JP3263162B2 - Sulfur-containing phosphate ester type internal release agent - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an internal release agent, a method for molding a resin using the same, and a resin molded product obtained by the method. The present invention is characterized in that a mold release property is improved and a transparent resin molded product with less turbidity is obtained. Therefore, the present invention is particularly useful in molding optical products such as plastic lenses that require surface accuracy and transparency, but is also useful in other resin moldings because of its excellent mold release properties.

[0002]

2. Description of the Related Art There are various methods for molding a resin, such as mold polymerization and injection molding. In each case, a so-called release agent is used to improve the releasability of a molded product from a mold. In particular, urethane resin, epoxy resin and the like have a strong adhesive force and the use of a release agent is essential.

[0003] Release agents are broadly classified into external release agents and internal release agents. Since the external release agent must be applied to the inner surface of the mold every time molding is performed, the productivity of the molded product is poor, and the external release agent migrates to the surface of the molded product, causing unevenness on the surface of the molded product. In addition, there are problems such as poor painting and dyeing, and turbidity of the transparent resin molded product. On the other hand, the internal release agent is a release agent added in advance to the resin material monomer, and it is not necessary to apply it to the mold every time, which is advantageous for improving productivity.

Conventionally known internal release agents include fluorine-based nonionic surfactants for molding urethane resins,
Silicon-based nonionic surfactant, alkyl quaternary ammonium salt, acidic phosphate ester, liquid paraffin, wax, higher fatty acid and its metal salt, higher fatty acid ester, higher aliphatic alcohol, bisamides, polysiloxanes, aliphatic There are amine ethylene oxide adducts and the like (JP-A-1-295201). Recently, a phosphate ester having a polyether substituent (Japanese Patent Laid-Open No. 3-28764)
Is also known.

[0005] In the reaction injection molding method of urethane resin, zinc stearate is generally used. However, since zinc stearate has poor solubility in raw materials, patents on various compatibilizers have been filed ( JP-A-3-273030, JP-B-3-27586).

In molding an epoxy resin, a method using zinc stearate as an internal mold release agent (Japanese Patent Laid-Open No.
213602), a method using a fluorine-based nonionic surfactant, a silicon-based nonionic surfactant, an alkyl quaternary ammonium salt, an acidic phosphate ester or the like as an internal mold release agent (JP-A-3-83320). A method in which an external release agent and an internal release agent are used in combination (JP-A-63-144)
302, JP-A-63-144303).

In addition, in molding a polyolefin resin, aliphatic alcohols, aliphatic esters, phthalic esters, triglycerides, fluorine-based surfactants, metal salts of higher fatty acids, and the like are used as internal mold release agents (Japanese Patent Laid-Open No. In the molding of polycarbonate resins, higher fatty acid esters, waxes, liquid paraffin, silicone oil, alkyl glyceryl ethers and the like are used as internal mold release agents (JP-A-1-315460, JP-A-2-315460). 1-3-15559), and also for acrylic resins, a molding method using higher alcohols, higher fatty acid esters, higher fatty acids and the like as an internal mold release agent is generally performed (JP-A-2-105844).

[0008]

Although these known internal mold release agents are more effective in improving productivity than external mold release agents, they do not have sufficient mold release performance, so that they do not adhere to the mold surface during mold release. Resin may remain, or in the case of a glass mold, the glass may be peeled off. Further, there is a case where an excessive stress is applied due to the resistance at the time of release, and warping or distortion occurs in the molded product. Furthermore, there is a problem that the molded product is liable to be turbid when the amount of use is sufficient to sufficiently release the mold. These drawbacks are particularly fatal in the molding of optical products such as plastic lenses and optical discs, for which surface accuracy and transparency are important, and significantly reduce the commercial value.
Therefore, there has been a strong demand for the development of a new internal release agent having sufficient release performance and not impairing the transparency in molding a transparent resin.

[0009]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, the following formula (1)

[0010]

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Wherein X and Y each represent an oxygen atom or a sulfur atom, and at least one of X and Y is a sulfur atom;
R ₁ and R ₂ represent an alkyl group. By using as an internal release agent containing one or two or more sulfur-containing phosphate esters selected from the group consisting of thiophosphate esters and dithiophosphate esters represented by It has been found that the transparency of the transparent resin can be sufficiently improved. Further, the sulfur-containing phosphoric acid ester according to the present invention has excellent compatibility with a resin or a monomer and is a compound which is extremely easily used as an internal mold release agent.

It is known that the thiophosphate represented by the formula (1) has an equilibrium represented by the following formula (2) and is generally present as a mixture (Method)
nder Organishen Chemie, B
and XII / 2, p604, 1964).

[0013]

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Most of the conventional uses of sulfur-containing phosphate esters are for pesticides as a raw material for insecticides and fungicides (US Pat. No. 3,742,097), and sulfur-containing phosphate esters are useful as internal mold release agents. This was not expected at all from conventional applications.

As specific examples of the internal mold release used in the present invention, for example, dimethyl thiophosphate, diethyl thiophosphate,
Dipropyl thiophosphate, diisopropyl thiophosphate, dibutyl thiophosphate, dioctyl thiophosphate, didecyl thiophosphate, didodecyl thiophosphate, ditetradodecyl thiophosphate, dihexadecyl thiophosphate, dioctadecyl thiophosphate.

Specific examples of the dithiophosphate represented by the formulas (1) and (2) include dimethyl dithiophosphate, diethyl dithiophosphate, dipropyl dithiophosphate, diisopropyl dithiophosphate, dibutyl dithiophosphate, dihexyl dithiophosphate, and dithiophosphoric acid. Dioctyl, didecyl dithiophosphate, didodecyl dithiophosphate, ditetradodecyl dithiophosphate, dihexadecyl dithiophosphate, dioctadecyl dithiophosphate.

The resin to be used in the present invention is not particularly limited. Examples of the thermosetting resin include urethane resin, epoxy resin, polyolefin resin, polyene-polythiol resin, unsaturated polyester resin, phenol resin, furan resin and xylene resin. , A formaldehyde resin, a ketone resin, a urea resin, a melamine resin, an aniline resin, a sulfonamide resin, an alkyd resin, and a composite resin thereof.

Examples of the thermoplastic resin include polyolefin resin, polycarbonate resin, thermoplastic polyester resin, polyether resin, polyamide resin, polyimide resin, urethane resin, polyvinyl ketone resin, polyvinyl ether resin, and composite resins thereof.

The molding method is appropriately selected depending on the characteristics of the resin. Generally, a thermosetting resin is molded by a mold polymerization method, a compression molding method or the like, and a thermoplastic resin is molded by an injection molding method, an extrusion molding method or the like. However, the present invention can be implemented in any of the methods. In the case of template polymerization, a sulfur-containing phosphoric acid ester is added to a monomer or a monomer mixture in advance, and then polymerized in a template.

In another molding method, a resin powder or a pellet is subjected to molding. A method in which a sulfur-containing phosphoric acid ester is mixed with a resin powder and then melted or plasticized and then injected into a mold, or molded. Any method may be used, such as a method in which a sulfur-containing phosphoric acid ester is added in advance during the production of a powder or a pellet, and the obtained resin powder or pellet is directly used for molding.

The amount of the sulfur-containing phosphoric acid ester used is preferably 0.01 to 5% by weight based on the total amount of the monomers, when the mold release is difficult as in the case of template polymerization of urethane resin or epoxy resin. If the amount is less than 5% by weight, the releasability tends to decrease.

In addition, since injection molding of a thermoplastic resin such as a polyolefin resin, a polycarbonate resin, or an acrylic resin is relatively easy to release, the amount of the sulfur-containing phosphoric acid ester to be used is 0.01 to 0.01% based on the resin. It is preferably carried out even at 1% by weight.

The alkyl groups of R ₁ and R _{2 in} the general formula (1) may be the same or different. In general, the shorter the alkyl chain, the higher the mold release performance and the sulfur-containing phosphorus of the C ₁ -C ₈ alkyl group. The use of acid esters is preferred. However, when a particularly high temperature is required in injection molding or the like, use of a sulfur-containing phosphoric acid ester having a high boiling point may be preferable, and in that case, those having up to _C18 are preferably used. In the case of sulfur-containing phosphoric acid esters in which R ₁ and R ₂ are alkyl groups larger than C ₁₈ , the mold release performance is lowered, and in molding a transparent resin, a molded article tends to be turbid.

As the mold material, generally used stainless steel, copper, aluminum and alloys thereof, wood, ceramics, glass and the like can be used.

Hereinafter, the present invention will be described in more detail with reference to some typical resins. As the urethane resin to be used in the present invention, one or two or more iso (thio) cyanate compounds and a polyol compound selected from a polyisocyanate compound, a polyisothiocyanate compound, and an isothiocyanate compound having an isocyanate group, Examples thereof include resins obtained by polymerizing one or more active hydrogen compounds selected from the group consisting of polythiol compounds and hydroxythiol compounds, and known chain extenders according to the purpose at the time of polymerization molding. , Crosslinker, light stabilizer,
Various additives such as an ultraviolet absorber, an antioxidant, an oil-soluble dye, a filler, and a polymerization catalyst may be added.

Examples of the polyisocyanate compound include ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, and 2,2 '. -Dimethylpentane diisocyanate, 2,2,4-trimethylhexane diisocyanate, decamethylene diisocyanate, butene diisocyanate, 1,3-butadiene-
1,4-diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,6,11-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanate 4-isocyanatomethyloctane, 2,5,7-trimethyl-
1,8-diisocyanato-5-isocyanatomethyloctane, bis (isocyanatoethyl) carbonate, bis (isocyanatoethyl) ether, 1,4-butyleneglycoldipropylether-α, α′-diisocyanate, lysinediamine Isocyanate methyl ester, lysine triisocyanate, 2-isocyanatoethyl-2,6
-Diisocyanatohexanoate, 2-isocyanatopropyl-2,6-diisocyanatohexanoate, xylylene diisocyanate, bis (isocyanatoethyl)
Benzene, bis (isocyanatopropyl) benzene,
α, α, α ′, α′-tetramethylxylylene diisocyanate, bis (isocyanatobutyl) benzene, bis (isocyanatomethyl) naphthalene, bis (isocyanatomethyl) diphenyl ether, bis (isocyanatoethyl) phthalate, mesylate Tyrylene triisocyanate,
Aliphatic polyisocyanates such as 2,6-di (isocyanatomethyl) furan, isophorone diisocyanate, bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, dicyclohexyl Dimethylmethane diisocyanate, 2,
2'-dimethyldicyclohexylmethane diisocyanate, bis (4-isocyanato-n-butylidene) pentaerythritol, diisocyanate dimerate, 2-isocyanatomethyl-3- (3-isocyanatopropyl)-
5-isocyanatomethyl-bicyclo [2,2,1] -heptane, 2-isocyanatomethyl-3- (3-isocyanatopropyl) -6-isocyanatomethyl-bicyclo [2,2,1] -heptane, 2-isocyanatomethyl-
2- (3-isocyanatopropyl) -5-isocyanatomethyl-bicyclo [2,2,1] -heptane, 2-isocyanatomethyl-2- (3-isocyanatopropyl)-
6-isocyanatomethyl-bicyclo [2,2,1] -heptane, 2-isocyanatomethyl-3- (3-isocyanatopropyl) -5- (2-isocyanatoethyl) -bicyclo- [2,2 1] -heptane, 2-isocyanatomethyl-3- (3-isocyanatopropyl) -6- (2
-Isocyanatoethyl) -bicyclo- [2,2,1]-
Heptane, 2-isocyanatomethyl-2- (3-isocyanatopropyl) -5- (2-isocyanatoethyl)-
Bicyclo- [2,2,1] -heptane, 2-isocyanatomethyl-2- (3-isocyanatopropyl) -6
(2-isocyanatoethyl) -bicyclo- [2,2
1] -heptane, alicyclic polyisocyanate such as 2,5 (or 6) -bis (isocyanatomethyl) -bicyclo [2,2,1] -heptane, phenylene diisocyanate, tolylene diisocyanate, ethyl Phenylene diisocyanate, isopropyl phenylene diisocyanate, dimethyl phenylene diisocyanate, diethyl phenylene diisocyanate, diisopropyl phenylene diisocyanate, trimethylbenzene triisocyanate, benzene triisocyanate, naphthalene diisocyanate, methyl naphthalene diisocyanate , Biphenyl diisocyanate, tolidine diisocyanate,
4,4′-diphenylmethane diisocyanate, 3,
3′-dimethyldiphenylmethane-4,4′-diisocyanate, bibenzyl-4,4′-diisocyanate,
Bis (isocyanatophenyl) ethylene, 3,3'-dimethoxybiphenyl-4,4'-diisocyanate, triphenylmethanetriisocyanate, polymeric
MDI, naphthalene triisocyanate, diphenylmethane 2,4,4'-triisocyanate, 3-methyldiphenylmethane-4,6,4'-triisocyanate,
4-methyl-diphenylmethane-3,5,2 ', 4',
6'-pentaisocyanate, phenylisocyanatomethylisocyanate, phenylisocyanatoethylisocyanate, tetrahydronaphthalenediisocyanate, hexahydrobenzenediisocyanate, hexahydrodiphenylmethane-4,4'-diisocyanate,
Diphenyl ether diisocyanate, ethylene glycol diphenyl ether diisocyanate, 1,3-propylene glycol diphenyl ether diisocyanate, benzophenone diisocyanate, diethylene glycol diphenyl ether diisocyanate, dibenzofuran isocyanate, carbazole diisocyanate, ethyl carbazole diisocyanate, And aromatic polyisocyanates such as dichlorocarbazole diisocyanate.

Examples of the polyisocyanate compound containing a sulfur atom include thiodiethylene diisocyanate, thiodipropyl diisocyanate, thiodihexyl diisocyanate, dimethyl sulfone diisocyanate, dithiodimethyl diisocyanate, and dithiodiethyl. Sulfur-containing aliphatic isocyanates such as diisocyanate and dithiodipropyl diisocyanate, diphenylsulfide-2,4'-diisocyanate, diphenylsulfide-4,4'-diisocyanate, 3,3'-dimethoxy- Aromatic having a sulfide bond such as 4,4'-diisocyanatodibenzylthioether, bis (4-isocyanatomethylphenyl) sulfide, 4,4'-methoxyphenylthioethylene glycol-3,3'-diisocyanate Isocyana , Diphenyl disulfide-4,4'-diisocyanate, 2,2'-dimethyl diphenyl disulfide-5,5'-diisocyanate, 3,3'-dimethyl diphenyl disulfide -5,
5′-diisocyanate, 3,3′-dimethyldiphenyldisulfide-6,6′-diisocyanate, 4,
4'-dimethyldiphenyldisulfide-5,5'-diisocyanate, 3,3'-dimethoxydiphenyldisulfide-4,4'-diisocyanate, 4,4'-dimethoxydiphenyldisulfide-3,3'-diisocyanate Aromatic isocyanates having a disulfide bond, such as nathate, diphenylsulfone-4,4'-diisocyanate, diphenylsulfone-3,3'-diisocyanate, benzidinesulfone-4,4'-diisocyanate, diphenylmethane Sulfone-4,4'-diisocyanate, 4-methyldiphenylsulfone-2,4'-
Diisocyanate, 4,4'-dimethoxydiphenylsulfone-3,3'-diisocyanate, 3,3'-dimethoxy-4,4'-diisocyanatobenzyldisulfone, 4,4'-dimethyldiphenylsulfone-3 , 3 '
-Diisocyanate, 4,4'-di-tert-butyldiphenylsulfone-3,3'-diisocyanate,
4,4'-methoxyphenylethylene sulfone-3,
Aromatic isocyanate having a sulfone bond such as 3'-diisocyanate, 4,4'-dicyclodiphenylsulfone-3,3'-diisocyanate, 4-methyl-3
Aromatic isocyanates having a sulfonic acid ester bond, such as -isocyanatophenylsulfonyl-4'-isocyanatophenol ester and 4-methoxy-3-isocyanatophenylsulfonyl-4'-isocyanatophenol ester, 4-methyl-3 -Isocyanatophenylsulfonylanilide-3'-methyl-4'-isocyanate, diphenylsulfonyl-ethylenediamine-
4,4'-diisocyanate, 4,4'-methoxyphenylsulfonyl-ethylenediamine-3,3'-diisocyanate, 4-methyl-3-isocyanatophenylsulfonylanilide-4-methyl-3'-isocyanate Such as aromatic isocyanates having a sulfonic acid amide bond, sulfur-containing heterocyclic compounds such as thiophene-2,5-diisocyanate, and 1,4-dithiane-2,5-diisocyanate.

As the polyisothiocyanate compound,
For example, 1,2-diisothiocyanatoethane, 1,3-
Diisothiocyanatopropane, 1,4-diisothiocyanatobutane, 1,6-diisothiocyanatohexane, P
-Aliphatic polyisothiocyanates such as phenylenediisopropylidene diisothiocyanate, aliphatic isothiocyanates such as cyclohexane diisothiocyanate,
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 (4-isothiocyanatobenzene ),
4,4'-diisothiocyanatobenzophenone, 4,
4'-diisothiocyanato-3,3'-dimethylbenzophenone, benzanilide-3,4'-diisothiocyanate, diphenylether-4,4'-diisothiocyanate, diphenylamine-4,4'-diisocyanate Aromatic polyisothiocyanates such as 2,4,6-
Heterocycle-containing isothiocyanates such as triisothiocyanato-3,5-triazine, and hexanedioildiisothiocyanate, nonanedioildiisothiocyanate, carbonic diisothiocyanate, and 1,3-benzenecarbonyldiisothiate. And carbonyl isothiocyanates such as ocyanate, 1,4-benzenecarbonyldiisothiocyanate, and (2,2′-bipyridine) -4,4′-dicarbonyldiisothiocyanate.

Further, as a polyisothiocyanate containing one or more sulfur atoms in addition to the isothiocyanate group,
For example, sulfur-containing aliphatic polyisothiocyanates such as thiobis (3-isothiocyanatopropane), thiobis (2-isothiocyanatoethane) and dithiobis (2-isothiocyanatoethane), 1-isothiocyanato-4-{(2
-Isocyanato) sulfonyl @ benzene, thiobis (4
-Isothiocyanatobenzene), sulfonylbis (4-
Isothiocyanatobenzene), sulfinylbis (4-
Isothiocyanatobenzene), dithiobis (4-isothiocyanatobenzene), 4-isothiocyanato-1-
{(4-Isocyanatophenyl) sulfonyl} -2-methoxy-benzene, 4-methyl-3-isothiocyanatobenzenesulfonyl-4′-isocyanatophenyl ester, 4-methyl-3-isothiocyanatobenzenesulfonylanilide- Sulfur-containing aromatic polyisothiocyanate such as 3'-methyl-4'-isocyanate, thiophenone-2,5-diisothiocyanate, 1,4-dithiane-
And sulfur-containing heterocyclic compounds such as 2,5-diisothiocyanate.

Further, examples of the isothiocyanate compound having an isocyanato group include 1-isocyanato-3-isothiocyanatopropane and 1-isocyanato-
5-isothiocyanatopentane, 1-isocyanato-6
Aliphatic or alicyclic compounds such as isothiocyanatohexane, isothiocyanatocarbonyl isocyanate, 1-isocyanato-4-isothiocyanatocyclohexane, 1-isocyanato-4-isothiocyanatobenzene, 4-methyl- Aromatic compounds such as 3-isothiocyanato-1-isothiocyanatobenzene, heterocyclic compounds such as 2-isocyanato-4,6-diisothiocyanato-1,3,5-triazine and 4-isothiocyanato-4 '-Isothiocyanatodiphenyl sulfide, 2-
Compounds containing a sulfur atom in addition to an isothiocyanato group such as isothiocyanato-2′-isothiocyanatodiethyl disulfide and the like can be mentioned.

Also, halogen-substituted compounds such as chlorine-substituted and bromine-substituted iso (thio) cyanate compounds,
Further, these buret forming reaction products, adduct reaction products with trimethylolpropane, dimerization or trimerization reaction products, and the like can also be used. These may be used alone or in combination of two or more.

Examples of the polyol compound include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane, butanetriol, 1,2-methylglucoside, and pentane. Erythritol, dipentaerythritol, tripentaerythritol, sorbitol, erythritol, threitol, ribitol, arabinitol, xylitol, allitol, mannitol, dolitol, iditol, glycol, inositol, hexanetriol, triglycerose, digliperol, triethylene glycol, polyethylene glycol, Tris (2-hydroxyethyl) isocyanurate, Black butanediol, cyclopentane diol, cyclohexane diol, cycloheptane diol, cyclooctane diol, cyclohexane dimethanol, hydroxypropyl cyclohexanol, tricyclo [5,2,1,0, ^{2, 6]} decane - dimethanol, bicyclo [4 , 3,0] -nonanediol, dicyclohexanediol, tricyclo [5,3
1,1] dodecanediol, bicyclo [4,3,0] nonanedimethanol, tricyclo [5,3,1,1] dodecane-diethanol, hydroxypropyltricyclo [5,3,1] dodecanol, spiro [ 3,4] octanediol, butylcyclohexanediol, 1,
Aliphatic polyols such as 1'-bicyclohexylidenediol, cyclohexanetriol, maltitol, lactitol, dihydroxynaphthalene, trihydroxynaphthalene, tetrahydroxynaphthalene, dihydroxybenzene, benzenetriol, biphenyltetraol, pyrogallol, (hydroxynaphthyl) pyrogallol , Trihydroxyphenanthrene, bisphenol A, bisphenol F, xylylene glycol, di (2
-Hydroxyethoxy) benzene, bisphenol A-
Bis- (2-hydroxyethyl ether), tetrabromobisphenol A, tetrabromobisphenol A-
In addition to aromatic polyols such as bis- (2-hydroxyethyl ether), halogenated polyols such as dibromoneopentyl glycol, and high molecular polyols such as epoxy resins, oxalic acid, glutamic acid, adipic acid, acetic acid, propionic acid, and cyclohexanecarboxylic acid Acid, β-oxocyclohexanepropionic acid, dimer acid, phthalic acid, isophthalic acid, salicylic acid, 3-bromopropionic acid, 2-bromopropionic acid
Bromoglycol, dicarboxycyclohexane, pyromellitic acid, butanetetracarboxylic acid, a condensation reaction product of an organic acid such as bromophthalic acid and the polyol, an addition reaction product of the polyol and an alkylene oxide such as ethylene oxide or propylene oxide, An addition reaction product of an alkylene polyamine with an alkylene oxide such as ethylene oxide or propylene oxide, and further, bis- [4- (hydroxyethoxy)
Phenyl] sulfide, bis- [4- (2-hydroxypropoxy) phenyl] sulfide, bis- [4-
(2,3-dihydroxypropoxy) phenyl] sulfide, bis- [4- (4-hydroxycyclohexyl ) phenyl
Phenyl] sulfide , bis- [2-methyl-4- (hydroxyethoxy) -6-butylphenyl] sulfide and compounds obtained by adding ethylene oxide and / or propylene oxide of an average of not more than 3 molecules per hydroxyl group to these compounds; (2-hydroxyethyl) sulfide, 1,2-bis- (2-hydroxyethylmercapto) ethane, bis (2-hydroxyethyl) disulfide, 1,4-dithiane-2,5-diol, bis (2
3-dihydroxypropyl) sulfide, tetrakis (4-hydroxy-2-thiabutyl) methane, bis (4
-Hydroxyphenyl) sulfone (trade name: bisphenol S), tetrabromobisphenol S, tetramethylbisphenol S, 4,4'-thiobis (6-tert
-Butyl-3-methylphenol), 1,3-bis (2
-Hydroxyethylthioethyl) -cyclohexane and other polyols containing a sulfur atom.

Examples of the polythiol compound include 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, bicyclo [2,2,
1] pepta-exo-cis-2,3-dithiol,
1,1-bis (mercaptomethyl) cyclohexane, thiomalic acid bis (2-mercaptoethyl ester),
2,3-dimercaptosuccinic acid (2-mercaptoethyl ester), 2,3-dimercapto-1-propanol (2-mercaptoacetate), 2,3-dimercapto-1-propanol (3-mercaptoacetate), 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 tris (2-mercaptoacetate), Trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), 1,2-bis (2-mercaptoethyl thio) -
Aliphatic polythiols such as 3-mercaptopropane),
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-
Bis (mercaptomethyleneoxy) benzene, 1,3-
Bis (mercaptomethyleneoxy) benzene, 1,4-
Bis (mercaptomethyleneoxy) benzene, 1,2-
Bis (mercaptoethyleneoxy) benzene, 1,3-
Bis (mercaptoethyleneoxy) benzene, 1,4-
Bis (mercaptoethyleneoxy) benzene, 1,2,2
3-trimercaptobenzene, 1,2,4-trimercaptobenzene, 1,3,5-trimercaptobenzene,
1,2,3-tris (mercaptomethyl) benzene,
1,2,4-tris (mercaptomethyl) benzene,
1,3,5-tris (mercaptomethyl) benzene,
1,2,3-tris (mercaptoethyl) benzene,
1,2,4-tris (mercaptoethyl) benzene,
1,3,5-tris (mercaptoethyl) benzene,
1,2,3-tris (mercaptomethyleneoxy) benzene, 1,2,4-tris (mercaptomethyleneoxy) benzene, 1,3,5-tris (mercaptomethyleneoxy) benzene, 1,2,3-tris ( Mercaptoethyleneoxy) benzene, 1,2,4-tris (mercaptoethyleneoxy) benzene, 1,3,5-tris (mercaptoethyleneoxy) benzene, 1,2,3
4-tetramercaptobenzene, 1,2,3,5-tetramercaptobenzene, 1,2,4,5-tetramercaptobenzene, 1,2,3,4-tetrakis (mercaptomethyl) benzene, 1,2,3 1,5-tetrakis (mercaptomethyl) benzene, 1,2,4,5-tetrakis (mercaptomethyl) benzene, 1,2,3,4-tetrakis (mercaptoethyl) benzene, 1,2,3
5-tetrakis (mercaptoethyl) benzene, 1,
2,4,5-tetrakis (mercaptoethyl) benzene, 1,2,3,4-tetrakis (mercaptoethyl)
Benzene, 1,2,3,5-tetrakis (mercaptomethyleneoxy) benzene, 1,2,4,5-tetrakis (mercaptomethyleneoxy) benzene, 1,2,3
4-tetrakis (mercaptoethyleneoxy) benzene, 1,2,3,5-tetrakis (mercaptoethyleneoxy) benzene, 1,2,4,5-tetrakis (mercaptoethyleneoxy) benzene, 2,2′-dimercaptophenyl 4,4′-dimercaptobiphenyl,
4,4′-dimercaptobibenzyl, 2,5-toluenedithiol 3,4-toluenedithiol, 1,4-naphthalenedithiol, 1,5-naphthalenedithiol,
2,6-naphthalenedithiol, 2,7-naphthalenedithiol, 2,4-dimethylbenzene-1,3-dithiol, 4,5-dimethylbenzene-1,3-dithiol, 9,10-anthracenedimethanethiol, , 3
-Di (p-methoxyphenyl) propane-2,2-dithiol, 1,3-diphenylpropane-2,2-dithiol, phenylmethane-1,1-dithiol, 2,4
Aromatic polythiols such as -di (p-mercaptophenyl) pentane and 2,5-dichlorobenzene-1,3
-Dithiol, 1,3-di (p-chlorophenyl) propane-2,2-dithiol, 3,4,5-tribromo-
Halogen-substituted aromatic polythiols such as chlorine-substituted products such as 1,2-dimercaptobenzene and 2,3,4,6-tetrachloro-1,5-bis (mercaptomethyl) benzene, and bromine-substituted products, and 2-methyl Amino-4,6-dithiol-sym-triazine, 2-ethylamino-4,6
-Dithiol-sym-triazine, 2-amino-4,
6-dithiol-sym-triazine, 2-morpholino-4,6-dithiol-sym-triazine, 2-cyclohexylamino-4,6-dithiol-sym-triazine, 2-methoxy-4,6-dithiol-sym-
Triazine, 2-phenoxy-4,6-dithiol-s
ym-triazine, 2-thiobenzeneoxy-4,6-
Heterocycle-containing polythiols such as dithiol-sym-triazine and 2-thiobutyloxy-4,6-dithiol-sym-triazine; furthermore, 1,2-bis (mercaptomethylthio) benzene, 1,3-bis (mercapto) Methylthio) benzene, 1,4-bis (mercaptomethylthio) benzene, 1,2-bis (mercaptoethylthio) benzene 1,3-bis (mercaptoethylthio) benzene, 1,4-bis (mercaptoethylthio)
Benzene, 1,2,3-tris (mercaptomethylthio)
E) benzene, 1,2,4-tris (mercaptomethyl
Thio) benzene, 1,3,5-tris (mercaptomethy
Ruthio) benzene, 1,2,3-tris (mercaptoethylthio) benzene, 1,2,4-tris (mercaptoethylthio) benzene, 1,3,5-tris (mercaptoethylthio) benzene, 1,2,2 3,4-tetrakis (mercaptomethylthio) benzene, 1,2,3,5-
Tetrakis (mercaptomethylthio) benzene, 1,
2,4,5-tetrakis (mercaptomethylthio) benzene, 1,2,3,4-tetrakis (mercaptoethylthio) benzene, 1,2,3,5-tetrakis (mercaptoethylthio) benzene, 1,2,4 , 5-tetrakis (mercaptoethylthio) benzene and the like, and aromatic polythiols containing a sulfur atom in addition to the mercapto group such as alkylated nuclei thereof, bis (mercaptomethyl) sulfide, bis (mercaptoethyl) sulfide, bis (mercapto) Propyl) sulfide, bis (mercaptomethylthio) methane, bis (2-mercaptoethylthio) methane, bis (3-mercaptopropyl) methane,
1,2-bis (mercaptomethylthio) ethane, 1,2
-(2-mercaptoethylthio) ethane, 1,2- (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-mercaptoethylthio) propane, 1,2,3-
Tris (3-mercaptopropylthio) propane, tetrakis (mercaptomethylthiomethyl) methane, tetrakis (2-mercaptoethylthiomethyl) methane, tetrakis (3-mercaptopropylthiomethyl) methane,
Bis (2,3-dimercaptopropyl) sulfide,
2,5-dimercapto-1,4-dithiane, 2,5-bis (mercaptomethyl) -1,4-dithiane, bis (mercaptomethyl) disulfide, bis (mercaptoethyl) disulfide, bis (mercaptopropyl) disulfide, etc. Esters of thioglycolic acid and mercaptopropionic acid, hydroxymethyl sulfide bis (2-mercaptoacetate), hydroxymethyl sulfide bis (3-mercaptopropionate),
Hydroxyethyl sulfide bis (2-mercaptoacetate), hydroxyethyl sulfide bis (3-mercaptopropionate), hydroxypropyl sulfidebis (2-mercaptoacetate), hydroxypropyl sulfide bis (3-mercaptopropionate), hydroxymethyl Disulfidebis (2-mercaptoacetate), hydroxymethyldisulfidebis (3-mercaptopropionate), hydroxyethyldisulfidebis (2-mercaptoacetate), hydroxyethyldisulfidebis (3-mercaptopropionate), hydroxypropyldisulfidebis (2
-Mercaptoacetate), hydroxypropyldisulfidebis (3-mercaptopropionate), 2-mercaptoethyletherbis (2-mercaptoacetate), 2-mercaptoethyletherbis (3-mercaptopropionate), 1,4- Dithiane-2,5-diol bis (2-mercaptoacetate), 1,4-dithiane-2,5-diol bis (3-mercaptopropionate), thioglycolic acid bis (2-mercaptoethyl ester), thiodipropionic acid Bis (2-mercaptoethyl ester), bis (2-mercaptoethyl ester) 4,4-thiodibutylate, bis (2-mercaptoethyl ester) dithiodiglycolate, bis (2-mercaptoethyl ester) dithiodipropionate,
Bis (2-mercaptoethyl ester) 4,4-dithiodibutyrate, bis (2,3-dimercaptopropyl ester) thiodiglycolate, bis (2,3-dimercaptopropyl ester) thiodipropionate, dithioglycol Aliphatic polythiols containing a sulfur atom in addition to a mercapto group such as bis (2,3-dimercaptopropyl ester) acid and dithiodipropionic acid (2,3-dimercaptopropyl ester); 3,4-thiophenedithiol; And heterocyclic compounds containing a sulfur atom in addition to a mercapto group such as 1,5-dimercapto-1,3,4-thiadiazole.

Examples of the hydroxy thiol compound include 2-mercaptoethanol, 3-mercapto-1,2-propanediol, glycerin di (mercaptoacetate), 1-hydroxy-4-mercaptocyclohexane, and 2,4-dimercapto. Phenol, 2-
Mercaptohydroquinone, 4-mercaptophenol, 3,4-dimercapto-2-propanol, 1,3
-Dimercapto-2-propanol, 2,3-dimercapto-1-propanol, 1,2-dimercapto-1,
3-butanediol, pentaerythritol tris (3
-Mercaptopropionate), pentaerythritol mono (3-mercaptopropionate), pentaerythritolbis (3-mercaptopropionate), pentaerythritol tris (thioglycolate), pentaerythritol pentakis (3-mercaptopropionate) ), Hydroxymethyl-tris (mercaptoethylthiomethyl) methane, 1-hydroxyethylthio-3-
Mercaptoethylthiobenzene, 4-hydroxy-4 '
-Mercaptodiphenylsulfone, 2- (2-mercaptoethylthio) ethanol, dihydroxyethylsulfidemono (3-mercaptopropionate) dimercaptoethanemono (sulfylate), hydroxyethylthiomethyl-tris (mercaptoethylthio) methane, etc. No.

Furthermore, a chlorine-substituted form of these active hydrogen compounds and a halogen-substituted form of bromine-substituted form may be used.
These may be used alone or in combination of two or more.

The usage ratio of these iso (thio) cyanate compounds and active hydrogen compounds is (NCO + NCS) /
The functional group molar ratio of (OH + SH) is usually in the range of 0.5 to 3.0, preferably in the range of 0.5 to 1.5.

As a method for molding the urethane resin, usually,
A template polymerization method and a reaction injection molding method are performed.

As a template polymerization method, for example, one or more sulfur-containing phosphoric acid esters are dissolved in a mixture of one or more polyisothiocyanate compounds and one or more active hydrogen compounds. After that, a defoaming operation is performed if necessary. Next, the mixture is poured into a mold, and the temperature is gradually raised in the range of -20 to 200 ° C, preferably room temperature to 150 ° C, more preferably 50 to 120 ° C, and the polymerization is carried out for 0.5 to 72 hours.

As a reaction injection molding method, for example, an active hydrogen compound in which a sulfur-containing phosphoric acid ester is dissolved and an isothiocyanate compound are separately charged into a high-pressure mixer tank, mixed with a high-pressure mixer under heating, and then mixed with a mold. Inject and mold inside.

The epoxy resin is a resin formed by polymerizing a raw material containing a monomer having an epoxy group, and is not particularly limited. Examples of the monomer having an epoxy group include the following.

(1) Amine type epoxy compound (Formula 4)

[0042]

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An epoxy compound having a group, for example,
Amino groups and amides such as N, N, N ', N'-tetraglycidylaminodiphenylmethane, meta-N, N-diglycidylaminophenylglycidyl ether, N, N, N', N'-tetraglycidylterephthalamide The compound is a compound synthesized from a compound having a group and an epihalohydrin such as epichlorohydrin, methyl epichlorohydrin, epibromohydrin and the like.

Specific examples of the compound having an amino group include diaminodiphenylmethane, metaxylylenediamine, paraxylylenediamine, metaaminobenzylamine, paraaminobenzylamine, 1,3-bisaminomethylcyclohexane, 1,4-bis Aminomethylcyclohexane, 1,3-diaminocyclohexane, 1,4-
Examples thereof include diaminocyclohexane, metaphenylenediamine, paraphenylenediamine, benzylamine, diaminodiphenylsulfone, diaminodiphenylether, diaminodiphenylsulfide, diaminodiphenylketone, naphthalenediamine, aniline, toluidine, metaaminophenol, paraaminophenol, and aminonaphthol.

Further, specific examples of the compound having an amide group include phthalamide, isophthalamide, terephthalamide, benzamide, toluamide, parahydroxybenzamide, metahydroxybenzamide and the like.

When the compound having an amino group or an amide group has a group other than the amino group or the amide group that reacts with an epihalohydrin such as a hydroxyl group, a carboxyl group, or a mercapto group, one of the groups that react with the epihalohydrin is included. Part or all may react with epihalohydrin and be substituted with an epoxy group.

(2) Phenolic epoxy compound This type of compound can be synthesized from a phenolic compound and epihalohydrin, such as bisphenol A diglycidyl ether and Epototo YDCN-220 (a product of Toto Kasei Co., Ltd.). .

Specific examples of the phenolic compound include hydroquinone, catechol, resorcin, bisphenol A, bisphenol F, bisphenol sulfone, brominated bisphenol A, novolak, cresol novolak, tetraphenylethane, triphenylethane and the like.

(3) Alcohol-based epoxy compound A compound that can be synthesized from an alcohol-based compound and epihalohydrin, such as trimethylolpropane triglycidyl ether and neopentyl glycol diglycidyl ether. Specific examples of alcohol compounds include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol,
Polypropylene glycol, 1,4-butanediol,
1,6-hexanediol, neopentyl glycol,
Dibromoneopentyl glycol, trimethylolpropane, glycerin, pentaerythritol, polycaprolactone, polytetramethylene ether glycol, polybutadiene glycol, hydrogenated bisphenol A, cyclohexane dimethanol, bisphenol A / ethylene oxide adduct, bisphenol A / propylene oxide adduct, etc. And polyester polyols made from these polyhydric alcohols and polycarboxylic acids.

(4) Epoxidized Unsaturated Compound Cyclopentadiene diepoxide, epoxidized soybean oil,
Epoxidized polybutadiene, vinylcyclohexene epoxide, trade name ERL-422 of Union Carbide
1, epoxidized unsaturated compounds known as ERL-4234, ERL-4299 and the like.

(5) Glycidyl ester epoxy compounds Compounds such as tetrahydrophthalic acid diglycidyl ester which can be synthesized from carboxylic acid and epihalohydrin.

Specific examples of the carboxylic acid include adipic acid, sebacic acid, dodecanedicarboxylic acid, dimer acid,
Phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, hexahydrophthalic acid, hexic acid, nadic acid, maleic acid, fumaric acid, trimellitic acid, benzenetetracarboxylic acid, butanetetracarboxylic acid, benzophenone Tetracarboxylic acid, 5- (2,5-dioxotetrahydrofuryl) -3
And polyvalent carboxylic acids such as -methyl-cyclohexene-1,2-dicarboxylic acid.

(6) Urethane epoxy compound The urethane epoxy compound can be synthesized from the polyhydric alcohol described in (3) and diisocyanate and glycidol or 3-hydroxypropylene sulfide.

Specific examples of diisocyanates include tolylene diisocyanate, diphenylmethane-4,4'-
Diisocyanate, hexamethylene diisocyanate,
Examples include isophorone diisocyanate, xylylene diisocyanate, and naphthalene diisocyanate.

(7) Alicyclic epoxy compound 3,4-epoxycyclohexyl-3,4-epoxycyclohexanecarboxylate, vinylcyclohexene dioxide, 2- (3,4-epoxycyclohexyl) -5,5-spiro-3 And alicyclic epoxy compounds such as 2,4-epoxy) cyclohexane-meta-dioxane and bis (3,4-epoxycyclohexyl) adipate.

(8) an epoxy compound having an unsaturated double bond: glycidyl methacrylate, glycidyl acrylate,
Allyl glycidyl ether, methacryl glycidyl ether, 4- (glycidyloxy) styrene, α-methyl-4- (glycidyloxy) styrene, 4-vinylbenzoic acid glycidyl ester, 4-isopropenyl benzoic acid glycidyl ester, 2,2′- Divinyl bisphenol A glycidyl ether, 2,2′-dipropenyl bisphenol A glycidyl ether, bis (2-vinyl benzoic acid glycidyl ester) methane, bis (2-propenyl benzoic acid glycidyl ester) methane, epoxy succinic acid diallyl ester, 3, 4-epoxymethacryloyloxytricyclo [5.2.1.0 ^2.6 ] decane and the like.

These epoxy compounds may be halogen-substituted compounds such as chlorine and bromine, and may be compounds in which an epoxy group is substituted with an episulfide group. Further, these epoxy compounds may be polymerized alone or in combination of two or more.

Further, the epoxy compound may be used together with known compounds such as alcohols, phenols, thiols, carboxylic acids, carboxylic anhydrides, amines, amides, sulfonic acids, isocyanates and the like which are generally classified as epoxy resin curing agents. It may be polymerized. Specific examples of these epoxy resin curing agents include, for example, alcohols such as ethylene glycol and trimethylolpropane; bisphenol A, tetrabromobisphenol A, bis (hydroxyethyl) sulfide, and bis- [4- (hydroxyethoxy) phenyl]. Phenols such as sulfides; thiols such as ethanedithiol, trithioglycerin, pentaerythritol tetrakis (thioglycolate) and bis (mercaptoethyl) sulfide; maleic acid, succinic acid, thiodiglycolic acid, 3,3′-thio Carboxylic acids such as dipropionic acid, phthalic acid, p-phenylenedithiodiglycolic acid; phthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, dodecylsuccinic anhydride, tetrabromophthalic anhydride, methylcyclopentadiene Carboxylic anhydrides such as adducts of ene and maleic anhydride; amines such as diethylenetriamine, triethylenetetraamine, metaphenylenediamine, diaminodiphenylamine, diaminodiphenylsulfone; fatty acids and fats such as fatty acids, dimer acid, and trimer acid Polyamides such as condensates with aromatic polyamines; sulfonic acids such as m-benzenedisulfonic acid and bis (4-sulfobenzene) disulfide; toluene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate And isocyanates such as isophorone diisocyanate; as a curing agent having two or more functional groups, 2-mercaptoethanol, thioglycolic acid, glycolic acid, 3- (hydroxysulfoxy) propionic acid, Aminobenzenesulfonic acid, 4-mercaptomethyl benzenesulfonic acid, 4-aminobenzene thiophenol, 2-mercaptoethylamine, and the like.

Further, salts of a complex of boron trifluoride and ethylamine, diazonium salts such as boron tetrafluoride and phosphorus hexafluoride, iodonium salts, bromonium salts and sulfinium salts are also included. These epoxy resin curing agents are 1
Species or two or more species may be used simultaneously.

When an epoxy compound having an unsaturated double bond is used as the epoxy compound, it may be copolymerized with a vinyl monomer such as acrylate, styrene, diallyl phthalate, diethylene glycol methacrylate, or diethylene glycol bisallyl carbonate.

When an epoxy resin curing agent is used,
The molar ratio of the reactive group of the curing agent to the functional group of the epoxy group of the epoxy compound is preferably in the range of 0.1 to 2.0.

The epoxy resin molding is usually carried out by mold polymerization, and the polymerization method includes a heat polymerization method and a photopolymerization method, and is appropriately selected depending on the type of the epoxy resin.

A general method of the heat polymerization method is to add a sulfur-containing phosphoric acid ester internal release agent and a polymerization catalyst to an epoxy monomer mixture, and inject the mixture into a mold obtained by combining a resin gasket and a metal or glass mold. 2-3 at 10-150 ° C
This is performed by heating for 0 hours.

As the polymerization catalyst in the heat polymerization method, known polymerization catalysts such as tertiary amines and salts thereof, quaternary ammonium salts, imidazoles, tin compounds, peroxides, metal salts of carboxylic acids, phosphines, tetraphenylboron salts and the like can be used. The catalyst is appropriately selected depending on the type of the epoxy resin.

In the case of the photopolymerization method, a known polymerization catalyst such as a sulfur-containing phosphoric acid ester internal release agent, peroxides, onium salts of Lewis acid anions, and silanol derivative aluminum chelate is added to the epoxy monomer mixture. A known additive such as an auxiliary agent and a sensitizer is added, and the mixture is injected into a mold obtained by combining a resin gasket and a glass mold, and irradiated with light of 180 to 700 nm for 0.5 to 15 minutes. In addition, known additives such as an ultraviolet absorber, an antioxidant, a dye, and a filler may be added as necessary in the template polymerization.

The polyolefin resin is a resin obtained by radical polymerization of a monomer having an unsaturated double bond, and examples of the monomer having an unsaturated double bond include the following. Aliphatic olefin compounds such as ethylene, propylene, and vinyl chloride; styrene, α-methylstyrene, p-methylthiostyrene, m-divinylbenzene, 3,3′-divinylbiphenyl, 2- (4-vinylbenzylthio) ethanol, iso- Propenylnaphthalene, 1,4-bis (4-vinylbenzylthio) benzene, 1,2-bis (4-vinylbenzylthio) ethane,
Aromatic vinyl compounds such as 2- (p-vinylphenylthio) benzothiazole and p-vinylbenzyl cinnamate; methyl acrylate, methyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, triphenylmethyl methacrylate, tribromophenyl methacrylate, isono Rubornyl methacrylate, 2-methacryloyloxymethylthiophene, 2-
Bicyclo [2.2.1] heptane methacrylate, ethylene glycol dimethacrylate, 2,2-bis- (4
-Methacryloxyphenyl) propane, 1,1,1-trimethylolpropane triacrylate, N, N ',
N "-isocyanuric triacrylate, bis (2-methacryloylthioethyl) sulfide, 2,5-di (methacryloyloxy) -1,4-dithiane, bis (acryloxymethyl) tricyclo [5.2.1.0 ^{2, 6} ] acrylate compounds such as decane, S-methylthiomethacrylate, 1,2-bis (methacryloylthio) ethane, bis (methacryloylthioethyl) sulfide, and 4,4′-dimercaptodiphenylsulfide dimethacrylate; acrylonitrile, methacryloyl Unsaturated nitrile compounds such as nitrile and cinnamonitrile; acrylamide compounds such as acrylamide and methacrylamide; allyl ester compounds such as diallyl phthalate, diallyl maleate, diallyl fumarate, allyl cinnamate and allyl benzoate Diallyl ether, bis (allyloxy) ethane, 2,2-bis (4-allyl-oxy) propane, 2,2-bis (4-allyl-oxy) propane, 1,4-bis (allylthio)
Allyl ether compounds such as benzene and dialylidenepentaerythritol; diethylene glycol bisallyl carbonate, β-thiodiglycol bisallyl carbonate, 2,2-bis [4- (2-allyloxycarbonyloxy) ethoxy-3,5-dibromo Allyl carbonate compounds such as [phenyl] propane; cyclohexylmaleimide, m-octylmaleimide, phenylmaleimide, chlorophenylmaleimide, N, N '-(4,4'
-Diphenylmethane) maleimide compounds such as bismaleimide, and these compounds having unsaturated double bonds may be polymerized singly or as a mixture of two or more. Usually, the thermoplastic polyolefin resin is molded by injection molding, and the thermosetting polyolefin resin is molded by mold polymerization.

The conditions for the template polymerization are appropriately selected depending on the monomers to be used. The sulfuric acid-containing phosphoric acid ester and the radical polymerization initiator are added to the raw material monomers, and if necessary, a degassing operation is carried out under reduced pressure. Radical polymerization by microwaves, infrared rays and ultraviolet rays. Examples of the radical polymerization initiator that can be used in polymerization by heat, microwaves, and infrared rays include 2,2′-azobisisobutyronitrile, 2,2′-azobisisovaleronitrile, and 2,2 ′
Azo compounds such as azobis (2,4-dimethylvaleronitrile); ketone peroxides such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide and acetylacetone peroxide; isobutyryl peroxide; Diacyl peroxides such as dichlorobenzoyl peroxide, o-methylbenzoyl peroxide, lauroyl peroxide, p-chlorobenzoyl peroxide;
Hydroperoxides such as 2,4,4-trimethylpentyl-2-hydroperoxide, diisopropylbenzene peroxide, cumene hydroperoxide, t-butyl peroxide; dicumyl peroxide, t-butylcumyl peroxide, Dialkyl peroxides such as -t-butyl peroxide and tris (t-butylperoxy) triazine; 1,1-di-t-butylperoxycyclohexane, 2,2-di (t-butylperoxy) butane and the like Peroxy ketals; t-butyl peroxypivalide, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxyisobutyrate, di-
t-butyl peroxyhexahydroterephthalate, di-t-butylperoxyazelate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxyacetate, t-butylperoxybenzoate, Alkyl peresters such as di-t-butyl peroxytrimethyl adipate; parker carbonates such as diisopropyl peroxy dicarbonate, di-sec-butyl peroxy dicarbonate and t-butyl peroxy isopropyl carbonate; Can be

Examples of the radical polymerization initiator that can be used in polymerization by ultraviolet rays include acetophenone,
2-dimethoxy-2-phenylacetophenone, 2,2
-Diethoxyacetophenone, 4'-isopropyl-2
-Hydroxy-2-methylpropiophenone, 2-hydroxy-2-methylpropiophenone, 4,4′-bis (diethylamino) benzophenone, benzophenone,
Methyl (o-benzoyl) benzoate, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o-benzoyl) oxime, benzoin , Benzoin methyl ether, benzoin ethyl ether,
Carbonyl compounds such as benzoin isopropyl ether, benzoin butyl ether, benzoin octyl ether, benzyl, benzyl dimethyl ketal, benzyl diethyl ketal, and diacetyl; methyl anthraquinone, chloroanthraquinone, chlorothioxanthone,
Anthraquinone or thioxanthone derivatives such as -methylthioxanthone, 2-isopropylthioxanthone;
Sulfur compounds such as diphenyl disulfide and dithiocarbamate are exemplified.

The amount of the radical polymerization initiator used is appropriately selected depending on the kind of the radical polymerization initiator, the kind of the raw material monomer and the like.
It is in the range of 10 mol%, preferably 0.1-3 mol%.

The amount of the radical polymerization initiator used is 0.001
When the amount is less than mol%, the polymerization does not substantially proceed, and when the amount exceeds 10 mol%, it is not economical, and in some cases, foaming occurs during the polymerization or the molecular weight of the cured product obtained by the polymerization becomes extremely small. Not preferred.

In the case of template polymerization, the monomer composition may be directly polymerized and cured, or depending on the purpose, may be preliminarily polymerized and then polymerized and cured to adjust the viscosity or reduce the shrinkage during polymerization. be able to.

When transparency is not particularly required, various fillers can be blended and used as necessary. Examples of the filler used here include powdered fillers such as silica, alumina, barium sulfate, and titanium oxide in addition to glass fiber, alumina fiber, carbon fiber, and aramid fiber. In addition, it goes without saying that flame retardants, dyes, pigments and the like can also be used.

The polymerization temperature and the polymerization time during the template polymerization cannot be unequivocally specified because they vary depending on the type of radical polymerization initiator used and the amount used, but the polymerization temperature is in the range of 0 to 150 ° C., preferably 20
To 120 ° C., and polymerization by heat is usually 10 to 3
It is carried out by gradually raising the temperature over a period of 0 hours, and in the case of ultraviolet rays, the polymerization can be completed by irradiation for 0.5 to 10 minutes.

Among the polyolefin resins, thermoplastic acrylic resin is shown as an example of injection molding. The homopolymer and copolymer of acrylic monomer, and the copolymer of acrylic monomer and other olefin monomer are shown. It may be united.

The acrylic monomers include, for example, the following. Examples of the acrylic acid compound include alkyl acrylates such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, bornyl acrylate, menthyl acrylate, adamantyl acrylate, and tricyclodecyl acrylate. Such as cycloalkyl acrylate, phenyl acrylate, benzyl acrylate, aromatic acrylate such as naphthyl acrylate, fluorophenyl acrylate, halogen-substituted acrylate acrylate such as chlorophenyl acrylate,
Fluoromethyl acrylate, chloroethyl acrylate,
Halogenated alkyl acrylates such as bromoethyl acrylate; hydroxyalkyl acrylates; S-thioacrylates such as S-methyl thioacrylate;
Alkyl esters and the like.

Examples of the methacrylic acid compound include methyl methacrylate, ethyl methacrylate, butyl methacrylate, alkyl methacrylate such as 2-ethylhexyl methacrylate, cyclohexyl methacrylate, bornyl methacrylate, menthyl methacrylate, adamantyl methacrylate, and methacrylic acid. Cycloalkyl methacrylates such as tricyclodecyl, phenyl methacrylate,
Aromatic esters of methacrylic acid such as benzyl methacrylate and naphthyl methacrylate; halogen-substituted aromatic esters of methacrylic acid such as fluorophenyl methacrylate and chlorophenyl methacrylate; fluoromethyl methacrylate; chloroethyl methacrylate; And thiomethacrylic acid S-alkyl esters such as hydroxyalkyl methacrylate, hydroxyalkyl methacrylate and S-methyl thiomethacrylate.

Examples of other olefin monomers include the following. Examples of the vinyl compound include aromatic vinyl compounds such as styrene, α-methylstyrene, α-ethylstyrene, fluorostyrene, chlorostyrene, bromostyrene, methylstyrene, and methylthiostyrene, and vinyl cyanide compounds such as acrylonitrile and methacrylonitrile. .

As unsaturated dibasic acids and derivatives thereof,
N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-octylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide and the like
-Substituted maleimides, dipropyl maleate, dibutyl maleate, dipropyl fumarate, dibutyl fumarate, maleic anhydride and the like.

As unsaturated fatty acids and their derivatives, there are acrylamides such as acrylamide and N, N-dimethylacrylamide.

The injection molding conditions are appropriately selected depending on the type of the resin. In general, the mixture of the acrylic resin and the sulfur-containing phosphoric ester is melted at a resin temperature of 220 to 320 ° C., and the mixture is melted at 50 to 150 ° C. by an extruder. It is injected into a mold and released after molding.

In the present invention, known additives such as antioxidants, ultraviolet absorbers, light stabilizers, coloring agents and fillers may be used according to the purpose.

The polyene-polythiol resin is a resin obtained by addition polymerization of a polyene compound having two or more unsaturated double bonds in a molecule and a polythiol compound having two or more mercapto groups in a molecule.

Examples of the polyene compound used for the polyene-polythiol resin include the following. aromatic vinyl compounds such as m-divinylbenzene, 3,3′-divinylbiphenyl, 1,4-bis (4-vinylbenzylthio) benzene, and 1,2-bis (4-vinylbenzylthio) ethane; Methacrylate, ethylene glycol diacrylate, 2,
2-bis- (4-methacryloxyphenyl) propane,
Bis (2-methacryloylthioethyl) sulfide,
Acrylic acid ester compounds such as 2,5-di (methacryloyloxy) -1,4-dithiane, 1,2-bis (acryloylthio) ethane, bis (4-methacryloylthiophenyl) sulfide, diallyl phthalate, diallyl maleate, Allyl ester compounds such as diallyl fumarate and allyl cinnamate, diallyl ether, diallyl sulfide, bis (allyloxy) ethane, 2,2
-Bis (4-allyloxyphenyl) propane, 2,2
-Bis (4-allyloxyethoxyphenyl) propane, 1,4-bis (allylthio) benzene, diarylidenepentaerythritol, diarylidene-2,2,6
Allyl ether compounds such as 6-tetramethylolcyclohexane, diethylene glycol bisallyl carbonate, β-thiodiglycol bisallyl carbonate,
2,2-bis [4- (allyloxycarbonyloxy)
Allyl carbonate compounds such as [phenyl] propane. These polyene compounds may be used alone or in combination of two or more.

Examples of the polythiol compound used for the polyene-polythiol resin include the following. 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, bicyclo [2.2.1] pepta-exo-cis-2,3-dithiol, 1,1-bis (mercaptomethyl ) Cyclohexane, bis (2-mercaptoethyl ester) thiomalate, 2,3-dimercaptosuccinic acid (2-mercaptoethyl ester), 2,3-dimercapto-1-propanol (2-mercaptoacetate), 2,3- Dimercapto-1-propanol (3-mercaptoacetate), diethylene glycol bis (2-mercaptoacetate), diethylene glycol bis (3-mercaptopropionate), 1,2-dimercaptopropyl methyl ether, 2,3-dimercaptopropylmethyl Ether, 2,2-bis (meth (Captomethyl) -1,3-propanedithiol, bis (2-mercaptoethyl) ether, ethylene glycol bis (2-mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), trimethylolpropanebis (2-mercaptoacetate) ), Trimethylolpropane bis (3
-Mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), 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 (mercaptoethylthio) ethane, 1,2-bis (mercaptopropylthio) 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, tetrakis (mercaptomethylthio) methane, tetrakis (2-mercaptoethylthiomethyl) methane, tetrakis (3-mercaptopropylthiomethyl) methane, bis (2,3-dimercaptopropyl) sulfide, 2, 5-dimercapto-1,4-dithiane, 2,5-bis (mercaptomethyl) -1,4-dithiane, bis (mercaptomethyl) disulfide, bis (mercaptoethyl) disulfide,
Bis (mercaptopropyl) disulfide and the like and esters of thioglycolic acid and mercaptopropionic acid, 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-mercapto Propionate), hydroxymethyl disulfide bis (2-mercaptoacetate), hydroxymethyl disulfide bis (3-mercaptopropionate), hydroxyethyl disulfide bis (2-
Mercaptoacetate), hydroxyethyldisulfidebis (3-mercaptopropionate), hydroxypropyldisulfidebis (2-mercaptoacetate), hydroxypropyldisulfidebis (3-mercaptopropionate), 2-mercaptoethyletherbis (2- Mercaptoacetate), 2-mercaptoethyl ether bis (3-mercaptopropionate), 1,4-dithiane-2,5-diolbis (2-
Mercaptoacetate), 1,4-dithiane-2,5-
Diol bis (3-mercaptopropionate), thioglycolic acid bis (2-mercaptoethyl ester),
Bis (2-mercaptoethyl ester) thiodipropionate, bis (2-mercaptoethyl ester) 4,4-thiodibutylate, bis (2-mercaptoethyl ester) dithiodiglycolate, bis (2-mercaptodithiodipropionate) Ethyl ester), bis (2-mercaptoethyl ester) 4,4-dithiodibutyrate, bis (2,3-dimercaptopropyl ester) thiodiglycolate, bis (2,3-dimercaptopropyl ester) thiodipropionate ), Bis (2,3-dimercaptopropyl ester) dithioglycolate, aliphatic polythiols such as bis (2,3-dimercaptopropyl ester) dithiodipropionate, 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 (mercaptoethyloxy) benzene, 1,2-bis (mercaptomethyleneoxy) benzene, 1,3-bis (mercaptomethyleneoxy) benzene, 1,4-bis (mercaptomethylene) Oxy) benzene, 1,2-bis (mercaptoethyleneoxy) benzene, 1,3-bis (mercaptoethyleneoxy) benzene, 1,4-bis (mercaptoethyleneoxy) benzene, 1,2,3-trimercaptobenzene, 1,2,4-trimercaptobenzene,
1,3,5-trimercaptobenzene, 1,2,3-tris (mercaptomethyl) benzene, 1,2,4-tris (mercaptomethyl) benzene, 1,3,5-tris (mercaptomethyl) benzene, 1,2,3-tris (mercaptoethyl) benzene, 1,2,4-tris (mercaptoethyl) benzene, 1,3,5-tris (mercaptoethyl) benzene, 1,2,3-tris (mercaptomethyleneoxy) Benzene, 1,2,4-
Tris (mercaptomethyleneoxy) benzene, 1,
3,5-tris (mercaptomethyleneoxy) benzene, 1,2,3-tris (mercaptoethyleneoxy)
Benzene, 1,2,4-tris (mercaptoethyleneoxy) benzene, 1,3,5-tris (mercaptoethyleneoxy) benzene, 1,2,3,4-tetramercaptobenzene, 1,2,3,5- Tetramercaptobenzene, 1,2,4,5-tetramercaptobenzene,
1,2,3,4-tetrakis (mercaptomethyl) benzene, 1,2,3,5-tetrakis (mercaptomethyl) benzene, 1,2,4,5-tetrakis (mercaptomethyl) benzene, 1,2,3 1,4-tetrakis (mercaptoethyl) benzene, 1,2,3,5-tetrakis (mercaptoethyl) benzene, 1,2,4,5-tetrakis (mercaptoethyl) benzene, 1,2,3
4-tetrakis (mercaptomethyleneoxy) benzene, 1,2,4,5-tetrakis (mercaptomethyleneoxy) benzene, 1,2,3,4-tetrakis (mercaptoethyleneoxy) benzene, 1,2,3,5- Tetrakis (mercaptoethyleneoxy) benzene, 1,
2,4,5-tetrakis (mercaptoethyleneoxy)
Benzene, 2,2′-dimercaptobiphenyl, 4,
4'-dimercaptobiphenyl, 4,4'-dimercaptobibenzyl, 2,5-toluenedithiol, 3,4-
Toluene dithiol, 1,4-naphthalenedithiol,
1,5-naphthalenedithiol, 2,6-naphthalenedithiol, 2,7-naphthalenedithiol, 2,4-dimethylbenzene-1,3-dithiol, 4,5-dimethylbenzene-1,3-dithiol, 9,10 -Anthracenedimethanethiol, 1,3-di (p-methoxyphenyl) propane-2,2-dithiol, 1,3-diphenylpropane-2,2-dithiol, phenylmethane-
1,1-dithiol, 2,4-di (p-mercaptophenyl) pentane, 1,2-bis (mercaptomethylthio) benzene, 1,3-bis (mercaptomethylthio)
Benzene, 1,4-bis (mercaptomethylthio) benzene, 1,2-bis (mercaptoethylthio) benzene, 1,3-bis (mercaptoethylthio) benzene,
1,4-bis (mercaptoethylthio) benzene, 1,
2,3-tris (mercaptomethylthio) benzene,
1,2,4-tris (mercaptomethylthio) benzene, 1,3,5-tris (mercaptomethylthio) benzene, 1,2,3-tris (mercaptoethylthio) benzene, 1,2,4-tris (mercaptoethyl) Thio)
Benzene, 1,3,5-tris (mercaptoethylthio) benzene, 1,2,3,4-tetrakis (mercaptomethylthio) benzene, 1,2,3,5-tetrakis (mercaptomethylthio) benzene, 1,2,2 4,5-
Tetrakis (mercaptomethylthio) benzene, 1,
2,3,4-tetrakis (mercaptoethylthio) benzene, 1,2,3,5-tetrakis (mercaptoethylthio) benzene, 1,2,4,5-tetrakis (mercaptoethylthio) benzene, and the like, and the like. Aromatic polythiols such as alkylated nuclei, 2-methylamino-4,
6-dithiol-sym-triazine, 2-ethylamino-4,6-dithiol-sym-triazine, 2-amino-4,6-dithiol-sym-triazine, 2-
Morpholino-4,6-dithiol-sym-triazine, 2-cyclohexylamino-4,6-dithiol-
sym-triazine, 2-methoxy-4,6-dithiol-sym-triazine, 2-phenoxy-4,6-dithiol-sym-triazine, 2-thiobenzeneoxy-4,6-dithiol-sym-triazine, 3, 4
-Heterocyclic polythiol compounds such as -thiophenedithiol, bismuthiol, and 2,5-dimercapto-1,3,4-thiadiazole. Further, these polythiol compounds may have a substituent such as a halogen group such as chlorine and bromine, a hydroxyl group, an amino group and the like. These polythiol compounds may be used alone or in combination of two or more.

The mixing ratio of the polyene compound and the polythiol compound is such that the molar ratio of the mercapto group to the functional group of the double bond is 0.1.
001-1.2, more preferably 0.01-1.
It is better to set the range to 0. When the proportion is more than 1.2, the hardness of the obtained resin is insufficient, and when the proportion is less than 0.001, the polyene-polythiol resin has sufficient physical properties such as high refractive index and low water absorption. It is not preferable because it is not exhibited.

For the purpose of adjusting the crosslinking density, a monoolefin compound such as methyl acrylate or styrene or a monothiol compound such as octyl mercaptan or dodecyl mercaptan may be added to a mixture of a polyene compound and a polythiol compound.

The conditions for the template polymerization are appropriately selected depending on the monomers to be used. The sulfur-containing phosphoric acid ester and the radical polymerization initiator are added to the starting monomers, and if necessary, a degassing operation is carried out under reduced pressure. It is radically polymerized by microwaves, infrared rays, ultraviolet rays and the like.

Examples of the radical polymerization initiator that can be used for polymerization by heat, microwaves, and infrared rays include, for example, 2,
2′-azobisisobutyronitrile, 2,2′-azobisisovaleronitrile, 2,2′-azobis (2,4-
Azo compounds such as dimethylvaleronitrile); ketone peroxides such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide and acetylacetone peroxide; isobutyryl peroxide, 2,4-dichlorobenzoyl peroxide, o- Diacyl peroxides such as methylbenzoyl peroxide, lauroyl peroxide, p-chlorobenzoyl peroxide; 2,4,4-trimethylpentyl-2-hydroperoxide, diisopropylbenzene peroxide, cumene hydroperoxide, t-
Hydroperoxides such as butyl peroxide; dicumyl peroxide, t-butylcumyl peroxide, di-
dialkyl peroxides such as t-butyl peroxide and tris (t-butylperoxy) triazine; 1,1
-Di-t-butylperoxycyclohexane, 2,2-
Peroxyketals such as di (t-butylperoxy) butane; t-butylperoxypivalide, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, di-t- Butylperoxyhexahydroterephthalate, di-t-butylperoxyazelate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxyacetate, t-butylperoxybenzoate, di- alkyl peresters such as t-butyl peroxytrimethyl adipate; diisopropyl peroxy dicarbonate;
Parker carbonates such as di-sec-butyl peroxy dicarbonate and t-butyl peroxy isopropyl carbonate are exemplified.

Examples of the radical polymerization initiator that can be used in polymerization by ultraviolet rays include acetophenone, 2,2
2-dimethoxy-2-phenylacetophenone, 2,2
-Diethoxyacetophenone, 4'-isopropyl-2
-Hydroxy-2-methylpropiophenone, 2-hydroxy-2-methylpropiophenone, 4,4′-bis (diethylamino) benzophenone, benzophenone,
Methyl (o-benzoyl) benzoate, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o-benzoyl) oxime, benzoin , Benzoin methyl ether, benzoin ethyl ether,
Carbonyl compounds such as benzoin isopropyl ether, benzoin butyl ether, benzoin octyl ether, benzyl, benzyl dimethyl ketal, benzyl diethyl ketal, and diacetyl; methyl anthraquinone, chloroanthraquinone, chlorothioxanthone,
Anthraquinone or thioxanthone derivatives such as -methylthioxanthone, 2-isopropylthioxanthone;
Sulfur compounds such as diphenyl disulfide and dithiocarbamate are exemplified.

The amount of the radical polymerization initiator used is appropriately selected depending on the kind of the radical polymerization initiator, the kind of the raw material monomer and the like.
It is in the range of 10 mol%, preferably 0.1-3 mol%. If the amount of the radical polymerization initiator is less than 0.001 mol%, the polymerization does not substantially proceed. It is not preferable because the molecular weight of the obtained cured product is significantly reduced.

In the case of template polymerization, the monomer composition may be directly polymerized and cured, or depending on the purpose, may be preliminarily polymerized and then polymerized and cured to adjust the viscosity or reduce the shrinkage during polymerization. be able to.

When transparency is not particularly required, various fillers can be blended and used as necessary. Examples of the filler used here include powdered fillers such as silica, alumina, barium sulfate, and titanium oxide in addition to glass fiber, alumina fiber, carbon fiber, and aramid fiber. In addition, it goes without saying that flame retardants, dyes, pigments and the like can also be used.

The polymerization temperature and the polymerization time during the template polymerization cannot be specified unequivocally because they vary depending on the type of radical polymerization initiator used and the amount used, but the polymerization temperature is in the range of 0 to 150 ° C., preferably 20
To 120 ° C., and polymerization by heat is usually 10 to 3
It is carried out by gradually raising the temperature over a period of 0 hours, and in the case of ultraviolet rays, the polymerization can be completed by irradiation for 0.5 to 10 minutes.

Polycarbonate resins include homopolymers and copolymers obtained by the reaction of a dihydric phenol with a carbonylating agent such as phosgene or diphenyl carbonate, and further branched or those having a long-chain alkyl group introduced into the terminal. Molecular weight 12,000-30,0
About 00.

Further, a modified polycarbonate resin obtained by using a bisphenol or vinylphenol having a carbon-carbon unsaturated double bond as a comonomer or a terminal stopper is obtained by grafting styrene or the like, and terephthalic acid is used as a part of phosgene. Any of those which use chloride and isophthalic acid chloride and partially have an ester bond, or those obtained by graft-polymerizing a polycarbonate resin to modified polystyrene into which a phenolic hydroxyl group or the like is introduced as a comonomer are exemplified. Also,
Reinforced resin composition composite-reinforced using glass fiber, carbon fiber, etc. in polycarbonate resin, ABS resin, polyester resin such as polyethylene terephthalate, PMM
The present invention is effectively used for a resin composition with A resin and the like.

Here, the dihydric phenols include 2,2
-Bis (4-hydroxyphenyl) propane, bis (4
-Hydroxyphenyl) methane, 1,2-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) -1-phenylmethane, , 1-bis (4-
(Hydroxyphenyl-1,1-diphenyl) methane,
1,1-bis (4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, and a lower alkyl group for these phenyl groups And those obtained by substituting a halogen atom. Further, in the present invention, known antioxidants, ultraviolet absorbers, coloring agents, fillers and the like may be added according to the purpose.

Examples of the polyester resin include a thermosetting polyester resin such as an alkyd resin and an unsaturated polyester resin, and a thermoplastic polyester resin represented by polyethylene terephthalate. Polyester resin is a resin formed by condensation of polybasic acid polyol,
Examples of the polybasic acid include phthalic anhydride, isophthalic acid, maleic acid, fumaric acid, sebacic acid, adipic acid, citric acid, tartaric acid, malic acid, diphenic acid, 1,8-naphthalylic acid, terephthalic acid and the like. . Examples of the polyol include glycerin, pentaerythritol, ethylene glycol, diethylene glycol, and trimethylolpropane. Further, known antioxidants, ultraviolet absorbers, coloring agents, fillers and the like may be added according to the purpose.

[0098]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples, but the present invention is not limited to only these Examples. Hereinafter, Examples 1 to 38 and Comparative Examples 1 to 7
The urethane resin of No. 6 is 70 mm in diameter and 9 mm in thickness by a mold.
Into a flat plate. The releasability was evaluated by placing a Teflon wedge between the molded product and the mold and easily releasing the mold, as follows: ○, when there was resistance but the mold was released, and when the mold could not be released, ×. In addition, the turbidity of the molded product was measured by Suga Test Machine Co., Ltd.
The haze (cloudiness value) of a 9 mm thick flat urethane resin was determined using a digital haze computer HGM-2DP manufactured by
It was measured according to 6.4 of ISK7105.

Examples 1 to 38 A mixture of a polyisocyanate compound, an active hydrogen compound and a sulfur-containing phosphoric acid ester shown in Table 1 (Tables 1 to 13) was poured into a glass mold. The temperature was gradually raised over time, and template polymerization was performed. The releasability after polymerization and the measured haze value of the urethane resin flat plate are shown in Table 1 (Tables 1 to 4).
13). In each case, the mold was easily released, and the haze of the urethane resin plate was small and good.

Comparative Examples 1 to 76 In the same manner as in Examples 1 to 38 except that a known internal release agent was used instead of the sulfur-containing phosphoric acid ester, and that no release agent was used, the same results were obtained. Table 1 (Table 1
To Table 13). Any known internal release agent for the sulfur-containing phosphate ester of the present invention is not easy to release,
The haze value of the urethane resin plate was also high. In addition, when no release agent was used, no release was possible, and the haze value could not be measured.

[0101]

[Table 1]

[0102]

[Table 2]

[0103]

[Table 3]

[0104]

[Table 4]

[0105]

[Table 5]

[0106]

[Table 6]

[0107]

[Table 7]

[0108]

[Table 8]

[0109]

[Table 9]

[0110]

[Table 10]

[0111]

[Table 11]

[0112]

[Table 12]

[0113]

[Table 13]

Example 39 A branched polyoxyalkylene ether polyol (OHV
28) To 100 parts, 0.1 part of triethylenediamine and 0.1 part of dibutyltin dilaurate were mixed as a polymerization catalyst, and 5 parts of diethyl thiophosphate was further added as an internal release agent to form a uniform solution. The amount of the urethane-modified diphenylmethane diisocyanate (isocyanate content: 23%) in the above solution was adjusted to an isocyanate index of 1
07, and formed into a flat plate having a diameter of 70 mm and a thickness of 9 mm in an aluminum mold by a reaction injection molding method. The release was easy, and the haze value of the obtained flat plate was as good as 0.4%.

Comparative Example 77 In Example 15, 2 parts of zinc stearate and 3 parts of N, N, N'-tris (2-hydroxypropyl) ethylenediamine were heated as an internal mold release agent to 90 to 100 ° C. to form a homogeneous solution. What was used was used. Demolding was easy, but the haze value of the obtained flat plate was as poor as 23.7%.

Examples 40 to 51 In the combinations of the epoxy compounds and various additives shown in Table 2 (Tables 14 to 17), a sulfur-containing phosphoric ester was mixed as an internal release agent, and then a resin gasket and a glass mold were mixed. Was poured into a mold and subjected to heat polymerization or photopolymerization to form a flat resin having a diameter of 70 mm and a thickness of 9 mm. The releasability was evaluated by placing a Teflon wedge between the molded product and the mold and easily releasing the mold, as follows: ○, when there was resistance but the mold was released, and when the mold could not be released, ×. The haze of the molded product was measured using a digital haze computer HGM-2DP manufactured by Suga Test Instruments Co., Ltd., and the haze (cloudiness value) of a flat epoxy resin having a thickness of 9 mm was measured according to JI SK7105.
And measured to one digit after the decimal point.
The results are shown in Table 2 (Tables 14 to 17).

COMPARATIVE EXAMPLES 78-101 The same procedure was carried out in the case of using the known monomer release agent instead of the sulfur-containing phosphoric acid ester in the raw material monomer combinations of the examples, and in the case where no release agent was used at all. The properties and haze values of the molded articles were measured. Table 2 shows the results.
17). Any of the known internal release agents for the sulfur-containing phosphoric acid ester of the present invention was not easy to release, and the haze value of the resin was high. In addition, when no release agent was used, no release was possible, and no haze value could be measured.

[0118]

[Table 14]

[0119]

[Table 15]

[0120]

[Table 16]

[0121]

[Table 17]

Examples 52 to 63 and Comparative Examples 102 to 12
5 Olefin monomer compositions shown in Table 3 (Tables 18 to 21) to which a sulfur-containing phosphoric ester was added as an internal release agent, those to which a known internal release agent was added, and that no release agent was used Each mold was polymerized in a mold composed of a resin gasket and a glass disk, and was 70 mm in diameter and 9 mm in thickness.
A flat molded product made of a polyene-polythiol resin having a thickness of 2 mm was prepared. The releasability was evaluated as ○ when a Teflon wedge was inserted between the molded product and the glass plate and easily released, and x when the mold had resistance to release. Also, the turbidity of the molded product was measured by Digital Haze Computer HG manufactured by Suga Test Instruments Co., Ltd.
Haze value (haze value) at a thickness of 9 mm using M-2DP
Was measured in accordance with 6.4 of JIS-K-7105, and calculated to one decimal place. The results are shown in Table 3 (Tables 18 to 2).
This is shown in 1).

[00123]

[Table 18]

[0124]

[Table 19]

[0125]

[Table 20]

[0126]

[Table 21]

Examples 64 to 74 and Comparative Examples 126 to 1
47 Use of acrylic resin composed of the monomer composition shown in Table 4 (Tables 22 to 25) to which sulfur-containing phosphoric acid ester is added as an internal release agent, to which a known internal release agent is added, or to an internal release agent Injection molding each for those not to be done, 70m in diameter
A flat plate having a thickness of 9 mm and a thickness of 9 mm was prepared. The releasability was evaluated as ○ when a wedge was inserted between the molded product and the mold to easily release the mold, and x when the mold had resistance to the release. The haze of the molded product was measured using a digital haze computer HGM-2DP manufactured by Suga Test Instruments Co., Ltd., and the haze value (cloudiness value) at a thickness of 9 mm was measured according to 6.4 of JIS-K-7105. Below, one digit was obtained. The results are shown in Table 4 (Table 2).
2 to 25).

[0128]

[Table 22]

[0129]

[Table 23]

[0130]

[Table 24]

[0131]

[Table 25]

Examples 75 to 84 and Comparative Examples 148 to 16
7 The raw material monomer compositions shown in Table 5 (Tables 26 to 29) to which sulfur-containing phosphoric acid esters were added as internal release agents, those to which known internal release agents were added, and that no release agents were used Each of them was subjected to mold polymerization in a mold in which a resin gasket and a glass disk were combined to prepare a flat molded product made of a polyene-polythiol resin having a diameter of 70 mm and a thickness of 9 mm. The releasability was evaluated as ○ when a Teflon wedge was inserted between the molded product and the glass plate and easily released, and x when the mold had resistance to release. In addition, the haze of the molded product was measured using a digital haze computer HGM-2 manufactured by Suga Test Instruments Co., Ltd.
Using DP, the haze value (haze value) at a thickness of 9 mm is determined by JI
The measurement was performed in accordance with 6.4 of SK-7105, and the value was calculated to one decimal place. The results are shown in Table 5 (Tables 26 to 29).

[0133]

[Table 26]

[0134]

[Table 27]

[0135]

[Table 28]

[0136]

[Table 29]

Examples 85 to 94 and Comparative Examples 168 to 1
73 2,2-bis (4-hydroxyphenyl) propane-type polycarbonate powder having an average molecular weight of 15,000 to which an internal release agent shown in Table 6 (Table 30) has been added, and a powder having no addition thereof at 250 ° C. After melting to a resin temperature of 270 ° C, 1
It was injected into a mold at 30 ° C. and formed into a flat plate having a diameter of 70 mm and a thickness of 9 mm. The releasability was evaluated as ○ when a wedge was inserted between the molds and easily released, and x when the mold was resistant to release. Optical distortion of molded products is measured by Toshiba Inspection Machine SVP-
The measurement was carried out according to 100, and those without distortion were evaluated as ○, and those with distortion were evaluated as ×. Furthermore, the haze of the molded product was measured using a digital haze computer HGM-2DP manufactured by Suga Test Instruments Co., Ltd., and the haze (cloudiness value) of a 9 mm-thick plate resin was measured according to JIS K
The measurement was performed according to 6.4 of 7105, and the value was calculated to one decimal place. The results are shown in Table 6 (Table 30).

[0138]

[Table 30]

[0139]

According to the molding method using the sulfur-containing phosphoric ester of the present invention as an internal mold release agent, the releasability between the resin and the mold is improved. And no contamination of the mold surface with resin. Further, in the molding of the transparent resin, the transparency is hardly impaired.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI G02B 1/04 G02B 1/04 // B29K 75:00 B29K 75:00 B29L 11:00 B29L 11:00 (31) Claim for priority No. Japanese Patent Application No. 4-26471 (32) Priority date February 13, 1992 (199.2.1.13) (33) Priority claiming country Japan (JP) (31) Priority claim number Japanese Patent Application No. 4-44532 (32) Priority date March 2, 1992 (1992.3.2) (33) Priority claiming country Japan (JP) (31) Priority claim number Japanese Patent Application No. 4-46661 (32) Priority date Heisei 4 March 4, 1992 (199.3.4) (33) Priority claiming country Japan (JP) (31) Priority claim number Japanese Patent Application No. 4-48277 (32) Priority date March 5, 1992 (1992) .3.5) (33) Priority country Japan (JP) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 18/00-18/87 B29C 39/02 B29C 45/00 C08K 5 / 5398 C 08L 1/00-101/16 G02B 1/04

Claims (15)

(57) [Claims] (1) Formula (1) (Formula 1) [Wherein, X and Y represent an oxygen atom or a sulfur atom,
At least one of X and Y is a sulfur atom, and R ₁ and R ₂
Represents an alkyl group. ] An internal mold release agent containing one or more sulfur-containing phosphoric acid esters selected from the group consisting of thiophosphate esters and dithiophosphate esters. 2. A resin molding method using the internal mold release agent according to claim 1. 3. The molding method according to claim 2, wherein the resin is a transparent resin. 4. The resin is a urethane resin, an epoxy resin, a polyolefin resin, a polyene-polythiol resin, an unsaturated polyester resin, a phenol resin, a furan resin, a xylene resin, a formaldehyde resin, a ketone resin, a urea resin, a melamine resin, an aniline resin, The molding method according to claim 2, which is a sulfonamide resin, an alkyd resin, a polycarbonate resin, a thermoplastic polyester resin, a polyether resin, a polyamide resin, a polyimide resin, a polyvinyl ketone resin, a polyvinyl ether resin, or a composite resin thereof. 5. A resin, wherein the resin is one or two or more iso (thio) cyanate compounds selected from the group consisting of a polyisocyanate compound, a polyisothiocyanate compound and an isothiocyanate compound having an isocyanate group, a polyol compound, and a polythiol. The molding method according to claim 2, wherein the molding method is a urethane resin obtained by polymerizing one or more active hydrogen compounds selected from the group consisting of a compound and a hydroxythiol compound. 6. A resin comprising an amine-based epoxy compound, a phenol-based epoxy compound, an alcohol-based epoxy compound,
Polymerization of one or more of epoxy compounds of unsaturated compounds, glycidyl ester epoxy compounds, urethane epoxy compounds, alicyclic epoxy compounds, and epoxy compounds having an epoxy group and an unsaturated double bond in the same molecule The molding method according to claim 2, which is an epoxy resin obtained by the above method. 7. An epoxy resin comprising an alcohol, a phenol, a thiol, a carboxylic acid, a carboxylic anhydride,
The molding method according to claim 6, wherein the resin is a resin using an epoxy resin curing agent selected from amines, amides, sulfonic acids, and isocyanates. 8. The resin is selected from the group consisting of aliphatic olefin compounds, aromatic vinyl compounds, acrylate compounds, unsaturated nitrile compounds, acrylamide compounds, allyl ester compounds, allyl ether compounds, allyl carbonate compounds, and maleimide compounds. The molding method according to claim 2, which is a polyolefin resin obtained by polymerizing one or more monomers having an unsaturated double bond. 9. The resin is selected from an aliphatic olefin compound, an aromatic vinyl compound, an acrylate compound, an allyl ether compound and an allyl carbonate compound, and a resin selected from an aliphatic polythiol, an aromatic polythiol and a heterocyclic polythiol. The molding method according to claim 2, which is a polyene-polythiol resin obtained by polymerizing a polythiol compound. 10. The molding method according to claim 2, wherein an internal release agent containing a sulfur-containing phosphoric ester in which R ₁ and R ₂ are C _{1 to} C ₁₈ alkyl groups is used. 11. The molding method according to claim 2, wherein the amount of the sulfur-containing phosphoric acid ester in the internal release agent is 0.01 to 5% by weight based on the total amount of the monomers or the resin. 12. A resin molded product obtained by the molding method according to claim 2. 13. The resin molded product according to claim 12, wherein the molded product is transparent. 14. The molded article is an optical product.
14. The resin molded product according to any one of 13. 15. The resin molded product according to claim 14, wherein the molded product is a plastic lens.