithiol (A). The physical properties of polythiocarbonate dithiol ditalylate (C) are shown in Table 1, and the iH-NMR measurement results are shown below.

[0140] — NMR (300MHz, CDC1) δ (ppm): 1.39 (m, CH), 1.62 (m, CH), 2

3 2 2

76- 2.86 (m, CH SCH), 2. 92—3.01 (m, CH SCO), 3.16—3.21 (m, CH SCO), 5.65-5.74 (m, CH CH), 6.26—6.42 (m, CH CH and CH)

2 2 2

[0141] [Reference Example 2]

[Production of bis (2-attalyloylthioethyl) sulfide]

A bis (2-attalyloylthioethyl) sulfide was produced with reference to JP-A-2004-128468.

[Example 3]

(Manufacture of optical material (D))

In a 30 mL glass vessel, polythiocarbonate dithiol ditalylate (C) l. 47 g, bis (2-attalyloylthioethyl) sulfide 5.85 g and 1-hydroxycyclohexylphenyl ketone 0. 0363 g was mixed to obtain a polymerizable composition. The polymerizable composition is poured into a mold with a 1 mm thick silicon rubber spacer sandwiched between two glass plates, and a UV lamp (preset type deep UV lamp; U XM— QQ255BY by USH IO SPOT CURE SP—ΠΙ) Xenon-mercury lamp (259W) was irradiated at room temperature (25 ° C) for 1 hour. The obtained polymerized cured product (optical material (D)) was released, cut into a predetermined size, and the optical properties and mechanical properties were measured. Table 2 shows the composition of the polymerizable composition and Table 3 shows the physical properties of the optical material.

[Example 4]

(Manufacture of optical material (E))

In the same container as in Example 3, 2.19 g of polythiocarbonate dithiol dichlore HC), bis (2-attalyloylthioethyl) sulfide 5. l lg and 1-hydroxycyclohexylphenol ketone 0.031 g Were mixed to obtain a polymerizable composition. In the same manner as in Example 3, an optical material (E) was obtained. Table 2 shows the composition of the polymerizable composition, and Table 3 shows the physical properties of the optical material.

[Example 5]

(Manufacture of optical material (F))

In the same container as in Example 3, 3.65 g of polythiocarbonate dithiol dichlore HC), 3.69 g of bis (2-allyloylthioethyl) sulfide and 1-hydroxycyclohexylphenol ketone 0 036 lg was mixed to obtain a polymerizable composition. Similar to Example 3 As a result, an optical material (F) was obtained. Table 2 shows the composition of the polymerizable composition and Table 3 shows the physical properties of the optical material.

[Example 6]

(Manufacture of optical material (G))

In the same container as in Example 3, 5.12 g of polythiocarbonate dithiol dichlore HC), 2.20 g of bis (2-attalyloylthioethyl) sulfide and 1-hydroxycyclohexylphenol ketone 0 0362 g was mixed to obtain a polymerizable composition. In the same manner as in Example 3, an optical material (G) was obtained. Table 2 shows the composition of the polymerizable composition, and Table 3 shows the physical properties of the optical material.

[Example 7]

(Manufacture of optical material (H))

In a container similar to that in Example 3, 3.02 g of polythiocarbonate dithiol dichlore HC) and 0.0146 g of 1-hydroxycyclohexyl phenol ketone were mixed to obtain a polymerizable composition. In the same manner as in Example 3, an optical material (H) was obtained. Table 2 shows the composition of the polymerizable composition and Table 3 shows the physical properties of the optical material.

[Reference Example 3]

[Manufacture of 3-chloro black 2-methinorepropio-norechloride]

3-Chloromethyl 2-methylpropiol chloride was produced by the method described in Farmacia (Bucharest, Romania), 15 (5), 263-268 (1967).

[Example 8]

[Production of polythiocarbonate dithiol bis 3-chloro-2-methylpropionate

]

Into the same reactor as in Example 1, 27.4 g (194 mmol) of 3-chloroprophyl-2-methylpropiochloride was injected, and polythiocarbonate dithiol (40 mg) was poured into the dropping funnel at 40 ° C under a nitrogen stream. A) A mixed solution of 50.0 g (94.2 mmol) and 1,2-dichloroethane 20 mL was added dropwise over 1 hour. After the reaction mixture was stirred with heating at the same temperature for 12 hours, 13.7 g (97.1 mmol) of 3-chloro-2-methylpropiochloride was added. The reaction mixture is stirred at the same temperature until the reaction is completed, then cooled to room temperature, and the same operation as in Example 1 is performed. As a result, 77.5 g of a colorless liquid polythiocarbonate dithiol bis 3 chloro-2 methyl propionate (1) was obtained.

[0149] Yeah! The NMR measurement results are shown below.

[0150] — NMR (300 MHz, CDC1) δ (ppm): 1.30 (d, J = 7. OHz, CH), 1.31 (

3 3 d, J = 7. OHz, CH), 1.38 (m, CH), 1.62 (m, CH), 2.73-2.84 (m, CH

3 2 2

SCH), 2.87-3.05 (m, CH SCO and CH), 3.11-3.23 (m, CH SCO)

2 2 2 2

3.51-3.58 (m, CH CI), 3.73-3.80 (m, CH CI)

twenty two

[Example 9]

[Production of polythiocarbonate dithiol dimethacrylate]

77.5 g (94.2 mmol) of polythiocarbonate dithiol bis 3 chloro-2-methylpropionate (1) and 200 mL of toluene were injected into the same reactor as in Example 2, and 76.3 g (754 mmol) of triethylamine injected into the dropping funnel. ) Was added dropwise at 25 ° C over 30 minutes. The reaction mixture was stirred at the same temperature for 165 hours, and then the solid was filtered and subjected to the same operation as in Example 2 to obtain 60.1 g of polythiocarbonate dithiol dimethaacrylate (J). The yield was 98.6% based on polythiocarbonate dithiol (A). The physical properties of polythiocarbonate dithiol dimethacrylate (J) are shown in Table 1, and the measurement results of 'Η-Ν MR are shown below.

[0152] 'H-NMROOOMHZ, CDC1) δ (ppm): 1.40 (m, CH), 1.62 (m, CH), 1

3 2 2

.97 (d, J = l.5Hz, CH), 1.98 (d, J = l.5Hz, CH), 2.74-2.86 (m, CH

3 3 2

SCH), 2.88-3.01 (m, CH SCO), 3.11— 3.25 (m, CH SCO), 5.56 (m

2 2 2

, CH C), 5.61 (m, CH C), 6.06 (m, CH C), 6.09 (m, CH C)

2 2 2 2

[Example 10]

(Manufacture of optical material (K))

In the same container as in Example 3, 3.76 g of polythiocarbonate dithiol dimethatalylate (J), 3.75 g of bis (2-attalyloylthioethyl) sulfide and 0.0362 g of 1-hydroxycyclohexylphenol ketone Were mixed to obtain a polymerizable composition. In the same manner as in Example 3, an optical material (K) was obtained. Table 2 shows the composition of the polymerizable composition, and Table 3 shows the physical properties of the optical material. [Example 11]

(Manufacture of optical material (L))

In the same container as in Example 3, 7.33 g of polythiocarbonate dithiol dimethacrylate (J) and 0.0377 g of 1-hydroxycyclohexylphenol ketone were mixed to obtain a polymerizable composition. In the same manner as in Example 3, an optical material (L) was obtained. Table 2 shows the composition of the polymerizable composition, and Table 3 shows the physical properties of the optical material.

[0155] [Comparative Example]

(Manufacture of optical material (M))

In a container similar to that in Example 3, 1.99 g of bis (2-allyloylthioethyl) sulfide and 0.0107 g of 1-hydroxycyclohexyl phenol ketone were mixed to obtain a polymerizable composition. . An attempt was made to obtain the optical material (M) in the same manner as in Example 3. However, cracking occurred at the time of curing molding, and sufficient bending strength and bending fracture strain were not obtained. Table 2 shows the composition of the polymerizable composition and Table 3 shows the physical properties of the optical material.

[0156] [Table 1]

[0157] [Table 2]

Polythiol Ponate Bis (2-acryloyl polymerizable dithiol thioethyl) Composition Di (meth) Content Sulfide

Key relay (wt%) Content (wt%) Example 3 D C 20 80 Example 4 E C 30 70 Example 5 F C 50 50 Example 6 G C 70 30 Example 7 H C 100 0

Example 1 0 K J 50 50

Example 1 1 and J 100 0

Comparative example ― 0 100

[0158] [Table 3]

Industrial applicability

[0159] The polythiocarbonate polythiol poly (meth) acrylate of the present invention can be polymerized and molded in a short time, and has excellent optical performance (high refractive index, high Abbe number) and excellent Plastic materials with mechanical performance (high bending strength, high bending fracture strain), such as plastic lenses, prisms, optical fibers, information recording substrates, colored filters, infrared absorption filters, optical adhesives, optical films, etc. Is expected to be used for optical materials. Furthermore, since the polythiocarbonate polythiol poly (meth) acrylate of the present invention has not only excellent optical performance but also excellent mechanical performance, it is expected to contribute to high strength of various optical materials. The

Claims

The scope of the claims

A polythiocarbonate polythiol poly (meth) acrylate having a structure in which a hydrogen atom of a mercapto group of a polythiocarbonate polythiol is substituted by a (meth) atalyloyl group represented by the general formula (1).

[Chemical 1]

(In the formula, X represents a hydrogen atom or a methyl group.)

The polythiocarbonate polythiol poly (meth) acrylate according to claim 1, wherein the polythiocarbonate polythiol has a repeating unit represented by the general formula (2).

[Chemical 2]

[3] The polythiocarbonate polythiol poly (meth) acrylate according to claim 1, wherein the polythiocarbonate polythiol has at least two types of repeating units represented by the general formula (2).

[4] The polycarbonate polythiol poly (meth) acrylate represented by the general formula (3) and having a number average molecular weight of 300 to 3000.

[Chemical 3]

[5] The polythiocarbonate polythiol poly (meth) acrylate according to any one of claims 14 to 14, which is liquid at room temperature.

[6] The degree of substitution of the hydrogen atom of the mercapto group by the (meth) ataryloyl group of the general formula (1) is 8

The polythiocarbonate polythiol poly (meth) acrylate is the polythiocarbonate polythiol poly (meth) acrylate according to any one of claims 14 to 14.

[7] The polythiocarbonate polythiol poly (meth) acrylate according to any one of claims 14 to 14, wherein APHA is 150 or less.

[8] The polythiocarbonate polythiol poly (meth) acrylate is the viscosity according to any one of claims 14 to 14, wherein the viscosity at 35 ° C is lOOOOmPa'sec or less.

[9] It is characterized by reacting polythiocarbonate polythiol with 3-logeno (2-methyl) propio-nornolide represented by the general formula (4), followed by the formation of a vinyl bond by dehalogenated hydrogen. The method for producing a polythiocarbonate polythiol poly (meth) acrylate according to claim 14.

[Chemical 4]

Polythiocarbonate polythiol poly 3-halogeno (mono-2-methyl) propionate in which the hydrogen atom of the mercapto group of polythiocarbonate polythiol is substituted with a 3-logeno (2-methyl) propiol group represented by the general formula (5) .

[Chemical 5]

(Wherein X and A are as defined above.)

11. The polythiocarbonate polythiol poly 3-halogeno (1-2-methyl) propionate represented by the general formula (6) and having a number average molecular weight of 350 to 3200.

[Chemical 6]

(In the formula, A and C each independently represent a halogen atom, and R, X, Y and n are as defined above.)

[12] A polymerizable composition comprising 3 to L00% of the polythiocarbonate polythiol poly (meth) acrylate according to any one of claims 1 to 8 on a weight basis.

[13] A polymer hardened material obtained by subjecting the polymerizable composition according to claim 12 to a radical polymerization reaction.

[14] An optical material using the polymerization cured product according to [13].