JP3483828B2 - Manufacturing method of plastic lens and plastic lens - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a plastic lens, a method for using a plastic lens and a neutralization type phosphoric acid ester, and more particularly, a plastic lens and a neutralization having good surface accuracy, transparency and hardness. The present invention relates to a method of using a phosphoric acid ester.

[0002]

2. Description of the Related Art In recent years, the demand for plastic lenses has increased because they are lighter than glass lenses, less likely to break, and have excellent dyeability. A plastic lens is manufactured by injecting a raw material monomer for a plastic lens into a lens mold, polymerizing the same, and taking out from the mold. Also, to make it easier to remove from the mold during manufacturing,
It is known to use an internal release agent such as an acidic phosphate ester. For example, in JP-A-64-45611 and JP-A-1-303302, when a polythiourethane lens containing a polyisocyanate compound and a polythiol compound is produced, diisopropyl acid phosphate and dibutyl acid are used. It has been disclosed to use certain internal mold release agents such as acid phosphates such as phosphates, diethyl acid phosphates, butyl acid phosphates and the like. However, when the internal mold release agents disclosed in these publications are used, a cloudy lens is likely to be obtained, and sufficient curing may not be obtained in some cases. In particular, when used in a lens made of a compound having an epithio group, a polyisocyanate compound, or a polythiol compound as a raw material, the lens surface is not transferred like a lens type, and it is difficult to have good transparency and hardness. there were.

[0003]

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and is a method for producing a plastic lens having good surface accuracy, transparency, and hardness, a plastic lens, and a neutralization type phosphorus. It is to provide a method of using an acid ester.

[0004]

DISCLOSURE OF THE INVENTION As a result of intensive studies to develop a plastic lens having the above-mentioned preferable properties, the present inventors have found that a neutralization type compound composed of a compound having a specific structure as an internal release agent. By using a phosphoric acid ester, it found out that the objective was achieved and came to complete the present invention. That is, the present invention is based on the following general formula (I)

[Chemical 4] (In the formula, R is an alkylene group having 1 to 12 carbon atoms, R '
Is an alkyl group having 1 to 20 carbon atoms , n is 1 to 15, m
Indicates 1 to 2. ) The first step of preparing a mixed solution by adding a neutralized phosphoric acid ester represented by
The method is characterized by comprising a second step of injecting the mixed solution into a plastic lens mold and then polymerizing it to obtain a polymer, and a third step of releasing the polymer from the plastic lens mold to obtain a plastic lens. A method for manufacturing a plastic lens is provided. Further, a plastic lens containing a polymer of a raw material monomer for a plastic lens and a neutralized phosphoric acid ester represented by the general formula (I), and a neutralized phosphoric acid represented by the above formula (I) Also provided is a method of using an ester as an internal mold release agent for producing a plastic lens.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The raw material monomer for a plastic lens used in the present invention is not particularly limited, and a raw material monomer for an acrylic resin lens, a raw material monomer for a lens using diethylene glycol bisallyl carbonate as a raw material, Examples thereof include raw material monomers for sulfur atom-containing resin lenses, raw material monomers for halogen atom-containing resin lenses, raw material monomers for polyurethane resin lenses, and raw material monomers for polyurethane resin lenses. Among them, a polyisocyanate compound, which is a raw material monomer for polyurethane lenses, and a mixed monomer of an active hydrogen compound such as polythiol, polyol and polyamine, and one of the raw material monomers for sulfur atom-containing resin lenses. A compound having a certain epithio group, a polyisocyanate compound, and a polythio-
And a mixed monomer with an active hydrogen compound such as polyol, polyamine and polyamine. The active hydrogen compound is preferably a polyamine compound or a polythiol compound.

The monomer of the polyisocyanate compound is not particularly limited, and examples thereof include hydrogenated 2,6-tolylene diisocyanate, hydrogenated meta and paraphenylene diisocyanate, and hydrogenated 2,4-tolylene diisocyanate. Aliphatic isocyanate compounds such as nato, hydrogenated diphenylmethane diisocyanate, hydrogenated metaxylylene diisocyanate, hydrogenated paraxylylene diisocyanate, isophorone diisocyanate, meta and paraphenylene diisocyanate, 2,6- Tolylene diisocyanate,
2,4-Tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, meta and para-xylylene diisocyanate, meta and para-tetramethyl xylylene diisocyanate, 2,6-naphthalene diisocyanate, 1,5- Naphthalene diisocyanate and the like can be mentioned, and preferred ones are 2,4- and 2,6-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, metaxylylene diisocyanate, metatetramethylxylylene diisocyanate. An isocyanate compound having an aromatic ring such as 2,6-naphthalene diisocyanate. Furthermore, hexamethylene diisocyanate, octamethylene diisocyanate, 2,2,4
-Trimethylhexamethylene diisocyanate, tetramethylene diisocyanate, Buremet reaction product of hexamethylene diisocyanate, hexamethylene diisocyanate trimer, 1,3- (diisocyanatomethyl) cyclohexane, lysine diisocyanate Aliphatic and aromatic ring-free isocyanate compounds such as nato, lysine triisocyanate, 1,6,11-undecane triisocyanate, and triphenylmethane triisocyanate, diphenyl disulfide-4,4′-diisocyanate Nato, 2,2'-dimethyldiphenyldisulfide-
5,5'-diisocyanate, 3,3'-dimethyldiphenyldisulfide-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, diphenylsulfone-4,4'-diisocyanate, diphenylsulfone-3,3 ' -Diisocyanate, benzylidene sulfone-4,4'-diisocyanate, diphenylmethane sulfone-4,4'-diisocyanate, 4-methyldiphenylmethane sulfone-2,4'-diisocyanate,
4,4'-dimethoxydiphenyl sulfone-3,3'-
Diisocyanate, 3,3'-dimethoxy-4,4'-
Diisocyanato dibenzyl sulfone, 4,4′-dimethyldiphenyl sulfone-3,3′-diisocyanate,
4,4'-di-tert-butyldiphenylsulfone-
3,3′-diisocyanate, 4,4′-dimethoxybenzeneethylenedisulfone-3,3′-diisocyanate, 4,4′-dichlorodiphenylsulfone-3,3 ′
-Diisocyanate, 4-methyl-3-isocyanatobenzenesulfonyl-4'-isocyanatophenol ester, 4-methoxy-3-isocyanatobenzenesulfonyl-4'-isocyanatophenol ester, 4-methyl-3-isocyanate Natobenzenesulfonylanilide-
3'-methyl-4'-isocyanate, dibenzenesulfonyl-ethylenediamine-4,4'-diisocyanate, 4,4'-dimethoxybenzenesulfonyl-ethylenediamine-3,3'-diisocyanate, 4-methyl- 3-isocyanatobenzenesulfonylanilide-4-
Methyl-3'-isocyanate, thiophene-2,5-
Diisocyanate, thiophene-2,5-diisocyanatomethyl, 1,4-dithiane-2,5-diisocyanate, 1,4-dithiane-2,5-diisocyanatomethyl, 1,4-dithiane- 2,3-Diisocyanatomethyl, 1,4-dithian-2-isocyanatomethyl-5-
Isocyanatopropyl, 1,3-dithiolane-4,5-
Diisocyanate, 1,3-dithiolane-4,5-diisocyanatomethyl, 1,3-dithiolane-2-methyl-
4,5-diisocyanatomethyl, 1,3-dithiolane-
2,2-Diisocyanatoethyl, tetrahydrothiophene-2,5-diisocyanate, tetrahydrothiophene-2,5-diisocyanatomethyl, tetrahydrothiophene-2,5-diisocyanatoethyl, tetrahydrothiophene-3,4 -Sulfur-containing isocyanate compounds such as diisocyanatomethyl. These compounds may be used alone or in combination of two or more.

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, 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, 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-mercapto) Acetate), trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3
-Mercaptopropionate), 1,2-bis (2-mercaptoethylthio) -3-mercaptopropane and other aliphatic thiols, 1,2-dimercaptobenzene, 1,3
-Dimercaptobenzene, 1,4-dimercaptobenzene, 1,2-bis (mercaptomethyl) benzene, 1,
3-bis (mercaptomethyl) benzene, 1,4-bis (mercaptomethyl) benzene, 1,3-bis (mercaptoethyl) benzene, 1,4-bis (mercaptoethyl) benzene, 1,2-bis (mercaptomethoxy) ) Benzene, 1,3-bis (mercaptomethoxy) benzene, 1,4-bis (mercaptomethoxy) benzene,
1,2-bis (mercaptoethoxy) benzene, 1,3
-Bis (mercaptoethoxy) benzene, 1,4-bis (mercaptoethoxy) 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, 1,3,3 5-tris (mercaptoethyl) benzene, 1,2,3-tris (mercaptomethoxy) benzene, 1,2,4-tris (mercaptomethoxy) benzene, 1,3,5-tris (mercaptomethoxy) benzene, 1, 2,3-tris (mercaptoethoxy) benzene, 1,2,4-tris (mercaptoethoxy) benzene, 1,3,5-tris (mercaptoethoxy) benzene, 1,2,3,4-tetramercaptobenzene, 1 , 2,3,5-tetramercaptobenzene, 1,2,4,5-tetramercaptobenzene, 1,2,3 -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 (mercaptomethoxy) benzene, 1,2,4,5-tetrakis (mercaptomethoxy) benzene, 1,2,3,4 -Tetrakis (mercaptoethoxy) benzene, 1,2,3,5-tetrakis (mercaptoethoxy) benzene, 1,2,
4,5-tetrakis (mercaptoethoxy) 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- Aromatic thiols such as methoxyphenyl) propane-2,2-dithiol, 1,3-diphenylpropane-2,2-dithiol, phenylmethane-1,1-dithiol, 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)
Chlorine substitution products such as benzene, halogen substitution aromatic thiols such as bromine substitution products, 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, 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. Aromatic thiol containing sulfur atom in addition to mercapto group such as nuclear alkylated product, 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, mercaptopropionic acid esters, hydroxymethylsulfide bis (2-mercaptoacetate), hydroxy Methyl sulfide bis (3-mercaptopropionate), hydroxyethyl sulfide bis (2-mercaptoacetate), hydroxyethyl sulfide bis (3-mercaptopropionate), hydroxypropyl sulfide bis (2-mercaptoacetate), hydroxypropyl sulfide Bis (3-mercaptopropionate), hydroxymethyldisulfide bis (2-mercaptoacetate), hydroxymethyldisulfide bis (3- Mercaptoethyloleates propionate),
Hydroxyethyl disulfide bis (2-mercaptoacetate), hydroxyethyl disulfide bis (3-
Mercaptopropionate), hydroxypropyl disulfide bis (2-mercaptoacetate), hydroxypropyl disulfide bis (3-mercaptopropionate), 2-mercaptoethyl ether bis (2-mercaptoacetate), 2-mercaptoethyl ether bis ( 3-mercaptopropionate), 1,4-dithian-2,5-diolbis (2-mercaptoacetate), 1,4-dithian-2,5-diolbis (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-mercaptoethyl ester), 4,4′-dithiodibutyric acid bis (2-mercapto) Ethyl ester), thiodiglycolic acid bis (2,3-dimercaptopropyl ester),
Thiodipropionic acid bis (2,3-dimercaptopropyl ester), dithiodiglycolic acid bis (2,3-dimercaptopropyl ester), dithiodipropionic acid (2,3-dimercaptopropyl ester), 4-mercapto Methyl-3,6-dithiaoctane-1,8-dithiol, bis (mercaptomethyl) -3,6,9-trithia-1,11-undecanedithiol, bis (1,3
An aliphatic thiol containing a sulfur atom in addition to a mercapto group such as -dimercapto-2-propyl) sulfide;
4-thiophenedithiol, tetrahydrothiophene-
2,5-dimercaptomethyl, 2,5-dimercapto-
1,3,4-thiadiazole, 2,5-dimercapto-
1,4-dithiane, 2,5-dimercaptomethyl-1,
Heterocyclic compounds containing a sulfur atom in addition to the mercapto group such as 4-dithiane and the like can be mentioned. These compounds 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, pentaerythritol, dipentaerythritol, tripentaerythritol , Triethylene glycol, polyethylene glycol, tris (2-hydroxyethyl) isocyanurate, cyclobutanediol, cyclopentanediol,
Cyclohexanediol, cycloheptanediol, cyclooctanediol, bicyclo [4,3,0] -nonanediol, dicyclohexanediol, tricyclo [5,3,1,1] dodecanediol, spiro [3,3]
4] Aliphatic polyols such as octanediol and butylcyclohexanediol, dihydroxynaphthalene, trihydroxynaphthalene, tetrahydroxynaphthalene,
Aromatic polyols such as dihydroxybenzene, benzenetriol, trihydroxyphenanthrene, bisphenol A, bisphenol F, xylylene glycol and tetrabromobisphenol A, and addition reaction products of them with alkylene oxides such as ethylene oxide and propylene oxide, 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]
Sulfides, and compounds in which an average of 3 or less molecules of ethylene oxide and / or propylene oxide per hydroxyl group are added to these compounds, 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-methylphenol), 1,3-
Examples thereof include polyols containing a sulfur atom such as bis (2-hydroxyethylthioethyl) -cyclohexane. These compounds may be used alone or in combination of two or more.

Examples of the polyamine compound include:
Ethylenediamine, diaminopropane, diaminobutane, diaminopentane, bisaminocyclohexane, bisaminomethylcyclohexane, 4,4'-diamino-
3,3'-Dimethyldicyclohexylmethane, 4,4 '
-Diamino-3,3'-dimethyldicyclohexyl,
4,4'-diamino-3,3'-dimethyldicyclohexyl sulfide, 4,4'-diamino-3,3 ', 5
5'-tetramethyldicyclohexylmethane, 4,4 '
-Diamino-3,3 ', 5,5'-tetramethyldicyclohexyl and the like. These compounds may be used alone or in combination of two or more.

The compound having an epithio group is
Any known one may be used, for example, Japanese Patent Laid-Open No. 09-0715.
No. 80, No. 09-110979, No. 09-255781, No. 03-081320.
JP-A-11-140070, JP-A-11-140070
183702, JP 11-189592, JP 11-180977, and JP 01-8.
No. 10575, etc. In particular,
1,3 and 1,4-bis (β-epithiopropylthio)
Cyclohexane, 1,3 and 1,4-bis (β-epithiopropylthiomethyl) cyclohexane, bis [4-
(Β-Epithiopropylthio) cyclohexyl] methane, 2,2 bis [4- (β-epithiopropylthio)
Episulfide compounds having an alicyclic skeleton such as cyclohexyl] propane, bis (β-epithiopropyl) sulfide, and bis [4- (β-epithiopropylthio) cyclohexyl] sulfide, 1,3 and 1,4-bis ( β
-Epithiopropylthio) benzene, 1,3 and 1,4
-Bis (β-epithiopropylthiomethyl) benzene,
Bis [4- (β-epithiopropylthio) phenyl] methane, 2,2-bis [4- (β-epithiopropylthio) phenyl] propane, bis [4- (β-epithiopropylthio) phenyl] Sulfide, bis [4- (β-
Epithiopropylthio) phenyl] sulfine, 4,4
-Episulfide compounds having an aromatic skeleton such as bis (β-epithiopropylthio) biphenyl, 2,5-bis (β-epithiopropylthiomethyl) -1,4-dithiane, 2,5-bis (β- Epithiopropylthioethylthiomethyl) -1,4-dithiane, 2,5-bis (β-epithiopropylthioethyl) -1,4-dithiane, 2,
3,5-tri (β-epithiopropylthioethyl)-
Episulfide compounds having a dithian ring skeleton such as 1,4-dithiane, 2- (2-β-epithiopropylthioethylthio) -1,3-bis (β-epithiopropylthio) propane, 1,2-bis [(2-β-Epithiopropylthioethyl) thio] -3- (β-epithiopropylthio) propane, tetrakis (β-epithiopropylthiomethyl) methane, 1,1,1-tris (β-epi Examples thereof include episulfide compounds having an aliphatic skeleton such as thiopropylthiomethyl) propane and bis- (β-epithiopropyl) sulfide. Particularly, bis (β-epithiopropyl) sulfide is preferable. These compounds may be used alone or in combination of two or more.

The internal release agent used in the present invention is represented by the following general formula (I).

[Chemical 5] (In the formula, R is an alkylene group having 1 to 12 carbon atoms, R '
Is an alkyl group having 1 to 20 carbon atoms or 7 to
26 alkylhydroxyphenyl groups, n is 1 to 15,
m shows 1-2. It is important that the phosphoric acid ester is a neutralized phosphoric acid ester. R in the general formula (I)
Examples thereof include alkylene groups such as methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group and octylene group. Further, R ′ is a methyl group, an ethyl group, a propyl group,
A butyl group, a pentyl group, a hexyl group, a heptyl group, an alkyl group such as an octyl group, and a phenol group having a hydroxyl group at the 2-, 3- or 4-position, which is different from the hydroxyl group.
Methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group at the-, 3- or 4-position,
Examples thereof include an alkylhydroxyphenyl group having an alkyl group such as an octyl group. These compounds may be used alone or in combination of two or more. The above general formula (I)
Examples of the neutralized phosphoric acid ester represented by
Is an alkylene group having 2 carbon atoms, and R'is 6 to 6 carbon atoms.
Examples thereof include 15 alkyl groups and neutralized phosphoric acid esters having an ethylene oxide number n of 6 to 10. By using the neutralized phosphoric acid ester represented by the general formula (I) as an internal mold release agent, it is possible to obtain a lens having not only excellent mold releasability but also good surface accuracy, transparency and hardness. You can

The amount of the internal release agent made of the neutralized phosphoric acid ester to be added is not particularly limited, but it is preferable to add 10 to 10,000 ppm to the raw material monomer of the plastic lens.

When producing a plastic lens by the method of the present invention, auxiliary agents such as an ultraviolet absorber, an antioxidant, a colorant and a catalyst can be added within the range where the effect is not impaired. As the catalyst, in the case of a lens obtained by polymerizing a polyisocyanate compound, a polythiol compound, a compound having an epithio group, tetra-methyl-diacetoxy-distannoxane, tetra-ethyl-diacetoxy-distannoxane, tetra-propyl-diacetoxy -Distannoxane or tetra-butyl-diacetoxy-distannoxane is preferably used, in the case of polyurethane or polythiourethane lenses, organic tin compounds such as dibutyltin dichloride or known amine compounds are preferably used, and in the case of acrylic lenses Azo type catalysts are preferably used. In addition, on the released plastic lens, in order to improve scratch resistance, a co-polymer having an inorganic compound such as tin oxide, silicon oxide, zirconium oxide or titanium oxide in an organic silicon compound or an acrylic compound is used.
A cured coating may be formed using a coating solution, and a primer layer containing polyurethane as a main component may be formed on a plastic lens in order to improve impact resistance. Further, in order to impart antireflection performance, an antireflection film made of an inorganic substance such as silicon oxide, titanium dioxide, zirconium oxide or tantalum oxide may be formed on the cured film to improve water repellency. A water repellent film made of an organic silicon compound containing a fluorine atom may be formed on the antireflection film.

[0014]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. The physical properties of the plastic lenses obtained in the examples and comparative examples were evaluated as follows. (1) Releasability The following evaluation criteria were evaluated. ○: When the plastic lens is peeled from the glass mold, it can be released without damaging the lens and the mold ×: It cannot be released at all, or the lens and the glass mold are broken △: Glass on the plastic lens A part of the plastic mold is attached, a part of the plastic lens is attached to the glass mold, or the plastic lens is cracked. (2) Appearance After the plastic lens was released from the mold, the lens was visually observed. (3) Refractive Index and Abbe's Number Using a precision refractive index meter KPR-200 manufactured by Karnew Co. 2
It was measured at 0 ° C.

Example 1 43.50 parts by weight of metaxylylene diisocyanate as a polyisocyanate compound, 0.05 part by weight of dibutyltin dilaurate as a catalyst, and the following general formula (I) as an internal release agent.

[Chemical 6] In, n = 10, m = 2, R ′ has 12 to 12 carbon atoms
0.30 parts by weight of monoethanolamine salt of ether phosphate having 15 alkyl groups and R being ethylene group (phosphanol RS-7108M: Toho Chemical Industry Co., Ltd.), 2- (2'- as UV absorber Hydroxy-4-
Octyloxyphenyl) benzotriazole 0.05
56 parts by weight of pentaerythritol tetrakismercaptopropionate as a polythiol compound was added, and then about 1333 Pa.
The mixture was stirred and mixed under reduced pressure for 30 minutes to prepare a lens monomer composition. This monomer composition for lenses was poured into a lens molding die (0.00D, lens diameter 80 mm, wall thickness 1.6 mm) consisting of a glass mold and a resin gasket, which had been prepared in advance, and was charged in an electric furnace for 20 minutes. ℃ to 12
Gradually raise the temperature to 0 ° C over 22 hours, then at 120 ° C for 3
Polymerization was carried out while keeping the temperature for a while. After the polymerization was completed, the resin gasket was removed, and then the mold was released from the glass mold to obtain a plastic lens. During mold release, the mold and the lens were not damaged and could be easily released.
The lens surface was transferred as the lens type. The above lenses (1) to (3) were evaluated. The results are shown in Table 1.

Example 2 47.538 parts by weight of 1,3- (diisocyanatomethyl) cyclohexane as a polyisocyanate compound, 0.45 part by weight of dimethyltin dichloride as a catalyst, and the above general formula as an internal mold release agent. In (I), n
= 4, m = 2, R ′ is an alkyl group having 10 to 14 carbon atoms, and R is an ethylene group, a monoethanolamine salt of an ether phosphate (phosphanol RA-6008).
M: Toho Chemical Industry Co., Ltd. 0.20 parts by weight, 0.05 parts by weight of 2- (2′-hydroxy-4-octyloxyphenyl) benzotriazole as an ultraviolet absorber were added and stirred to dissolve, 2,5 as a polythiol compound
-Dimercaptomethyl-1,4-dithiane 26.467
Weight part and 25.995 parts by weight of pentaerythritol tetrakismercaptoacetate are added, and about 1333 Pa
The mixture was stirred and mixed under reduced pressure for 30 minutes to prepare a lens monomer composition. This monomer composition for lenses was poured into a lens molding die (0.00D, lens diameter 80 mm, wall thickness 1.6 mm) consisting of a glass mold and a resin gasket, which had been prepared in advance, and was charged in an electric furnace for 20 minutes. ℃ to 12
Gradually raise the temperature to 0 ° C over 22 hours, then at 120 ° C for 3
Polymerization was carried out while keeping the temperature for a while. After the polymerization was completed, the resin gasket was removed, and then the mold was released from the glass mold to obtain a plastic lens. During mold release, the mold and the lens were not damaged and could be easily released.
The lens surface was transferred as the lens type. The above lenses (1) to (3) were evaluated. The results are shown in Table 1.

Example 3 80.0 parts by weight of bis (β-epithiopropyl) sulfide as a compound having an epithio group and 15.65 parts by weight of bis (mercaptomethyl) -1,4-dithiane as a polythiol compound, Bis (diisocyanatomethyl) bicycloheptane, which is a polyisocyanate compound 4.
35 parts by weight are mixed by stirring, and in the above general formula (I), n = 3, m = 2, and R ′ has 1 carbon atom as an internal mold release agent.
Monoethanolamine salt of ether phosphate having 2 to 15 alkyl groups and R being ethylene group (phosphanol RS-4108M: Toho Chemical Industry Co., Ltd.) 0.10
Parts by weight, 2- (2'-hydroxy-
4-octyloxyphenyl) benzotriazole 0.
05 parts by weight, 0.05 parts by weight of tetrabutylphosphonium bromide as a catalyst and tetra-n-butyl-1,3
-After adding 0.005 parts by weight of diacetoxy-distannoxane, stirring and dissolving, 1 under reduced pressure of about 1333 Pa.
The mixture was stirred and mixed for 0 minutes to prepare a lens monomer composition. A lens mold (0.00D, lens diameter 80 mm, wall thickness 1.6 mm) consisting of a glass mold and a resin gasket prepared in advance with this lens monomer composition.
In an electric furnace from 20 ℃ to 120 ℃ 22
Polymerization was carried out by gradually raising the temperature over a period of time and keeping the temperature at 100 ° C. for 1 hour. After the polymerization was completed, the resin gasket was removed, and then the mold was released from the glass mold to obtain a plastic lens. During mold release, the mold and the lens were not damaged and could be easily released. The lens surface was transferred as the lens type. The above lenses (1) to (3) were evaluated. The results are shown in Table 1.

Example 4 52.02 parts by weight of metaxylylene diisocyanate as a polyisocyanate compound, 0.01 parts by weight of dimethyltin dichloride as a catalyst, and n = in the above general formula (I) as an internal release agent. 4, m = 2, R ′ is an alkyl group having 10 to 14 carbon atoms, and R is an ethylene group, a monoethanolamine salt of an ether phosphate (phosphanol RA-6008M: Toho Chemical Industry Co., Ltd.)
0.20 parts by weight, 0.05 parts by weight of 2- (2'-hydroxy-4-octyloxyphenyl) benzotriazole as an ultraviolet absorber were added and stirred and dissolved, and then 1,2- as a polythiol compound. Bis [(2-mercaptoethyl) thio] -3-mercaptopropane (47.98 parts by weight) was added, and the mixture was stirred and mixed under reduced pressure of about 1333 Pa for 30 minutes to prepare a lens monomer composition. A lens molding die (0.00) made of a glass mold and a resin gasket prepared in advance with this lens monomer composition.
(D, lens diameter 80 mm, wall thickness 1.6 mm), gradually heated from 20 ° C. to 120 ° C. over 22 hours in an electric furnace, and kept at 120 ° C. for 3 hours to carry out polymerization. . After completion of polymerization, after removing the resin gasket,
The plastic lens was obtained by releasing from the glass mold. During mold release, the mold and the lens were not damaged and could be easily released. The lens surface was transferred as the lens type. The above lenses (1) to (3) were evaluated. The results are shown in Table 1.

Example 5 26.79 parts by weight of 1,3,5- (triisocyanatomethyl) cyclohexane as a polyisocyanate compound, 0.10 part by weight of dimethyltin dichloride as a catalyst, and the above-mentioned internal release agent as a releasing agent. In the general formula (I),
n = 4, m = 2, R ′ is an alkyl group having 10 to 14 carbon atoms, and R is an ethylene group, a monoethanolamine salt of an ether phosphate (phosphanol RA-600
8M: 0.20 parts by weight of Toho Chemical Industry Co., Ltd., 0.05 parts by weight of 2- (2′-hydroxy-4-octyloxyphenyl) benzotriazole as an ultraviolet absorber were added and stirred and dissolved, 2, as a polythiol compound
5-bismercaptoethyl-1,4-dithiane 43.3
5 parts by weight and 29.86 parts by weight of 2,5-bisthioobthenyl-1,4-dithiane were added, and the mixture was stirred and mixed under a reduced pressure of about 1333 Pa for 30 minutes to prepare a monomer composition for lenses. A lens molding die (0.00D, lens diameter 80 mm, wall thickness 1.6 m) consisting of a glass mold and a resin gasket prepared in advance with this lens monomer composition.
m), the temperature was gradually raised from 20 ° C. to 120 ° C. over 22 hours in an electric furnace, and the temperature was kept at 120 ° C. for 3 hours to carry out polymerization. After the polymerization was completed, the resin gasket was removed, and then the mold was released from the glass mold to obtain a plastic lens. During mold release, the mold and the lens were not damaged and could be easily released. The lens surface was transferred as the lens type. The above lenses (1) to (3) were evaluated. The results are shown in Table 1.

Example 6 51.16 parts by weight of metaxylylene diisocyanate as a polyisocyanate compound, 0.05 part by weight of dibutyltin dilaurate as a catalyst, and n in the above general formula (I) as an internal release agent were used. = 10, m = 2, R'is an alkyl group having 12 to 15 carbon atoms, and R is an ethylene group, a monoethanolamine salt of an ether phosphate (phosphanol RS-7108M: Toho Chemical Industry Co., Ltd.) 0 40 parts by weight, as an ultraviolet absorber 2-
(2'-Hydroxy-4-octyloxyphenyl) benzotriazole (0.05 parts by weight) was added, stirred and dissolved, and then, as a polythiol compound, pentaerythritol tetrakismercaptopropionate (39.84 parts by weight) and 2,3 -Dimercapto-1-propanol 9.0
0 parts by weight was added, and the mixture was stirred and mixed under a reduced pressure of about 1333 Pa for 30 minutes to prepare a lens monomer composition. A lens molding die (0.0%) made of a glass mold and a resin gasket prepared in advance with this lens monomer composition.
0D, lens diameter 80 mm, wall thickness 1.6 mm), gradually raised from 20 ° C. to 120 ° C. in an electric furnace over 22 hours, and kept at 120 ° C. for 3 hours to carry out polymerization. . After completion of polymerization, after removing the resin gasket,
The plastic lens was obtained by releasing from the glass mold. During mold release, the mold and the lens were not damaged and could be easily released. The lens surface was transferred as the lens type. The above lenses (1) to (3) were evaluated. The results are shown in Table 1.

Comparative Example 1 Polymerization was carried out in the same manner as in Example 1 except that the internal mold release agent was not used. After the polymerization was completed, the resin gasket was removed, and then the mold was released from the glass mold. I made the mold, but could not release it. Comparative Example 2 Polymerization was performed in the same manner as in Example 2 except that the internal mold release agent was not used. After the polymerization was completed, the resin gasket was removed, and then the mold was released from the glass mold. However, I could not release it.

Comparative Example 3 In Example 2, instead of 0.20 part by weight of phosphanol RA-6008M as the internal release agent, the following general formula (II) was used.

[Chemical 7] In the same manner as above, except that n = 4, m = 2, and 0.10 part by weight of sodium salt of an ether phosphoric acid ester in which R ′ is an alkyl group having 12 carbon atoms were used, polymerization was performed in the same manner, and the polymerization was completed. After that, the resin gasket was removed, and then the mold was released from the glass mold. Although the mold was released, the lens was still white. The above lenses (1) to (3) were evaluated. The results are shown in Table 2.

Comparative Example 4 Polymerization was carried out in the same manner as in Example 3 except that the internal mold release agent was not used. After completion of the polymerization, the resin gasket was removed, and then the mold was released from the glass mold. Molding was performed, but when releasing the mold, the lens cracked, and deposits remained on a part of the mold, and sufficient mold release was not possible. The above lenses (1) to (3) were evaluated. The results are shown in Table 2.

Comparative Example 5 In Example 3, instead of phosphanol RS-4108M as the internal release agent, the following general formula (III) was used.

[Chemical 8] In n = 1, m = 2 and 1 (ratio of m = 2: m = 1 is about 4: 6), and the same applies except that R ′ is an alkyl phosphate having 4 carbon atoms. However, the composition was not sufficiently cured and was in the form of a soft jelly. Regarding the obtained lens, the above (1) to
(3) was evaluated. The results are shown in Table 1.

Comparative Example 6 Polymerization was carried out in the same manner as in Example 4 except that the internal mold release agent was not used. After the polymerization was completed, the resin gasket was removed, and the mold was then separated from the glass mold. I made the mold, but could not release it. Comparative Example 7 Polymerization was performed in the same manner as in Example 5 except that the internal mold release agent was not used, and after the polymerization was completed, the resin gasket was removed, and then the mold was released from the glass mold. However, I could not release it. Comparative Example 8 Polymerization was performed in the same manner as in Example 6 except that the internal mold release agent was not used, and after the polymerization was completed, the resin gasket was removed, and then the mold was released from the glass mold. However, I could not release it.

[0026]

[Table 1]

* M-XDI: metaxylylene diisocyanate PETMP: pentaerythritol tetrakismercaptopropionate PETMA: pentaerythritol tetrakismercaptoacetate HXDI: 1,3- (diisocyanatomethyl) cyclohexane DMMD: 2,5-dimercapto Methyl-1,4-dithiane BEPS: bis (β-epithiopropyl) sulfide NBDI: bis (isocyanatomethyl) bicycloheptane BETMP: 1,2-bis [(2-mercaptoethyl)
Thio] -3-mercaptopropane HMTI: 1,3,5- (triisocyanatomethyl)
Cyclohexane TBD: 2,5-bisthiobutenyl-1,4-dithiane DMP: 2,3-dimercapto-1-propanol

[0028]

[Table 2]

[0029]

As described above in detail, in the plastic lens obtained by the manufacturing method of the present invention, the lens surface is transferred as the lens type, has sufficient hardness, and can be easily peeled off. , Colorless and transparent with high transparency. Further, the plastic lens of the present invention has a high refractive index and a high Abbe number.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI // B29K 75:00 B29K 75:00 B29L 11:00 B29L 11:00 (56) Reference JP-A-3-281312 (JP, JP, A) JP-A 1-213601 (JP, A) JP-A 7-276381 (JP, A) JP-A 9-99441 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) ) B29C 39/00-39/44 C08K 3/08-13/08 C08L 1/00-101/14 G02B 1/04 C08G 18/00-18/87

Claims (9)

(57) [Claims] 1. A raw material monomer for a plastic lens,
The following general formula (I): (In the formula, R is an alkylene group having 1 to 12 carbon atoms, R '
Is an alkyl group having 1 to 20 carbon atoms , n is 1 to 15, m
Indicates 1 to 2. ) A first step of preparing a mixed solution by adding a neutralized phosphoric acid ester represented by as an internal mold release agent, a second step of injecting the mixed solution into a plastic lens mold and then polymerizing the mixture to obtain a polymer.
A method for producing a plastic lens, which comprises a step, and a third step of releasing the polymer from the plastic lens mold to obtain a plastic lens. 2. A raw material monomer for the plastic lens.
Is a mixed monomer containing a polyisocyanate compound and an active hydrogen compound.
A method for manufacturing the described plastic lens. 3. A raw material monomer for the plastic lens.
Is a mixed monomer containing a compound having an epithio group, a polyisocyanate compound, and an active hydrogen compound, and the method for producing a plastic lens according to claim 1. 4. The method for producing a plastic lens according to claim 3, wherein the compound having an epithio group is bis (β-epithiopropyl) sulfide. 5. The method for producing a plastic lens according to claim 2, wherein the active hydrogen compound is a polyamine compound. 6. The method for producing a plastic lens according to claim 2, wherein the active hydrogen compound is a polythiol compound. 7. The method for producing a plastic lens according to claim 1, wherein the neutralized phosphoric acid ester is added to the raw material monomer of the plastic lens in an amount of 10 to 10,000 ppm. 8. A polymer of a raw material monomer for a plastic lens and the following general formula (I): (In the formula, R is an alkylene group having 1 to 12 carbon atoms, R '
Is an alkyl group having 1 to 20 carbon atoms , n is 1 to 15, m
Indicates 1 to 2. ) A neutralizing phosphoric acid ester represented by 9. The following general formula (I): (In the formula, R is an alkylene group having 1 to 12 carbon atoms, R '
Is an alkyl group having 1 to 20 carbon atoms , n is 1 to 15, m
Indicates 1 to 2. ) A method of using a neutralized phosphoric acid ester, characterized in that the neutralized phosphoric acid ester represented by the formula (4) is used as an internal mold release agent for producing a plastic lens.