JPH0892345A - Production of thermosetting polyurethane resin-based molded article - Google Patents

Abstract

PURPOSE: To obtain the subject molded article having excellent face accuracy, transparency, moldability, etc., by reacting a specific isocyanate compound with an active hydrogen compound in a casting mold without using a mold release agent and readily releasing a molded article. CONSTITUTION: This molded article is obtained by reacting (A) a xylylene diisocyanate derivative of the formula (R1 to R4 are each a 1-3C lower alkyl) with (B) an active hydrogen compound in a casting mold without using a mold release agent by casting mold polymerization method or reaction injection molding method. The blending ratio of the component A and the component B is 0.5-3.0, preferably 0.5-1.5 as the molar ratio of functional group of (NCO)/(OH+SH+amino). For example, a prepolymer of α,α,α',α'-tetramethyl-m- xylylene diisocyanate and a polypropylene glycol is used as the component A and 4,4'-methylene-bis(2-chloroaniline) as the component B to give the objective molded article.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a thermosetting polyurethane resin-based molded article. More specifically, when a thermosetting polyurethane resin-based molded product is obtained by reacting an isocyanate compound and an active hydrogen compound in a template, by using a specific isocyanate compound, surface accuracy can be improved without using a release agent. , A method for easily producing a thermosetting polyurethane resin-based molded product having excellent transparency and moldability.

[0002]

2. Description of the Related Art Polyurethane resins are excellent in heat resistance, impact resistance, transparency, and moldability. Therefore, building materials, automobile materials typified by bumpers, heat insulating materials, optical materials utilizing transparency, etc. Widely used in.

Polyurethane resins are roughly classified into thermoplastic polyurethane resins composed of linear polymers and thermosetting polyurethane resins composed of three-dimensionally crosslinked polymers.
The thermosetting polyurethane resin of the present application is usually molded by a mold polymerization method or a reaction injection molding method.

The template polymerization method is, for example, after defoaming a mixture of one or more kinds of polyisocyanate compounds and one or more kinds of active hydrogen compounds, if necessary,
It is a method of injecting into a mold and heating to convert it into a polymer resin.

The reaction injection molding method is, for example, one kind or two or more kinds of polyisocyanate compounds and one kind or two or more kinds of active hydrogen compounds are charged into separate mixing tanks, and each is heated and kept warm. Defoam. Next, the two liquids are rapidly mixed, allowed to stand for several tens of seconds to several minutes, and then poured into a mold that has been heated and kept warm in the same manner to form a polymerized resin in a short time.

However, although this polyurethane resin has almost no adhesive force in the case of a thermoplastic resin, it has an extremely strong adhesive force so that it can be used as an adhesive in the case of a thermosetting resin. Therefore, generally in the production of thermosetting polyurethane resin using a metal or glass mold,
With a molding method that does not use a mold release agent, a resin cannot be separated from the mold to obtain a molded body. Also, if a mold made of polyolefin resin is used, a molded product can be obtained by releasing the mold without using a mold release agent, but the surface accuracy is poor, and as a method for manufacturing a molded product that requires high surface accuracy. Is not practical. Therefore, in the production of thermosetting polyurethane resin, it is usually essential to use a release agent.

[0007]

The release agent is roughly classified into an external release agent and an internal release agent. Since the external release agent needs to be applied to the inner surface of the mold each time it is molded, the operation is complicated and the productivity is poor, and the external release agent migrates to the surface of the molded product, causing unevenness, coating and There have been problems such as causing dyeing failure and causing the transparent molded product to become turbid due to the migration.

On the other hand, the internal release agent is a release agent added in advance to the resin raw material monomer. Since this internal release agent does not need to be applied to the mold every time, the productivity is dramatically improved as compared with the external release agent, but the point that it must be added in advance is still a little complicated, and further used. If the type and amount of the internal mold release agent is not appropriate, the same problems as the external mold release agent such as not releasing from the mold, conversely causing unevenness on the surface of the molded product, or causing turbidity in the transparent molded product was there. These problems are fatal particularly in the molding of optical products such as plastic lenses and optical discs, where surface accuracy and transparency are extremely important, and significantly reduce the commercial value. Therefore, even if such a release agent is not used, it has sufficient releasability, high surface accuracy, and in the case of a transparent molded product, high-quality polyurethane resin-based molding without any loss of transparency. It has been strongly desired to develop a manufacturing method capable of efficiently producing a body.

[0009]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have surprisingly found that a polyurethane resin-based molded product can be produced by using a specific isocyanate compound. , A molded product is easily released from the mold without using a mold release agent, and the resulting molded product is free from unevenness and turbidity, and is a high-quality thermosetting polyurethane resin-based molded product with extremely good surface accuracy. The inventors have found that they can be manufactured with high productivity and arrived at the present invention.

That is, the present invention provides the following general formula (1) (formula 2)

[Chemical 2] (Wherein R ₁ , R ₂ , R ₃ and R ₄ may be the same or different and each represents a lower alkyl group having 1 to 3 carbon atoms) and a xylylene diisocyanate derivative and an active hydrogen compound To obtain a molded body by reacting and in a mold without using a release agent, a method for producing a thermosetting polyurethane resin-based molded body, a polyurethane resin-based molded body obtained therefrom, a transparent polyurethane resin-based molded body, and It is a polyurethane resin plastic lens.

The thermosetting polyurethane resin-based molded product of the present invention comprises a polyisocyanate compound represented by the general formula (1) (formula 2), a hydroxy compound, a mercapto compound,
It is obtained by reacting in the template one or more active hydrogen compounds selected from a mercapto compound having a hydroxy group, an amine compound, an amine compound having a hydroxy group, and an amine compound having a mercapto group.

General formulas (1) and (2) used in the present invention
The specific polyisocyanate compound represented by is a xylylene diisocyanate derivative, specifically, α, α,
α ', α'-tetramethylxylylenediisocyanate, α, α, α', α'-tetraethylxylylenediisocyanate, α, α, α ', α'-tetra-n-propylxylylenediisocyanate, α , Α, α ', α'
-Tetraisopropyl xylylene diisocyanate,
α, α-dimethyl-α ′, α′-diisopropylxylylene diisocyanate, α-methyl-α-ethyl-α ′
Examples include -propyl-α'-isopropylxylylene diisocyanate. In addition, halogen substitution products such as chlorine substitution products and bromine substitution products, alkyl substitution products, alkoxy substitution products, nitro substitution products, prepolymer modification products with polyhydric alcohols, carbodiimide modification products, urea modification products, and burette modification products. Body, dimerization or trimerization reaction products and the like can also be used.

Examples of the hydroxy compound used as the raw material of the present invention include methanol, benzyl alcohol, phenol, ethoxyethanol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, neopentyl glycol, glycerin and trimethylol. Ethane, trimethylolpropane, butanetriol,
1,2-methylglucoside, pentaerythritol,
Dipentaerythritol, tripentaerythritol,
Sorbitol, erythritol, threitol, ribitol, arabinitol, xylitol, allitol, mannitol, dorsitol, iditol, glycol,
Inositol, hexanetriol, triglycerose, diglycerol, triethylene glycol, polyethylene glycol, tris (2-hydroxyethyl) isocyanurate, cyclobutanediol, cyclopentanediol, cyclohexanediol, cycloheptanediol, cyclooctanediol, cyclohexanedimethanol, Hydroxypropylcyclohexanol,
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 [5,5]
3,1,1] dodecanol, spiro [3,4] octanediol, butylcyclohexanediol, 1,1′-
Aliphatic polyols such as bicyclohexylidenediol, cyclohexanetriol, maltitol, lactitol, dihydroxynaphthalene, trihydroxynaphthalene, tetrahydroxynaphthalene, dihydroxybenzene, benzenetriol, biphenyltetraol, pyrogallol, (hydroxynaphthyl) pyrogallol, trihydroxy Phenanthrene, bisphenol A, bisphenol F, xylylene glycol, di (2-hydroxyethoxy) benzene, bisphenol A-bis (2
-Hydroxyethyl ether), tetrabromobisphenol A, tetrabromobisphenol A-bis (2-
(Hydroxyethyl ether) and other aromatic polyols, dibromoneopentyl glycol and other halogenated polyols, epoxy resin and other polymeric polyols, as well as oxalic acid, glutamic acid, adipic acid, acetic acid, propionic acid,
Cyclohexanecarboxylic acid, β-oxocyclohexanepropionic acid, dimer acid, phthalic acid, isophthalic acid,
Condensation reaction product of an organic acid such as salicylic acid, 3-bromopropionic acid, 2-bromoglycol, dicarboxycyclohexane, pyromellitic acid, butanetetracarboxylic acid, bromophthalic acid and the polyol, the polyol and ethylene oxide or propylene oxide. Addition reaction products with alkylene oxides, alkylene polyamines with ethylene oxide, addition reaction products with alkylene oxides such as 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-Hydroxycyclohexyloxy) phenyl] sulfide, bis [2-methyl-4- (hydroxyethoxy) -6-butylphenyl] sulfide and ethylene oxide and / or propylene oxide having an average of 3 molecules or less per hydroxyl group are added to these compounds. Compound, di- (2-hydroxyethyl) sulfide, 1,2
-Bis (2-hydroxyethylmercapto) ethane, bis (2-hydroxyethyl) disulfide, 1,4-dithian-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-)
Examples thereof include polyols containing a sulfur atom such as methylphenol) and 1,3-bis (2-hydroxyethylthioethyl) -cyclohexane.

Examples of the mercapto compound include methyl mercaptan, benzenethiol, benzylthiol, methanedithiol, 1,2-ethanedithiol, 1,1-propanedithiol, 1,2-propanedithiol, 1,3. -Propanedithiol, 2,2-propanedithiol, 1,6-hexanedithiol, 1,
2,3-Propanetrithiol, Tetrakis (mercaptomethyl) methane, 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] hepta-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-mercaptoethylthio) -3-mercaptopropane) and other aliphatic polythiols, 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 (mercapto) Ethyleneoxy) 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, 1,2,3,4-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′-dimercaptobiphenyl, 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-anthracene dimethanethiol, 1,3-di (p-methoxyphenyl) propane-2,2-dithiol, 1,3-diphenylpropane-2,2-dithiol, phenylmethane-1,1-dithiol, Aromatic polythiols such as 2,4-di (p-mercaptophenyl) pentane, 2,5-dichlorobenzene-1,3-dithiol, 1,3-di (p-chlorophenyl) propane-2,2-dithiol , 3,4,5-tribromo-1,
2-Dimercaptobenzene, 2,3,4,6-tetrachloro-1,5-bis (mercaptomethyl) benzene and other chlorine-substituted compounds, bromine-substituted and other halogen-substituted aromatic polythiols, and 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-sy
Polythiols containing a heterocycle such as m-triazine, 2-thiobenzeneoxy-4,6-dithiol-sym-triazine, and 2-thiobutyloxy-4,6-dithiol-sym-triazine, and 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 (mermercaptomethylthio) benzene, 1,2,4-tris (mermercaptomethylthio) benzene, 1,3,5-tris (mermercaptomethylthio) benzene, 1,2,3- Tris (mercaptoethylthio) benzene, 1,2,4-tris (mercaptoethylthio) benzene, 1,3,5-tris (mercaptoethylthio) benzene, 1,2,3,4
-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, etc., and aromatic polythiols containing a sulfur atom in addition to the mercapto group of these alkylated products, bis (mercaptomethyl) sulfide, bis (mercaptoethyl) sulfide, bis (mercaptopropyl) 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-bis (2-mercaptoethylthio) -3- Mercaptopropane, 2-mercaptoethylthio-1,3-propanedithiol, 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 Bis (mercaptomethyl) disulfide, bis (mercaptoethyl) disulfide, bis (mercaptopropyl) disulfide, etc., and their thioglycolic acid and mercaptopropionic acid esters, hydroxymethylsulfide bis (2-mercaptoacetate), hydroxymethylsulfide bis (3-
Mercaptopropionate), hydroxyethyl sulfide bis (2-mercaptoacetate), hydroxyethyl sulfide bis (3-mercaptopropionate), hydroxypropyl sulfide bis (2-mercaptoacetate), hydroxypropyl sulfide bis (3-mercaptopropionate) Pionate), hydroxymethyldisulfidebis (2-mercaptoacetate), hydroxymethyldisulfidebis (3-mercaptopropionate), hydroxyethyldisulfidebis (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-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), 4,4-thiodibutyric acid bis (2-mercaptoethyl ester), dithiodiglycolic acid bis (2-mercaptoethyl ester), dithiodipropionic acid bis (2-mercapto) Ethyl ester), 4,4-dithiodibutyric acid bis (2-mercaptoethyl ester), thiodiglycolic acid bis (2,3-dimercaptopropyl ester), thiodipropionic acid bis (2,3-dimercaptopropyl ester) ), Dithioglycolic acid bis (2,3-dimercaptopropyl ester), dithiodipropionic acid (2,3-dimercaptopropyl ester) and the like, an aliphatic polythiol containing a sulfur atom in addition to the mercapto group, 3,4- Thiophenedithiol, 2,5
-Dimercapto-1,3,4-thiadiazole, 2,5
Examples thereof include heterocyclic compounds containing a sulfur atom in addition to the mercapto group such as -dimercapto-1,4-dithiane and 2,5-dimercaptomethyl-1,4-dithiane.

Examples of the mercapto compound having a hydroxy group include 2-mercaptoethanol and 3
-Mercapto-1,2-propanediol, glycerin di (mercaptoacetate), 1-hydroxy-4-mercaptocyclohexane, 2,4-dimercaptophenol, 2-mercaptohydroquinone, 4-mercaptophenol, 1,3-dimercapto- 2-propanol, 2,3-dimercapto-1-propanol, 1,2
-Dimercapto-1,3-butanediol, pentaerythritol tris (3-mercaptopropionate),
Pentaerythritol mono (3-mercaptopropionate), pentaerythritol bis (3-mercaptopropionate), pentaerythritol tris (thioglycolate), pentaerythritol pentakis (3-
Mercaptopropionate), hydroxymethyl-tris (mercaptoethylthiomethyl) methane, 1-hydroxyethylthio-3-mercaptoethylthiobenzene,
4-hydroxy-4′-mercaptodiphenyl sulfone, 2- (2-mercaptoethylthio) ethanol, dihydroxyethyl sulfide mono (3-mercaptopropionate), dimercaptoethane mono (sulfylate), hydroxyethylthiomethyl-tris ( Examples thereof include mercaptoethylthio) methane.

Examples of the amine compound include methylamine, propylamine, butylamine, cyclohexylamine, hexamethylenediamine, isophoronediamine, diaminocyclohexane, xylylenediamine, bis (aminomethyl) cyclohexane, bis (aminocyclohexyl) methane, 2 , 2-bis (aminocyclohexyl) propane, bis (aminomethyl) norbornane,
Aliphatic amines such as bis (aminoethyl) sulfide, bis (aminoethyl) disulfide, aniline, diaminobenzene, diaminotoluene, bis (aminophenyl) methane, bis (aminophenyl) propane, bis (aminophenyl) sulfide, bis (Aminophenyl) sulfone, diaminodiethyltoluene, methoxydiaminobenzene, t-butoxydiaminotoluene,
7,8-Dihydro-6,6-dimethyl-1-methyl-
Examples include aromatic amines such as 2,4-diaminobenzocyclopentane.

Examples of the amine compound having a hydroxy group include hydroxyethylamine and aminophenol.

Examples of the amine compound having a mercapto group include cysteamine and aminothiophenol.

Further, a chlorine-substituted product or a bromine-substituted product of these active hydrogen compounds may be used.
These may be used alone or in combination of two or more.

The blending ratio of at least one isocyanate compound selected from the above xylylene diisocyanate derivative and at least one selected from the above active hydrogen compound is (NCO) / (OH + SH + amino group) The group molar ratio is usually within the range of 0.5 to 3.0, preferably within the range of 0.5 to 1.5.

The polyurethane resin-based molded product of the present invention is mainly composed of urethane bond, thiourethane bond, urea bond, but depending on the purpose, other than this, dithiourene bond, alohanate bond, thiourea bond, burette bond, etc. Of course, it does not matter if it is contained. For example, it is often preferable to react the urethane bond with an isocyanato compound and to react the thiourethane bond with an isothiocyanate compound to increase the crosslink density. In this case, the reaction temperature is raised to at least 100 ° C. or higher and a large amount of isocyanate component or isothiocyanate component is used. Alternatively, the urea bond can be further reacted with an isocyanate compound to utilize the biuret bond. When using a compound other than the above-mentioned active hydrogen compound that reacts with an isocyanate compound, it is necessary to pay particular attention to coloring.

Depending on the purpose, as in the known molding method, a chain extender, a crosslinking agent, a light stabilizer, an ultraviolet absorber,
Various substances such as antioxidants, oil-soluble dyes and fillers may be added. In order to adjust the reaction rate to a desired value, a known reaction catalyst used in the production of polyurethane can be appropriately added.

The thermosetting polyurethane resin-based molding of the present invention is usually obtained by cast polymerization or reaction injection molding. In the template polymerization method, specifically, an isocyanate compound represented by the formula (1) and an active hydrogen compound are mixed, and the mixed solution is defoamed by an appropriate method as needed, and then the mixture is placed in the template. Inject and usually
Polymerization is performed at room temperature to about 200 ° C. Specifically, the reaction injection molding method uses the formula (1)
The isocyanate compound and the active hydrogen compound represented by are charged into separate mixing tanks, and each is degassed while maintaining a temperature between room temperature and 200 ° C. Then, both liquids are rapidly degassed while degassing. After mixing for 10 minutes to several minutes, the mixture is poured into a mold that is kept at a temperature of about room temperature to 200 ° C. to be polymerized resin in a short time.

The thermosetting polyurethane resin-based molded product according to the present invention thus obtained is extremely excellent in impact resistance and heat resistance, has good dimensional stability of the molded product, good surface accuracy, and dyeability. Since it has excellent characteristics such as workability, it is suitable as a material for building materials, automobile materials, heat insulating materials, general plastic materials, optical element materials such as plastic lenses and camera lenses, and glazing materials.

Further, the optical lens made of the thermosetting polyurethane resin according to the present invention may be used as necessary to prevent reflection, impart high hardness, improve abrasion resistance, improve chemical resistance, provide anti-fog property, or In order to improve fashionability and the like, physical or chemical treatments such as surface polishing, antistatic treatment, hard coat treatment, antireflection coat treatment, dyeing treatment, and light control treatment can be performed.

[0026]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples. In the performance test of the obtained optical lens, the refractive index, Abbe number and heat resistance were evaluated by the following test methods.

Refractive index, Abbe number: Measured at 20 ° C. using a Bruchrich refractometer. Heat resistance: Tg point was measured by TMA method.

Example 1 α, α, α ′, α′-tetramethyl-m-xylylene diisocyanate (hereinafter abbreviated as TMXDi) (molecular weight =
244.3) 100 parts (0.409 mol) and polypropylene glycol having an average molecular weight of 300 (PPG300) 7
170 parts of prepolymer A (NCO = 8.7% by weight, isocyanate equivalent = 483) in which 0 part (0.233 mol) had been preliminarily reacted was charged into a reactor and mixed with 8 parts.
Defoaming was performed under reduced pressure at 0 ° C. (5 to 10 mmHg) for 1 hour. Next, 23.5 parts (0.04) of 4,4'-methylenebis (2-chloroaniline) (melting point 104 ° C, molecular weight = 267.2) whose defoaming was completed at 110 ° C in another mixer in the same manner.
88 mol) was rapidly added to the reactor containing the prepolymer A, and the mixture was stirred under reduced pressure (5 to 10 mmHg) for 3 minutes and allowed to stand for 20 seconds, after which the external release agent (silicone DC-2
0, made by Daw Corning) 120 ° C. without applying
It was poured into a stainless steel mold preheated to, held for 15 minutes, and then cooled to room temperature. As a result, the resin molded product was easily released from the mold, and the obtained resin molded product had no surface unevenness, and was a resin molded product having extremely high surface accuracy.

Example 2 With the mold of Example 1, the same test as in Example 1 was repeated 10 times. As a result, the mold releasability did not change until the end, and the resin molded body could be easily taken out. No abnormality was found in the ten resin molded bodies and the molds thus obtained.

Example 3 TMXDi without adding an internal mold release agent (acidic phosphate ester)
58.4 parts (0.239 mol), 1,2-bis (2-mercaptoethylthio) -3-propanethiol 41.6
Parts (0.160 mol) and dibutyltin dichloride 0.5
Parts (0.5% by weight) were mixed and dissolved, degassed under reduced pressure at room temperature for 1 hour, and then poured into a mold composed of a glass plate and a resin gasket. Then, the mold was gradually heated and polymerized from room temperature to 120 ° C. over 20 hours, and then cooled to room temperature. As a result, the resin molded body was easily released from the mold, and the obtained resin molded body was colorless and transparent,
There was no unevenness in the surface, the surface precision was extremely high, and the resin molded product was excellent as an optical plastic lens. The physical properties of this resin are 1.62 (nd) for refractive index and 3 for Abbe number.
The heat resistance was 3 (νd), the specific gravity was 1.25, and the heat resistance was 100 ° C.

Comparative Example 1 The test of Example 1 was conducted using m-xylylene diisocyanate (hereinafter abbreviated as XDi) instead of TMXDi. As a result, the resin was not released from the mold and a molded body could not be obtained.

Comparative Example 2 External mold release agent (Silicone DC-20, Daw Corn
ing) was applied to the mold and the test of Comparative Example 1 was performed. As a result, the resin was released from the mold to obtain a molded body,
There was some unevenness on the surface, and it could not be said to be a high quality molded product.

Comparative Example 3 The test of Example 3 was conducted using XDi instead of TMXDi. As a result, the resin was not released from the mold to obtain a molded body.

[0034]

According to the method of the present invention, as is clear from the examples and comparative examples, it is possible to obtain a polyurethane resin-based molding and a plastic lens which have good transparency and surface accuracy and are free from unevenness due to polymerization. It is possible to simplify the process of manufacturing the resin-based molded product and the plastic lens.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Teruyuki Nagata 30 Asamuta-cho, Omuta-shi, Fukuoka Mitsui Toatsu Chemical Co., Ltd.

Claims (4)

[Claims] 1. The following general formula (1) (Chemical formula 1) (Wherein R ₁ , R ₂ , R ₃ and R ₄ may be the same or different and each represents a lower alkyl group having 1 to 3 carbon atoms) and a xylylene diisocyanate derivative and an active hydrogen compound A method for producing a thermosetting polyurethane resin-based molded product, wherein a molded product is obtained by reacting and in a mold without using a release agent. 2. A thermosetting polyurethane resin-based molded product obtained by the manufacturing method according to claim 1. 3. A thermosetting transparent polyurethane resin-based molding obtained by the manufacturing method according to claim 1. 4. A thermosetting polyurethane resin-based plastic lens obtained according to claim 3.