JPH08252829A - Manufacture of plastic lens, and laminated body - Google Patents

Abstract

PURPOSE: To exhibit good surface hardness after mold releasing, to provide a reflection preventing film with good adhesiveness and consisting of an inorg. substance on the surface and to make high productiity and high quality possible. CONSTITUTION: In a method for cast polymerization using a glass-made mold for casting, a film consisting of a polymerizable hard coat for forming an org. crosslinkable polymer body is formed on the inner face of the glass mold in advance. All the problems such as a plastic lens with low surface hardness, a plastic lens with poor peeling off properties with the glass mold and a hard coat with no adhesiveness with a reflection preventing film consisting of an inorg. substance can be thereby solved and a lens product with high qualities can be obtd. and manufacturing with good efficiency can become possible.

Description

Detailed Description of the Invention

[0001]

INDUSTRIAL APPLICABILITY The present invention makes it possible to easily form a hard coat film having good surface hardness on the surface of a plastic lens, and to provide an antireflection film made of an inorganic substance having good adhesion on the surface. A method for producing a plastic lens having high productivity and high quality, which enables the above, and a laminated body.

[0002]

2. Description of the Related Art Heretofore, there has been known a method of obtaining a transparent resin composite by applying a hard coat material composed of an organic silicon compound on the inner surface of a mold and curing the same to inject and cure a thermosetting monomer (Japanese Patent Publication No. S52-52). 13536, Japanese Patent Publication No.53-1574
3) actually has a strong adhesion between the organic silicon compound and the glass type (since it contains silicon oxide as the main component), and damages the mold surface and the lens surface.

By limiting the polymerizable monomer, for example, an isocyanate compound having two or more isocyanate groups in one molecule and an alcohol compound or a thiol compound having two or more hydroxyl groups and / or mercapto groups in one molecule are used. Urethane resin is produced by a polymerization method by reacting in a mold. The urethane resin produced by this method is particularly used as an optical material for optical lenses, spectacle lenses, optical disk substrates, transparent plates and the like, and therefore requires high surface accuracy. For this reason, the mold used in the cast polymerization method is most often made of glass. However, it is almost impossible to peel the urethane resin from the mold. Therefore, a method using an external release agent (JP-A-62-267316), a method using a polyolefin resin mold (JP-A-62-236818), and a method using an internal release agent (JP-A-1-213601). Is proposed. However, when a release agent is used, the adhesion to the hard coat is poor and sufficient quality cannot be obtained. Moreover, the resin mold does not have repeated durability of the mold itself, and has a problem in surface accuracy.

On the other hand, the urethane resin has drawbacks that the surface is soft and is easily scratched. Therefore, when urethane resin is used for optical materials such as lenses, an organic silicon-based hard coat material containing an organic silicon compound as a main component or a polymerizable hard coat material for forming an organic crosslinkable polymer is used. A method such as hard coating is used. However, these hard coat treatments are laborious and are not always efficient methods. In order to solve this problem, Japanese Patent Publication No. 6-20756 describes that a film made of a hydrolyzed condensate of an organosilicon compound having a specific functional group is previously formed on the inner surface of a glass mold, and then cast polymerization is performed. However, as described above, the affinity between the organosilicon compound and the glass type (because silicon oxide is the main component) is good, and the mold surface and the lens surface are damaged. Further, when a release agent is added to the hard coat material, the adhesion between the lens material and the hard coat or between the hard coat and the inorganic vapor deposition film is poor and sufficient quality cannot be obtained.

Further, the (meth) acrylic resin has a higher polymerization rate than the urethane resin, and the (meth) acrylic resin by photocuring can improve the productivity (JP-A-3-231908, JP-A-3-3908). -239711
etc). However, because the hard coat is performed after demolding,
Productivity will decrease.

[0006]

As a result of intensive studies to solve the above problems, the present inventor has found that the glass mold and the hard coat have good releasability, and the lens material, the hard coat and the hard coat. The present invention has been completed by finding a method for producing a plastic lens which is excellent in adhesiveness with the inorganic vapor-deposited film, has high surface hardness, has excellent scratch resistance, has good appearance quality, and has high productivity.

[0007]

The present inventor has found that the above-mentioned problems can be solved all at once by not containing a hydrolyzate of an organic silicon compound as a main component in an organic crosslinkable monomer.

That is, according to the present invention, as the polymerizable monomer, a urethane monomer resin obtained by reacting an isocyanate compound with an alcohol compound or a thiol compound in a template or a cured product of a monomer which is photocured or cured by light and heat is used as a template. To facilitate peeling from the surface of the urethane resin and the organic crosslinkable polymer on the surface of the polymer, and to provide an antireflection film made of an inorganic oxide having good adhesion on the surface. is there.

The organic crosslinkable monomers used in the present invention include general monofunctional and polyfunctional (meth) acrylates, as well as epoxy (meth) acrylates, epoxidized oil (meth) acrylates, urethane (meth) acrylates, They can be used alone or as a mixture based on saturated polyester, polyester (meth) acrylate, polyether (meth) acrylate, vinyl / (meth) acrylate, polyene / thiol, polybutadiene, and polystyrylethyl methacrylate.

Further, for the purpose of adjusting the refractive index with the lens substrate, Al, Sn, S having a particle size of 1 to 100 mm.
b, Ta, Ce, La, Fe, Zn, W, Zr, In,
Fine particles composed of one or more metal oxides selected from Ti and / or Si, Al, Sn, Sb, Ta, Ce,
Composite fine particles composed of two or more kinds of metal oxides selected from La, Fe, Zn, W, Zr, In and Ti may be mixed. Further, a small amount of an organosilicon compound may be added for the purpose of controlling the adhesiveness with the glass type, but when an organosilicon compound having a silanol group and an alkoxysilane group is used, a chemical bond is formed with the glass type. , Be careful when using.

These organic crosslinkable monomers have a weak affinity for glass with respect to the organosilicon compound and its hydrolyzate and do not damage the glass mold. Therefore, the expensive glass mold can be repeatedly used. In addition, as said suitable solvent, C1-C4 methanol,
Lower alcohols such as ethanol, propanol, butanol; lower carboxylic acids such as acetic acid and methyl acetate or alkyl esters thereof; cellosolves such as methyl cellosolve and ethyl cellosolve; ethers such as dioxane; ketones such as acetone; methylene chloride Halogenated hydrocarbons such as benzene and aromatic hydrocarbons such as benzene and toluene.

Further, a silicone-based or fluorine-based surfactant may be added to the coating solution of the present invention to improve the smoothness of the obtained coating and form a uniform coating. Do not use in large amounts for sexual purposes. In addition, other various additives, for example, an ultraviolet absorber,
Antioxidants, dyes and pigments may be added.

In the present invention, the method of forming the coating film of the organic crosslinkable polymer on the surface of the glass mold is not particularly limited, and a method of attaching the organic crosslinkable monomer to the mold according to a generally known method. Is adopted. For example, dipping method, spin coating method, spray coating method is generally adopted, after applying, heat curing,
A film is formed by ultraviolet curing or infrared curing. The temperature at the time of heat-curing or infrared-curing was 150 ° C in the conventional plastics, but it became possible to heat at high temperature. Also in the case of UV curing,
Since the hard coat is indirectly provided on the surface of the plastic lens, the problem of yellowing of the plastic lens due to ultraviolet rays could be solved. These curing conditions have great merits in manufacturing and quality such as short-time curing and improvement of coating film level. Further, in the case of dyeing in the subsequent step, it is desirable that the film formed of the organic crosslinkable polymer is a film that can be dyed with a disperse dye or an oil soluble dye.

The thickness of the organic crosslinkable polymer film is 0.
The thickness can be about 1 μm to 50 μm, but the thickness of 1 μm to 10 μm is particularly suitable for obtaining a desired effect.

Next, the compound having two or more isocyanate groups in one molecule and the compound having two or more hydroxyl groups and / or mercapto groups in one molecule which can be used in the present invention will be explained. It goes without saying that this is not a limitation.

The isocyanate compound used in the present invention is selected from the group consisting of polyisocyanate compounds and isocyanate compounds having an isothiocyanate group.
Examples of the polyisocyanate compound include ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate and nonamethylene diisocyanate. Isocyanate, 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 -To, 1,8-diisocyanato-4-isocyanatomethyloctane, 2,5,7-trimethyl-1,8-diisocyanato-5-i Socianatomethyloctane, bis (isocyanatoethyl) carbonate, bis (isocyanatoethyl) ether, 1,4-butylene glycol dipropyl ether-α, α'-diisocyanate, lysine diisocyanatomethyl 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, mesitylylene triisocyanate, 2,6
-Di (isocyanatomethyl) furan, isophorone diisocyanate, bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane diisocyanate, cyclohexanediisocyanate, methylcyclohexanediisocyanate, dicyclohexyldimethylmethane Diisocyanate, 2,2'-dimethyldicyclohexylmethane diisocyanate, bis (4-isocyanato-n-butylidene) pentaerythritol, diisocyanate diisocyanate, 2-isocyanatomethyl-3- (3- Isocyanatopropyl) -5-isocyanatomethyl-dicyclo [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, 2,5 ( Or 6)
-Bis (isocyanatomethyl) -bicyclo [2,2,2
1] -Aliphatic polyisocyanate such as 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 (diphenylmethane diisocyanate), naphthalene triisocyanate, diphenylmethane 2,4,4'-triisocyanate, 3-methyldiphenylmethane-4,6,4'-triisocyanate
4-methyl-diphenylmethane-3,5,2 ',
4 ', 6'-Pentaisocyanate, Phenylisocyanatomethylisocyanate, Phenylisocyanatoethylisocyanate, Tetrahydronaphthalene diisocyanate, Hexahydrobenzene diisocyanate, 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, dibenzofurandiisocyanate, carbazole diisocyanate, ethylcarbazole diisocyanate, diclocarbazole diisocyanate Aromatic polyisocyanates such as isocyanate can be mentioned.

Examples of the polyisocyanate compound containing a sulfur atom include thiodiethylene diisocyanate, thiodipropyl diisocyanate, thiodihexyl diisocyanate and dimethyl sulfone diisocyanate. , Dithiodimethyl diisocyanate, dithiodiethyl diisocyanate, dithiodipropyl diisocyanate, and other sulfur-containing aliphatic isocyanates, diphenyl sulfide-2,4'-diisocyanate, diphenyl sulfide- 4,4'-diisocyanate, 3,3'-dimethoxy-4,4'-diisocyanatodibenzylthioether, bis (4-isocyanatomethylphenyl) sulfide, 4,4'-methoxyphenylthioethylene glycol-3 Aromatic Isocyanates Having Sulfide Bonds such as 3'-diisocyanate -, diphenyl disulfide-4,4' Jiisoshiana - DOO, 2,2'-dimethyl diphenyl disulfide-5,5'-Jiisoshiana -
G, 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 Aromatic diisocyanate having disulfide bond, diphenylsulfone-4,4'-diisocyanate, diphenylsulfone-3,3'-diisocyanate, benzidine sulfone-4,4'-diisocyanate, Diphenylmethanesulfone-4,4'-diisocyanate, 4-methyldiphenylsulfone-2,4'-
Diisocyanate, 4,4'-dimethoxydiphenylsulfone-3,3'-diisocyanate, 3,3'-dimethoxy-4,4'-diisocyanatobenzylsulfone,
4,4'-Dimethyldiphenylsulfone-3,3'-diisocyanate, 4,4'-di-tert-butyldiphenylsulfone-3,3'-diisocyanate, 4,
4'-methoxyphenylethylene sulfone-3,3'-
Aromatic isocyanate having sulfone bond such as diisocyanate and 4,4'-dicyclodiphenylsulfone-3,3'-diisocyanate, 4-methyl-3-isocyanatophenylsulfonyl-4'-isocyanate Aromatic isocyanate having sulfonic acid ester bond such as phenol ester, 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, etc. Aromatic isocyanate having sulfonic acid amide bond
And sulfur-containing heterocyclic compounds such as thiophene-2,5-diisocyanate and 1,4-diamine-2,5-diisocyanate.

Further, examples of the isocyanate compound having an isothiocyanato group include 1-isocyanato-
3-isothiocyanatopropane, 1-isocyanato-
5-isothiocyanatopentane, 1-isocyanato-6
Aliphatic compounds such as isothiocyanatohexane, isothiocyanatocarbonyl isocyanate, 1-isocyanato-4-isothiocyanatocyclohexane, 1-isocyanato-4-isothiocyanatobenzene, 4-methyl-
Aromatic compounds such as 3-isocyanato-1-isothiocyanatobenzene, heterocyclic compounds such as 2-isocyanato-4,6-diisothiocyanato-1,3,5-triazine, and further 4-isocyanato-4 '-Isothiocyanato diphenyl sulfide, 2-isocyanato-2'-
In addition to isothiocyanato groups such as isothiocyanatodiethyldisulfide, compounds containing a sulfur atom and the like can be mentioned.

Further, halogen-substituted compounds such as chlorine-substituted compounds and bromine-substituted compounds of these isocyanate compounds, and further, their burette reaction products, adduct reaction products with trimethylolpropane, dimerization or trimerization reactions. Products and the like can also be used. These may be used alone or in combination of two or more.

The active hydrogen compound used in the present invention is selected from polyol compounds, polythiol compounds and hydroxythiol compounds. 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, sorbitol, erythritol, threitol, ribitol, arabinitol, xylitol, allitol, mannitol, dorsitol, iditol, glycol, inositol, hexanetriol, triglycellulose, diglycerol, triethylene glycol, polyethylene glycol, Tris (2-hydroxyethyl) isocyanurate, cyclobutanediol, cyclopentanediol, cyclohexanediol, cycloheptanediol, cyclooctanediol, cyclohexanedimethanol, hydroxypropylcyclohexanol, tricyclo [5,2,1,1]
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-, Aliphatic compounds such as hydroxypropyltricyclo [5,3,1,1] dodecanol, spiro [3,4] octanediol, butylcyclohexanediol, 1,1'-bicyclohexylidenediol, cyclohexanetriol, maltitol, lactose Polyol, dihydroxynaphthalene, trihydroxynaphthalene, tetrahydroxynaphthalene, dihydroxybenzene, benzenetriol,
Biphenyltetraol, pyrogallol, (hydroxynaphthyl) pyrogallol, trihydroxyphenanthrene, 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, polymer polyols such as epoxy resins, oxalic acid, glutamic acid, adibic acid, acetic acid, propionic acid, cyclohexanecarboxylic acid. Acid, β-oxocyclohexanepropionic acid, dimer acid, phthalic acid, isophthalic acid, salicylic acid, 3-bromopropionic acid, 2-
Condensation reaction product of an organic acid such as bromoglycol, dicarboxycyclohexane, pyromellitic acid, butanetetracarboxylic acid, bromophthalic acid and the above polyol, addition reaction product of the above polyol and an alkylene oxide such as ethylene oxide or propylene oxide Products, addition reaction products of alkylene polyamines with ethylene oxide and 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 compounds obtained by adding an average of 3 molecules or less of ethylene oxide and / or propylene oxide per hydroxyl group to these compounds, di- (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-te
Examples thereof include polyols containing a sulfur atom such as rt-butyl-3-methylphenol) and 1,3-bis (2-hydroxyethylthioethyl) -cyclohexane.

As the polythiol, for example, 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-dimethyl Propane-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,
Aliphatic polythiols such as 2-bis (2-mercaptoethylthio) -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 (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 (mercaptomethyl) 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, 2,4-di (p-
Aromatic polythiols such as mercaptophenyl) pentane, 2,5-dichlorobenzene-1,3-dithiol, 1,3-di (p-chlorophenyl) propane-
2,2-dithiol, 3,5,4-tribromo-1,2
-Chlorine-substituted aromatic polythiols such as dimercaptobenzene and 2,3,4,6-tetrachloro-1,5-bis (mercaptomethyl) benzene, and bromine-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-sym
-Triazine, 2-thiobenzeneoxy-4,6-dithiol-sym-triazine, 2-thiobutyloxy-
Polythiols containing heterocycles such as 4,6-dithiol-sym-triazine, 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 (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 such as the alkylated products thereof, 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, 1,2,3 -Tris (mercaptomethylthio) propane, 1,2,3-tris (2-mercaptoethylthio) propane, 1,2,3-
Tris (3-tris (3-mercaptopropylthio) propane, tetrakis (mercaptomethylthiomethyl) methane, tetrakis (2-mercaptoethylthioethyl)
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), hydroxymethyl disulfide bis (2-
Mercaptoacetate), hydroxymethyldisulfidebis (3-mercaptopropionate), hydroxyethyldisulfidebis (2-mercaptoacetate), hydroxyethyldisulfidebis (3-mercaptopropionate), hydroxypropyldisulfidebis (2-mercaptoacetate) ), Hydroxypropyl disulfide bis (3-mercaptopropionate), 2-mercaptoethyl ether bis (2-mercaptoacetate), 2-mercaptoethyl ether bis (3-mercaptopropionate), 1,4-dithiane-2. , 5-diolbis (2-mercaptoacetate), 1,4-dithiane-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-
Mercaptoethyl ester), thiodiglycolic acid bis (2,3-dimercaptopropyl ester), thiodipropionic acid bis (2,3-dimercaptopropyl ester), thiodipropionic acid bis (2,3-dimercaptopropyl) Ester), bis (2,3) dithioglycolate
-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 And a heterocyclic compound containing a sulfur atom in addition to a mercapto group such as 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), pentaerythritol bis (3-mercaptopropionate), pentaerythritol tris (thioglycolate), pentaerythritol pentakis (3-mercaptopropionate) ), Hydroxymethyl-tris (mercaptoethylthioethyl) methane, 1-hydroxyethylthio-3-
Mercaptoethylthiobenzene, 4-hydroxy-4 '
-Mercaptodiphenyl sulfone, 2- (2-mercaptoethylthio) ethanol, dihydroxyethyl sulfide mono (3-mercaptopropionate), dimercaptoethane mono (sulfylate), hydroxyethylthiomethyl-tris (mercaptoethylthio) methane, etc. Is mentioned.

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 ratio of these isocyanate compounds and active hydrogen compounds used is (NCO + NCS)
/ (OH + SH) functional group molar ratio is usually 0.5 to 3.
It is in the range of 0, preferably in the range of 0.5 to 1.5.

Known chain extenders, cross-linking agents, light stabilizers, ultraviolet absorbers, antioxidants, oil-soluble dyes,
You may add various substances, such as a filler and an internal mold release agent.
However, the internal mold release agent is useful in a portion where the organic crosslinkable polymer is not applied to the glass type, and is essentially not used because it lowers the adhesion between the organic crosslinkable polymer and the plastic lens. Is desirable. Further, in order to control the reaction rate, a known reaction catalyst used in the production of polyurethane can be appropriately added.

The photocurable and light and heat curable monomers are suitable for short time curing. It is possible to make to order by taking advantage of short-time curing, but when using a heat-curing hard coat, the maximum temperature during curing is limited because the plastic is the object to be coated, and the curing time Since it takes a long time, make-to-order manufacturing is difficult. However, in the present invention, since the glass mold is coated with a hard coat and cured, there is almost no restriction on the maximum curing temperature,
It became possible to cure the hard coat in a short time. As a result, the productivity could be greatly improved.

Next, the monomer for which the casting polymerization monomer is photocurable or cured by light and heat will be described. Monomers used in the present invention are monofunctional and polyfunctional (meth).
In addition to acrylate, epoxy (meth) acrylate, epoxidized oil (meth) acrylate, urethane (meth) acrylate, unsaturated polyester, polyester (meth) acrylate, polyether (meth) acrylate, vinyl / (meth) acrylate, polyene / The thiol, polybutadiene, and polystyrylethyl methacrylate can be used as a main component, or a mixture thereof can be used. For details, see JP-A-3-231908 and JP-A-3-231908.
-239711, JP-A-4-080212, JP-A-4-080213, JP-A-4-065406, JP-A-4-0
65407, JP-A-5-032735, JP-A-5-13
It is preferable to use the monomers and polymerization initiators described in 4101 and the like, and the curing method may be the same.

Another advantage of the present invention is that the adhesion between the hard coat and the antireflection film made of an inorganic material is excellent. Conventional hard coats are mainly composed of organic silicon compounds, especially components containing silanol groups.
Reacts with the glass mold to form a siloxane bond. Therefore, the peelability between the hard coat and the glass mold is poor, and the mold is damaged. A release agent such as a surfactant is added to the hard coat in order to improve the peeling property. However, the amount of the surfactant contained in the hard coat increases, and the adhesion to the antireflection film is significantly reduced. Since the present invention does not contain an organosilicon compound as a main component, these problems can be solved.

When a hard coat made of a crosslinked organic polymer is applied to a lens and cured to form an inorganic vapor deposition film, the adhesion between the hard coat and the inorganic vapor deposition film cannot be obtained.

However, as in the present invention, coating on a glass mold,
After curing, transfer to a lens provides adhesion between the hard coat and the inorganic vapor deposition film. This is because in the above method, the hard coat surface is in contact with air so that the hydrophobic groups are oriented on the surface, and in the method described below, the hard coat surface is in contact with the hydrophilic glass mold and therefore the hydrophilic groups are oriented in the surface. are doing. From this, it is considered that the higher the hydrophilicity of the hard coat surface of the inorganic oxide such as SiO _2, the higher the adhesion.

In the present invention, for the above reason, it is possible to use an acrylic hard coat or the like, which has not been able to obtain adhesion with inorganic vapor deposition until now.

Examples of the film forming method for forming the antireflection film made of an inorganic material in the present invention include a vacuum vapor deposition method, an ion plating method and a spattering method.
In the vacuum vapor deposition method, an ion beam assist method in which an ion beam is simultaneously irradiated during vapor deposition may be used. As the film structure, either a single-layer antireflection film or a multilayer antireflection film may be used.

Specific examples of the inorganic material used include Si
O ₂ , SiO, ZrO ₂ , TiO ₂ , TiO, Ti ₂ O ₃ ,
Ti ₂ O ₅ , Al ₂ O ₃ , Ta ₂ O ₅ , CeO ₂ , MgO, Y ₂
O ₃ , SnO ₂ , MgF ₂ , WO _{3 and the} like can be mentioned. These inorganic substances may be used alone or in a mixture of two or more.

When forming the antireflection film, it is desirable to perform surface treatment of the hard coat film. Specific examples of the surface treatment include acid treatment, alkali treatment, ultraviolet irradiation treatment, plasma treatment by high frequency discharge in an argon or oxygen atmosphere, and ion beam irradiation treatment of argon, oxygen or nitrogen.

[0034]

EXAMPLES The present invention will be described in detail, but the present invention is not limited to these examples.

The performance of the plastic lens having the curable coating and the vapor deposited film was evaluated by the following method.

(1) Releasability When casting polymerization of a polymerizable monomer in a glass mold,
○ If the molded product can be easily peeled from the glass mold,
Those that could not be peeled off were evaluated by x.

(2) Appearance The appearance of the plastic lens molded product having a coating film was visually evaluated.

(3) Adhesion Adhesion between the substrate and the hard coat film and between the hard coat film and the multi coat film was determined by a cross-cut tape test according to JIS D-0202. That is, cut into 1 mm intervals on the surface of the substrate using a knife, and
100 squares are formed. Then, after strongly pressing the cellophane adhesive tape (trade name "Cellotape" manufactured by Nichiban Co., Ltd.) on top of it, it was pulled by 90 degrees from the surface and peeled off rapidly. It was used as an index.

Example 1 A liquid composition obtained by adding 2 g of benzoin isopropyl ether as a photosensitizer to a monomer composition consisting of 40 g of pentaerythritol tetraacrylate, 30 g of trimethylolpropane triacrylate and 30 g of ethylene glycol diacrylate on the surface of a glass mold. The product was applied at room temperature by a spin coating method to a thickness of 3 μm. After the coating, a 200 w high pressure mercury lamp was used for irradiation in a nitrogen stream from a distance of 25 cm for 30 seconds to obtain a cured coating film.

1,2-Bis [(2-mercaptoethyl) thio] -3- was placed in a mold composed of a glass mold and a silicon gasket on which a coating film was thus formed.
87 g mercaptopropane, 94 g m-xylylene diisocyanate, 0.000 di-n-butyltin dichloride
A liquid curable composition consisting of 2 g and 0.2 g of 2- (2-hydroxy-5-ethyl) benzotriazole was injected and 3
The temperature was raised from 0 ° C. to 120 ° C. over 12 hours and kept constant at 120 ° C. for 2 hours to complete the polymerization. After gradually cooling to room temperature, the polymerized molded product was evaluated according to the above evaluation method. The results are shown in Table 1.

COMPARATIVE EXAMPLE 1 50 g of γ-glycidoxypropyltrimethoxysilane and 50 g of γ-glycidoxypropylmethyldiethoxysilane were added to 0.1N hydrochloric acid 25
Hydrolyze with g and stir at 20 ° C. for 15 hours. Next, methanol-dispersed silica sol (MA-ST manufactured by Nissan Chemical Industries, Ltd.)
300 g, Zonial FSN (manufactured by Du Pont) as a surfactant, 0.1 g of aluminum acetylacetonate as a curing agent and 350 g of methanol were mixed to prepare a hard coat solution. This hard coat solution was applied to the glass mold surface at room temperature by a spin coating method to a thickness of 3 μm. After coating, baking was performed at 130 ° C. for 2 hours in a hot air oven to obtain a cured coating film.

Polymerization was carried out and evaluated in the same manner as in Example 1 except that the glass mold on which the film was formed in this manner was used, and the results are shown in Table 1.

Example 2 The following antireflection film was provided on the lens surface obtained in Example 1 and evaluated according to the above evaluation method. The results are shown in Table 1.

After the lens surface is subjected to plasma treatment (400 W of argon plasma for 60 seconds), SiO ₂ , ZrO ₂ , SiO ₂ , ZrO ₂ , in order from the substrate to the atmosphere,
An antireflection multilayer film consisting of 5 layers of SiO ₂ was formed by a vacuum evaporation method (manufactured by Vacuum Instrument Co., Ltd .; BMC-1000). The optical thickness of each layer is the first SiO ₂ layer,
Equivalent layer of the next ZrO ₂ and SiO ₂ layer and the next ZrO
_{The two} layers and the uppermost SiO ₂ layer were formed to have λ / 4, respectively. The design wavelength λ was 520 nm.

Comparative Example 2 50 g of γ-glycidoxypropyltrimethoxysilane, 50 g of γ-glycidoxypropylmethyldiethoxysilane and 2 g of 3,3,3-trifluoropropyltrimethoxysilane were added to 0.1 N. It is hydrolyzed with 27 g of hydrochloric acid and stirred at 20 ° C. for 15 hours. Next, 300 g of methanol-dispersed silica sol (MA-ST manufactured by Nissan Chemical Industries, Ltd.) and Zonial FSN as a surfactant.
0.1 g (manufactured by DuPont), 0.5 g of aluminum acetylacetonate as a curing agent and 350 g of methanol
Was mixed to prepare a hard coat liquid. This hard coat solution was applied to the glass mold surface at room temperature by a spin coating method to a thickness of 3 μm. After coating 130 ° C in a hot air oven
Firing was performed for a time to obtain a cured coating film.

Polymerization was carried out in the same manner as in Example 1 except that the glass mold having the film thus formed was used. Example 2 and the antireflection film were formed on the surface of the obtained lens, and evaluated according to the above evaluation method. The results are shown in Table 1.

(Example 3) 30 g of dipentaerythritol pentaacrylate, 40 g of 1,4-butylene glycol diacrylate, 17 g of tri (acryloxyethyl) isocyanurate and 2- (2-hydroxy-5-tert-butylphenyl) benzo on the surface of a glass mold. A liquid composition consisting of 10 g of triazole and 3 g of methylphenylglyoxylate was applied at room temperature by a spin coating method to a thickness of 3 μm. After the coating, a 200 w high pressure mercury lamp was used for irradiation in a nitrogen stream from a distance of 25 cm for 30 seconds to obtain a cured coating film.

140 g of urethane dimethacrylate obtained by reacting isophorone diisocyanate and 2-hydroxylpropyl methacrylate in a mold consisting of a glass mold and a polyethylene gasket on which a film is thus formed, and nonabutylene glycol 20 g of dimethacrylate, 5 g of 1,6-hexanediol dimethacrylate, 20 g of isobornyl methacrylate,
0.03 g of 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 0.1 g of t-butylperoxyisobutyrate, 0.05 g of 2-hydroxy-4-methoxybenzophenone and 0.2 g of tridecyl phosphate were mixed at room temperature. After stirring well with 50mmH
The raw material depressurized to 10 g and degassed for 10 minutes was injected.

Then, after irradiating 30 J / cm ² of ultraviolet rays from both sides of the mold with a metal halide lamp of 3 kW and gradually cooling to room temperature, an inorganic antireflection film was formed on the polymerized molded product in the same manner as in Example 2. Then, the evaluation was performed according to the above evaluation method. The results are shown in Table 1. (Comparative Example 3) 140 g of urethane dimethacrylate obtained by reacting isophorone diisocyanate with 2-hydroxylpropyl methacrylate in a mold made of a glass mold and a polyethylene gasket, 20 g of nonabutylene glycol dimethacrylate, 1,6 -Hexanediol dimethacrylate 5 g, isobornyl methacrylate 20 g, 2,4,6-trimethylbenzoyldiphenylphosphine oxide 0.03 g, t-butylperoxyisobutyrate 0.1 g, 2-hydroxy-4-methoxybenzophenone 0.05 g , Tridecyl phosphate (0.2 g) were mixed and well stirred at room temperature.
The raw material depressurized to mmHg and degassed for 10 minutes was injected.
Then, 30 J / cm ² of ultraviolet light was irradiated from both sides of the mold by a metal halide lamp of 3 kW, and then gradually cooled to room temperature, and then a polymerized molded product was obtained.

30 g of dipentaerythritol pentaacrylate, 40 g of 1,4-butylene glycol diacrylate, 17 g of tri (acryloxyethyl) isocyanurate, and 2- (2-hydroxy-5-tert-butylphenyl) benzotriazole 1 were formed on the surface of the obtained lens.
A liquid composition consisting of 0 g and 3 g of methylphenylglyoxylate was spin-coated at room temperature to a thickness of 3
It was applied to a thickness of μm. After the coating, a 200 w high pressure mercury lamp was used for irradiation in a nitrogen stream from a distance of 25 cm for 30 seconds to obtain a cured coating film. Further, an inorganic antireflection film was prepared in the same manner as in Example 2 and evaluated according to the above evaluation method. The results are shown in Table 1.

[0051]

[Table 1]

[0052]

According to the present invention, (1) a hard coat film can be provided on the surface of a plastic lens having a low surface hardness without handling.

(2) A monomer having poor releasability between the glass mold and the plastic lens can be used.

(3) It is possible to construct a manufacturing process in which the merit of the photocurable lens monomer that is cured for a short time can be maximized.

(4) It is possible to form a hard coat having good adhesion to an antireflection film made of an inorganic material.

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Claims (6)

[Claims] 1. A method of casting polymerization using a glass mold, characterized in that a coating made of a polymerizable hard coat material for forming an organic crosslinkable polymer is previously provided on the inner surface of the glass mold. Manufacturing method of plastic lens. 2. The method for producing a plastic lens according to claim 1, wherein the polymerizable hard coat material is made of an ultraviolet curable resin. 3. The method for producing a plastic lens according to claim 1, wherein the polymerizable hard coat material does not contain a hydrolyzate of an organosilicon compound as a main component. 4. A compound for casting polymerization comprising a compound having two or more isocyanate groups in one molecule and a compound having two or more hydroxyl groups and / or mercapto groups in one molecule. The method of manufacturing a plastic lens according to claim 1. 5. The method for producing a plastic lens according to claim 1, wherein the casting polymerization monomer is a compound which is photocurable or is cured by light and heat. 6. A laminate comprising an antireflection film made of an inorganic material provided on the surface of a plastic lens obtained by the method according to claim 1.