JP4485838B2 - Manufacturing method of polarizing plastic lens and manufacturing method of polarizing plastic film - Google Patents

Description

The present invention for example, various optical lenses such as lenses for spectacles, the image display body such as polarizing plastic lens for use in a liquid crystal display device, a method for manufacturing a polarization plastic film arm.

  Conventionally, the following are known as polarizing materials such as this type of polarizing plastic lens (for example, see Patent Document 1). That is, this is a type in which a polarizing film made of polyvinyl alcohol resin is held in a lens made of diethylene glycol bisallyl carbonate resin.

  This polarizing plastic lens has a cylindrical shape, and is provided with a support protrusion on the inner surface and a gasket with a resin injection portion protruding at two locations on the outer surface, and can be fitted to the inner periphery. It is manufactured using a pair of mold members.

In manufacturing the polarizing plastic lens, first, the peripheral edge of the polarizing film is placed on the support protrusion, and then the mold member is fitted to the inner peripheral part of the gasket. Subsequently, diethylene glycol bisallyl carbonate resin is filled between the mold members through the resin injection part. Then, the resin is polymerized and cured, and then the molded members of the desired polarizing plastic lens are obtained by releasing the mold members and the gaskets.
Japanese Patent Laid-Open No. 2001-311804 (pages 2 and 3, FIGS. 2 and 3)

  However, in the conventional polarizing plastic lens, there is a possibility that the polarizing film may be peeled off from the lens over time due to environmental changes such as temperature changes due to different thermal expansion coefficients of the lens and the polarizing film.

The present invention has been made paying attention to the problems existing in the prior art as described above. And has as its object, method of manufacturing a polarizing plastic film arm capable of suppressing method for producing polarizing plastic lens capable of suppressing the peeling of the polarizing film from the lens body, the peeling of the polarizing film from the film body Is to provide.

To achieve the above object, the inventions according to claim 1, polymerization raw material a compound having an isocyanato group or an isothiocyanato group and a compound having a hydroxyl group or a mercapto group as the main component, containing a polymerization catalyst lens obtained by polymerizing a is formed is provided on both surfaces of the polarizing film is formed of a resin having a hydroxyl group, and an isocyanato group or an isothiocyanato group is contained in the polymerization raw material of the lens body, the polarizing film A method for producing a polarizing plastic lens in which a hydroxyl group contained in a resin to be bonded is bonded by a urethane bond or a thiourethane bond, and a pair of molding dies formed in a gently curved shape and one molding The mold is composed of a fixing member for fixing the polarizing film to the mold, and the polarizing film is used for one molding. Place on the bottom of the mold and fix its peripheral edge to one molding die with a fixing member, and then have the other molding die have a molding recess between its inner surface and one side of the polarizing film An intermediate molding in which a lens body is provided on one side surface of a polarizing film by placing the polymerization raw material in a molding recess in a state of being clamped to the one molding die and then polymerizing and curing the polymerization raw material The intermediate molded body is then placed with a new molding recess between the other side surface of the polarizing film and the inner surface of one molding die, and again in this new molding recess. The gist is to fill the polymerization raw material and to cure this .
The invention according to claim 2 is the glass according to claim 1, wherein the polymerization raw material on one side of the polarizing film and the polymerization raw material on the other side of the polarizing film are polymerized and cured. The gist is to perform the heat treatment within a range from the transition point to a temperature 20 ° C. higher than the glass transition point.

The inventions of claim 3, a compound having an isocyanato group or an isothiocyanato group, as a main component a compound having a hydroxyl group or a mercapto group, a film obtained by polymerizing a polymerizable material containing the polymerization catalyst is provided on both surfaces of the polarizing film is formed of a resin having a hydroxyl group, and an isocyanato group or an isothiocyanato group is contained in the polymerization raw material of the film body, and a hydroxyl group contained in the resin for forming the polarizing film Is a method for producing a polarizing plastic film bonded by a urethane bond or a thiourethane bond, and a pair of molding dies having an inner surface formed in a flat shape, and a polarizing film on one molding die Using a molding die composed of a fixing member for fixing, the polarizing film is arranged on the bottom surface of one molding die and the The edge is fixed to one molding die by a fixing member, and then the other molding die is disposed so as to have a molding recess between the inner surface and one side surface of the polarizing film, and the one molding is performed. An intermediate molded body having a film body provided on one side surface of the polarizing film is molded by filling a polymerization raw material into a molding recess while being clamped in a mold for use, and then polymerizing and curing the polymerization raw material. The intermediate molded body is arranged so as to have a new molding recess between the other side surface of the polarizing film and the inner surface of one molding die, and the polymerization raw material is again filled in the new molding recess. The gist is to polymerize and cure .
The invention according to claim 4 is the glass according to claim 3, wherein the polymerization raw material on one side of the polarizing film and the polymerization raw material on the other side of the polarizing film are polymerized and cured. The gist is to perform the heat treatment within a range from the transition point to a temperature 20 ° C. higher than the glass transition point.

As described in detail above, the present invention has the following effects.
According to inventions set forth in claims 1 and 2, it is possible to produce a polarizing plastic lens that suppress separation of the polarizing film from the lens body. Moreover, it can suppress that the polarizing film of a polarizing plastic lens softens and flatness is impaired.

According to inventions set forth in claims 3 and 4, it is possible to manufacture the polarizing plastic film that suppresses peeling of the polarizing film from the film body. Moreover, it can suppress that the polarizing film of a polarizing plastic film softens and flatness is impaired.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The best mode for embodying the present invention in a polarizing plastic lens will be described below in detail with reference to the drawings.
(First embodiment)
As shown in FIG. 1, the polarizing plastic lens 11 is formed in a gently curved surface (a cross-sectional arc that is convex downward), and a pair of synthetic resin lens bodies 12 each having a different thickness have a hydroxyl group. It is provided on both surfaces of a polarizing film 13 formed from a polyvinyl alcohol resin as a resin. This polarizing plastic lens 11 is used for a lens for sunglasses or the like.

  First, the polarizing film 13 will be described. The polarizing film 13 is formed by uniaxially stretching a polyvinyl alcohol resin and impregnating an iodine compound as a polarizer, and its thickness is set to about 20 μm. In addition, you may use the polarizing film 13 which uses a polyester polyol resin as a raw material.

  On the other hand, the lens body 12 is obtained by polymerizing a polymerization raw material containing a compound having an isocyanato group or an isothiocyanato group and a compound having a hydroxyl group or a mercapto group as main components and containing a polymerization catalyst. Further, when the lens body 12 is molded, an internal mold release agent and an ultraviolet absorber are added to the polymerization raw material. That is, a lens raw material is constituted by the polymerization raw material, the internal mold release agent, and the ultraviolet absorber. The thickness of each lens body 12 is set to approximately 1 mm and 1.5 mm, respectively, the refractive index thereof is 1.6 to 1.7, the Abbe number is 32 to 43, and the specific gravity is 1.3 to 1. 37.

  In the polarizing plastic lens 11, the isocyanato group or isothiocyanate group contained in the polymerization raw material of the lens body 12 and the hydroxyl group of the polyvinyl alcohol resin forming the polarizing film 13 are bonded by a urethane bond or a thiourethane bond. Is formed.

  Examples of the compound having an isocyanato group include an isocyanate compound and an isothiocyanate compound having an isocyanato group, and examples of the compound having an isothiocyanate group include an isothiocyanate compound. In addition, examples of the compound having a hydroxyl group include a hydroxy compound and a mercapto compound having a hydroxyl group, and examples of the compound having a mercapto group include a mercapto compound.

  Specific examples of the isocyanate compound include m-xylylene diisocyanate, p-xylylene diisocyanate, tetrachloro-m-xylylene diisocyanate, hydrogenated xylylene diisocyanate, tetramethylxylylene diisocyanate, hydrogenated diphenylmethane. Diisocyanate, phenyl isocyanate, phenylene diisocyanate, tolylene diisocyanate, ethylphenylene diisocyanate, isopropylphenylene diisocyanate, dimethylphenylene diisocyanate, diethylphenylene diisocyanate, diisopropylphenylene diisocyanate, trimethylbenzene Triisocyanate, benzene triisocyanate, naphthalene diisocyanate, methyl naphthalene diisocyanate, biphenyl dii Cyanate, 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, triphenylmethane triisocyanate, polymeric MDI, naphthalene triisocyanate, diphenylmethane-2,4,4′-triisocyanate, 3- Methyldiphenylmethane-4,6,4′-triisocyanate, 4-methyl-diphenylmethane-3,5,2 ′, 4 ′, 6′-pentaisocyanate, phenylisocyanatomethylisocyanate, phenylisocyanatoethylisocyanate , Tetrahydronaphth Range isocyanate, hexahydrobenzene diisocyanate, hexahydrodiphenylmethane-4,4'-diisocyanate, diphenyl ether diisocyanate, ethylene glycol diphenyl ether diisocyanate, 1,3-propylene glycol diphenyl ether diisocyanate, benzophenone diisocyanate Nert, diethylene glycol diphenyl ether diisocyanate, dibenzofurandiocyanate, carbazole diisocyanate, ethyl carbazole diisocyanate, dichlorocarbazole diisocyanate and other aromatic isocyanates, 1,4-bis (isocyanatomethyl) cyclohexane, cyclohexylisocyanate Narate, isophorone diisocyanate, bis (isocyanatomethyl) cyclohex Sun, dicyclohexylmethane diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, dicyclohexyldimethylmethane diisocyanate, 2,2'-dimethyldicyclohexylmethane diisocyanate, bis (4-isocyanato-n-butylidene) pentaerythritol Diisocyanate, diisocyanate, 2-isocyanatomethyl-3- (3-isocyanatopropyl) -5-isocyanatomethyl-bicyclo [2,2,1] -heptane, 2-isocyanatomethyl-3- (3 -Isocyanatopropyl) -6-isocyanatomethyl-bicyclo [2,2,1] -heptane, 2-isocyanatomethyl-2- (3-isocyanatopropyl) -5-isocyanatomethyl-bicyclo [2,2 , 1] -heptane, 2-iso Anatomethyl-2- (3-isocyanatopropyl) -6-isocyanatomethyl-bicyclo [2,2,1] -heptane, 2-isocyanatomethyl-3- (3-isocyanatopropyl) -6- (2- Isocyanatoethyl) -bicyclo [2,2,1] -heptane, 2-isocyanatomethyl-3- (3-isocyanatopropyl) -6- (2-isocyanatoethyl) -bicyclo [2,1,1] -Heptane, 2-isocyanatomethyl-2- (3-isocyanatopropyl) -5- (2-isocyanatoethyl) -bicyclo [2,2,1] -heptane, 2-isocyanatomethyl-2- (3 Fats such as -isocyanatopropyl) -6- (2-isocyanatoethyl) -bicyclo [2,2,1] -heptane, 1,3,5-tris (isocyanatomethyl) cyclohexane Group isocyanate, butyl isocyanate, ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, 2,2'-dimethylpentane Diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, decamethylene diisocyanate, butene diisocyanate, 1,3-butadiene-1,4-diisocyanate, 2,4,4-trimethylhexa Methylene diisocyanate, 1,6,11-undecatriisocyanate, 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanato-4-isocyanatomethyloctane, 2,5,7-trimethyl-1 , 8-Diisocyanato- 5-isocyanatomethyloctane, bis (isocyanatoethyl) carbonate, bis (isocyanatoethyl) ether, 1,4-butylene glycol dipropyl ether-ω, ω′-diisocyanate, lysine diisocyanatomethyl ester, lysine Triisocyanate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate, 2-isocyanatopropyl-2,6-diisocyanatohexanoate, bis (isocyanatoethyl) benzene, bis (isocyanato Propyl) benzene, α, α, α ′, α′-tetramethylxylylene diisocyanate, bis (isocyanatobutyl) benzene, bis (isocyanatomethyl) naphthalene, bis (isocyanatomethyl) diphenyl ether, bis (isocyanatoethyl) ) Phthalate, mesitiri In addition to aliphatic isocyanates such as N-triisocyanate and 2,6-di (isocyanatomethyl) furan, for example, sulfur-containing aliphatic isocyanates, aromatic sulfide isocyanates, aromatic disulfide isocyanates, aromatic Examples include sulfone isocyanates, aromatic sulfonic acid amides, and sulfur-containing heterocyclic compounds.

  Specific examples of the isothiocyanate compound include phenyl isothiocyanate, 1,2-diisothiocyanatobenzene, 1,3-diisothiocyanatobenzene, 1,4-diisothiocyanatobenzene, 2,4. -Diisothiocyanatotoluene, 2,5-diisothiocyanato-m-xylene, 4,4'-diisothiocyanato-1,1'-biphenyl, 1,1'-methylenebis (4-isothiocyanatobenzene ), 1,1′-methylenebis (4-isothiocyanato-2-methylbenzene), 1,1′-methylenebis (4-isothiocyanato-3-methylbenzene), 1,1 ′-(1,2-ethanediyl) bis ( 4-isothiocyanatobenzene), 4,4′-diisothiocyanatobenzophenone, 4,4′-diisothiocyanato-3,3′-dimethyl Aromatic isothiocyanates such as rubenzophenone, benzanilide-3,44'-diisothiocyanate, diphenyl ether-4,4'-diisothiocyanate, diphenylamine-4,4'-diisothiocyanate, butyl isothiocyanate 1,2-diisothiocyanatoethane, 1,3-isothiocyanatopropane, 1,4-diisothiocyanatobutane, 1,6-diisothiocyanatohexane, p-phenylenediisopropylidenediisothiocyanate Aliphatic isothiocyanates such as aliphatic isothiocyanates such as cyclohexyl isothiocyanate, cyclohexane diisothiocyanate, and heterocyclic rings such as 2,4,6-triisothiocyanato-1,3,5-triazine Isothiocyanate, and also hexanedioyl diisothio Anato, nonane oil diisothiocyanate, carbonic diisothiocyanate, 1,3-benzenedicarbonyldiisothiocyanate, 1,4-benzenedicarbonyldiisothiocyanate, (2,2′-bipyridine) -4 And carbonyl isothiocyanate such as 4'-dicarbonyldiisothiocyanate.

  This isothiocyanate compound includes a compound containing a sulfur atom in addition to the isothiocyanate group. Specific examples of the bifunctional or higher functional isothiocyanate having one or more sulfur atoms in addition to the isothiocyanato group include thiobis (3-isothiocyanatopropane) and thiobis (2-isothiocyanatoethane). ), Sulfur-containing aliphatic isothiocyanates such as dithiobis (2-isothiocyanatoethane), 1-isothiocyanato-4-{(2-isothiocyanato) sulfonyl} benzene, thiobis (4-isothiocyanatobenzene), sulfonylbis ( 4-isothiocyanatobenzene), sulfinylbis (4-isothiocyanatobenzene), dithiobis (4-isothiocyanatobenzene), 4-isothiocyanato-1-{(4-isothiocyanatophenyl) sulfonyl} -2-methoxy -Benzene, 4-methyl-3-isothiocyanatoben Sulfonyl-4'-isothiocyanatophenyl ester, sulfur-containing aromatic isothiocyanates such as 4-methyl-3-isothiocyanatobenzenesulfonylanilide-3'-methyl-4'-isothiocyanate, thiophene-2, And sulfur-containing heterocyclic compounds such as 5-diisothiocyanate and 1,4-dithiane-2,5-diisothiocyanate.

  Examples of the isothiocyanate compound having an isocyanato group include aromatic compounds such as 1-isocyanato-4-isothiocyanatobenzene and 4-methyl-3-isocyanato-1-isothiocyanatobenzene, 1-isocyanato-3- Aliphatic or fat such as isothiocyanatopropane, 1-isocyanato-5-isothiocyanatopentane, 1-isocyanato-6-isothiocyanatohexane, isocyanatocarbonyl isothiocyanate, 1-isocyanato-4-isothiocyanatocyclohexane Cyclic compounds, heterocyclic compounds such as 2-isocyanato-4,5-diisothiocyanato-1,3,5-triazine, 4-isocyanato-4'-isothiocyanatodiphenyl sulfide, 2-isocyanato- 2'-isothiocyanatodiethyldi Compounds that also contain sulfur atoms in addition to isothiocyanate groups such Rufido like.

  In addition, these compounds having an isocyanato group or isothiocyanato group may be used alone or in combination of two or more. As a polymerization raw material of the lens body 12 of the present embodiment, an aromatic isocyanate compound excellent in reactivity with the hydroxyl group of the polyvinyl alcohol resin forming the polarizing film 13 is preferable, and among these, m-xylylene diisocyanate is preferable. Particularly preferred.

  Examples of the hydroxy compound include methanol, benzyl alcohol, phenol, ethoxyethanol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane, and butane. Triol, 1,2-methylglucoside, pentaerythritol, dipentaerythritol, tripentaerythritol, sorbitol, erythritol, threitol, ribitol, arabinitol, xylitol, allitol, mannitol, dolitol, iditol, glycol, inositol, hexanetriol, triglycerol , 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 [5,3,1,1] dodecanol, spiro [3,4] octanediol, butylcyclohexanediol, 1,1'-bicyclohexyl Den Aliphatic alcohols and polyols such as all, cyclohexanetriol, maltitol, lactitol, dihydroxynaphthalene, trihydroxynaphthalene, tetrahydroxynaphthalene, dihydroxybenzene, benzenetriol, biphenyltetraol, pyrogallol, (hydroxynaphthyl) pyrogallol, trihydroxyphenanthrene, Aromatic alcohols and polyols such as bisphenol A, bisphenol F, xylylene glycol and tetrabromobisphenol A, addition reaction products of these with alkylene oxides such as ethylene oxide and propylene oxide, halogenated alcohols such as dibromoneopentyl glycol and the like In addition to polymer polyols such as polyols and epoxy resins, oxalic acid and glutamic acid , Adipic acid, acetic acid, propionic acid, cyclohexanecarboxylic acid, β-oxocyclohexanepropionic acid, dimer acid, phthalic acid, isophthalic acid, salicylic acid, 3-bromopropionic acid, 2-bromoglycol, dicarboxycyclohexane, pyromellitic acid, A condensation reaction product of an organic acid such as butanetetracarboxylic acid or bromophthalic acid and the polyol, an addition reaction product of the polyol and an alkylene oxide such as ethylene oxide or propylene oxide, an alkylene polyamine and ethylene oxide or an alkylene such as propylene oxide Products of addition reaction with oxide, bis- [4- (hydroxyethoxy) phenyl] sulfide, bis- [4- (2-hydroxypropoxy) phenyl] sulfide, bis- [4- ( , 3-dihydroxypropoxy) phenyl] sulfide, bis- [4- (4-hydroxycyclohexyloxy) phenyl] sulfide, bis- [2-methyl-4- (hydroxyethoxy) -6-butylphenyl] sulfide and compounds thereof A compound in which ethylene oxide and / or propylene oxide having an average of 3 molecules or less per hydroxyl group is added to di- (2-hydroxyethyl) sulfide, 1,2-bis- (2-hydroxyethylmercapto) ethane, bis (2-hydroxy) Ethyl) 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), Tetrabu Contains sulfur atoms such as lomobisphenol S, tetramethylbisphenol S, 4,4′-thiobis (6-tert-butyl-3-methylphenol), 1,3-bis (2-hydroxyethylthioethyl) -cyclohexane A polyol etc. are mentioned.

  Examples of the mercapto compound include pentaerythritol tetrakis (3-mercaptopropionate), 1,2-bis (2-mercaptoethylthio) -3-mercaptopropane, 4-mercaptomethyl-3,6-dithio-1, 8-octanedithiol, 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-di Toxibutane-1,2-dithiol, 2-methylcyclohexane-2,3-dithiol, bicyclo [2,2,1] pepta-exo-cis-2,3-dithiol, 1,1-bis (mercaptomethyl) cyclohexane, Bis (2-mercaptoethyl ester) thiomalate, 2,3-dimercaptosuccinic acid (2-mercaptoethyl ester), 2,3-dimercapto-1-propanol (2-mercaptoacetate), 2,3-dimercapto-1 -Propanol (3-mercaptoacetate), diethylene glycol bis (2-mercaptoacetate), diethylene glycol bis (3-mercaptopropionate), 1,2-dimercaptopropyl methyl ether, 2,3-dimercaptopropyl methyl ether, 2 , 2-bis (mercap) Methyl) -1,3-propanedithiol, bis (2-mercaptoethyl) ether, ethylene glycol bis (2-mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), trimethylolpropane tris (2-mercaptoacetate) ), Aliphatic thiols such as trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), 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 (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 (mercap) Ethyl) benzene, 1,2,4-tris (mercaptoethyl) benzene, 1,3,5-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 4-tetrakis (mercaptomethyl) benzene, 1,2,3,5-tetrakis (mercaptomethyl) benzene, 1,2,4 -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′-dimercapto Biphenyl, 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 thiols such as 2,4-di (p-mercaptophenyl) pentane, etc., for example, halogen-substituted aromatic thiols, thiols containing heterocycles, Aromatic thiols containing sulfur atoms in addition to mercapto groups, sulfur atoms in addition to mercapto groups Aliphatic thiol, heterocyclic compounds containing a sulfur atom other than mercapto group.

  Examples of the mercapto compound having a hydroxyl group include 2-mercaptoethanol, 3-mercapto-1,2-propanediol, glycerol 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-mercapto Propionate), pentaerythritol mono (3-mercaptopropionate), pentaerythritol bis (3-mercaptopropionate), pentaerythritol tris (thioglycolate), pentaerythritol Ntakis (3-mercaptopropionate), hydroxymethyl-tris (mercaptoethylthiomethyl) methane, 1-hydroxyethylthio-3-mercaptoethylthiobenzene, 4-hydroxy-4'-mercaptodiphenylsulfone, 2- (2 -Mercaptoethylthio) ethanol, dihydroxyethyl sulfide mono (3-mercaptopropionate), dimercaptoethane mono (sulcylate), hydroxyethylthiomethyltris (mercaptoethylthio) methane and the like.

  Furthermore, you may use the chlorine substitution body of these active hydrogen compounds, and the halogen substitution body of a bromine substitution body. Each of the above active hydrogen compounds may be used alone or in combination of two or more. The polymerization raw material for the lens body 12 of the present embodiment is preferably a mercapto compound that enables the lens body 12 to have a high refractive index, and among them, a polyfunctional mercapto compound having at least four mercapto groups in one molecule. Pentaerythritol tetrakis (3-mercaptopropionate) or 1,2-bis (2-mercaptoethylthio) -3-mercaptopropane is preferred.

  The blending ratio of the compound having the isocyanato group (—NCO) or isothiocyanato group (—NCS) and the compound having a hydroxyl group (—OH) or mercapto group (—SH), which is the polymerization raw material of the present embodiment, is [ The functional group equivalent ratio of (-NCO) + (-NCS)] / [(-OH) + (-SH)] is preferably 0.5 to 1.5, and more preferably 0.8 to 1.2.

  When the functional group equivalent ratio is less than 0.5, there is almost no functional group (-NCO or -NCS) that reacts with the hydroxyl group contained in the resin forming the polarizing film 13, and as a result, the lens There is a possibility that no urethane bond or thiourethane bond is formed between the body 12 and the polarizing film 13. On the other hand, when the functional group equivalent ratio is larger than 1.5, the number average molecular weight of the resin formed from the compound having an isocyanato group or an isothiocyanato group is increased, and accordingly, the polymerization raw material has a high viscosity. . For this reason, when the lens body 12 is molded, the time required for deaeration, which will be described later, becomes long, and the production efficiency may be reduced.

  Next, examples of the polymerization catalyst used in the present embodiment include tertiary phosphine, tertiary amine, and Lewis acid. The amount of the polymerization catalyst used is preferably in the range of 0.0005 to 5 mass%, more preferably 0.001 to 2 mass%, based on the total amount of the compound having an isocyanato group or isothiocyanato group and the active hydrogen compound. Is set to

  When the amount used is less than 0.0005% by mass, the progress of the polymerization reaction may be reduced. On the other hand, when it is greater than 5% by mass, the reaction proceeds during the preparation of the polymerization raw material, and the viscosity is May increase.

  Examples of the tertiary phosphine include tri-n-butylphosphine, triphenylphosphine, trimethylphosphine, triethylphosphine, tripropylphosphine, triisopropylphosphine, trit-butylphosphine, tricyclohexylphosphine, tribenzylphosphine, diphenylmethylphosphine, Dimethylphenylphosphine, diethylphenylphosphine, tri-o-tolylphosphine, trimesitylphosphine, 1,2-bis (dimethylphosphino) ethane, 1,4-bis (diphenylphosphino) butane, 2,3-bis (diphenylphosphine) Fino) butane, 1,2-bis (diphenylphosphino) ethane, bis (diphenylphosphino) methane, 1,3-bis (diphenylphosphino) propane, 1,2-bis (diphenyl) Niruhosufino) propane, 1,5-bis (diphenylphosphino) pentane, and the like.

  Examples of the tertiary amine include N, N-dimethylcyclohexylamine, N, N-diethylcyclohexylamine, tributylamine, triethylamine, tripropylamine, dipropylethylamine, trihexylamine, dimethylcyclohexylamine, dicyclohexylmethylamine, Cyclohexylamine, diethylcyclohexylamine, dicyclohexylethylamine, dipropylcyclohexylamine, dicyclohexylpropylamine, dibutylcyclohexylamine, dicyclohexylbutylamine, N, N-dimethylbenzylamine, N, N-diethylbenzylamine, N, N-dipropylbenzylamine N, N-dibutylbenzylamine, N-methyldibenzylamine, 2-dimethylaminomethylphenol 2,4,6-tris (N, N-dimethylaminomethyl) phenol, triethylenediamine and the like.

  Examples of Lewis acids include dibutyltin dichloride, dimethyltin dichloride, trimethyltin chloride, tributyltin chloride, triphenyltin chloride, dibutyltin sulfide, di (2-ethylhexyl) tin oxide, tetrafluorotin, tetrachlorotin, and four. Tin compounds such as tin bromide, tetraiodotin, methyltin trichloride, butyltin trichloride, zinc compounds such as zinc chloride, acetylacetone zinc and zinc dibutyldithiocarbamate, iron compounds such as iron chloride and acetylacetone iron, alumina , Aluminum compounds such as aluminum fluoride, aluminum chloride and triphenylaluminum, titanium compounds such as tetrachlorotitanium, antimony compounds such as trichloroantimony, pentachloroantimony and dichlorotriphenylantimony Uranium compounds such as nitrouranium, cadmium compounds such as nitrocadmium, cobalt compounds such as cobalt chloride and cobalt bromide, thorium compounds such as nitrothorium, mercury compounds such as diphenylmercury, nickel compounds such as nickelocene Compounds, calcium compounds such as nitrocalcium and calcium acetate, vanadium compounds such as trichlorovanadium, copper compounds such as copper chloride and copper iodide, manganese compounds such as manganese chloride, zirconium compounds such as zirconium chloride, Examples thereof include arsenic compounds such as phenylarsenic and trichloroarsenic, and boron compounds such as boron trifluorolide.

  As the polymerization catalyst, tertiary phosphine, tertiary amine and Lewis acid may be used singly, but a combined catalyst of tertiary phosphine and Lewis acid or a combined catalyst of tertiary amine and Lewis acid may be used. preferable. Of the combined catalysts, a combination of tri-n-butylphosphine and dibutyltin dichloride is particularly preferable.

  The internal mold release agent is used for the purpose of preventing the molded product from adhering to the inner surface of the mold, which will be described later, after molding the lens body 12 and making it difficult to release the mold. Specific examples thereof include acidic phosphoric acid alkyl esters (Zelec UN manufactured by Du Pont), isopropyl acid phosphate, diisopropyl acid phosphate, butyl acid phosphate, dibutyl acid phosphate, octyl acid phosphate, dioctyl acid phosphate, Examples include isodecyl acid phosphate, diisodecyl acid phosphate, tridecyl acid phosphate and bis (tridecyl acid phosphate). In this embodiment, it is preferable to use Zelec UN among these, and the amount of use is in the range of 1 to 5000 ppm.

  The ultraviolet absorber is used for the purpose of absorbing ultraviolet rays that adversely affect the cornea and lens of the eye when a polarizing lens is used. Specific examples thereof include 2- (2-hydroxy-5-tert-butylphenyl) benzotriazole, 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chloro-2H-benzotriazole. 2- (2-hydroxy-5-tert-octylphenyl) -2H-benzotriazole, 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chloro-2H-benzotriazole, 2 -(2-hydroxy-5-methylphenyl) -2H-benzotriazole, 2- (2-hydroxy-3,5-di-tert-butylphenyl) benzotriazole, 5-chloro-2- (3,5-di -Tert-butyl-2-hydroxyphenyl) -2H-benzotriazole, 2- (3,5-di-tert-penty -2-hydroxyphenyl) -2H-benzotriazole, 2- (3,5-di-tert-butyl-2-hydroxyphenyl) -2H-benzotriazole, 2- (2H-benzotriazol-2-yl) -4 -Methyl- (3,4,5,6-tetrahydrophthalimidylmethyl) phenol and the like. In this embodiment, among these, 2- (2-hydroxy-5-methylphenyl) -2H-benzotriazole, 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chloro-2H -Benzotriazole or 2- (2-hydroxy-5-tert-octylphenyl) -2H-benzotriazole is preferably used, and the amount used is the above-mentioned compound having an isocyanato group or isothiocyanato group and a hydroxyl group or a mercapto group. 0.1-1.0 mass% is preferable with respect to the total amount with a compound to have, and 0.3-0.8 mass% is further more preferable.

Next, the manufacturing apparatus (molding die 21) and manufacturing method of the polarizing plastic lens 11 will be described.
As shown in FIG. 2, the mold 21 constitutes a lower mold, and includes a gasket 23 having an annular support protrusion 22 extending inwardly from the inner peripheral surface of the cylinder, and a first lower mold 24 attached to the lower part thereof. A cylindrical fixing member 25 disposed on the annular support protrusion 22 and an upper molding die are configured, and the first upper mold 26 and the like are disposed in the first fixing member 25.

  The first lower mold 24 and the first upper mold 26 are formed of a glass material into a curved shape that gently swells downward in accordance with the curvature of the lens body 12 to be manufactured. The upper and lower openings are sealed. The annular support ridge 22 is formed to be slightly inclined downward, and a space formed by the tip surface thereof and the inner surface of the first lower mold 24 is a first molding recess 27. Further, a locking portion 25a extending slightly inclined downward is provided on the inner peripheral surface of the first fixing member 25 along the circumferential direction, and is constituted by the front end surface and the inner surface of the first upper mold 26. The second space is a second molding recess 28.

  When the polarizing plastic lens 11 is manufactured, first, the lens raw material is deaerated under vacuum, and then the first molding recess 27 is filled with a predetermined amount. Thereby, the first layer is formed. Next, the polarizing film 13 is placed on the first layer so that the peripheral portion of the polarizing film 13 that has been previously bent according to the curvature of the lens body 12 to be manufactured is positioned on the annular support ridge 22. 1 The fixing member 25 is placed on the peripheral edge of the polarizing film 13. At this time, the polarizing film 13 is fixed in the gasket 23 by the first fixing member 25. Subsequently, a predetermined amount of the lens material is filled in the second molding recess 28. Thereby, the second layer is formed. Thereafter, the first upper mold 26 is disposed in the first fixing member 25, and both the molds 24 and 26 are fixed by the clips 29.

  Next, the mold 21 is gradually heated to about 140 ° C. to polymerize and cure the lens materials of the first layer and the second layer. Thereafter, the clip 29 is removed, and then the molds 24 and 26, the first fixing member 25, and the gasket 23 are released, whereby the polarizing plastic lens 11 is manufactured. At this time, since the internal mold release agent is contained in the lens material, the molds 24 and 26, the first fixing member 25, and the gasket 23 are easily released.

The effects exhibited by the first embodiment will be described below.
In the polarizing plastic lens 11 of the present embodiment, the isocyanato group or isothiocyanato group contained in the resin forming the lens body 12 and the hydroxyl group contained in the resin forming the polarizing film 13 are urethane bonds or thiourethane bonds. Are formed in a coupled state. That is, since the lens body 12 and the polarizing film 13 are directly bonded by chemical bonding, the adhesive force between them is improved. As a result, even when the thermal expansion coefficients of the lens body 12 and the polarizing film 13 are different from each other, it is possible to effectively suppress the peeling of the polarizing film 13 from the lens body 12 without decreasing the adhesive force due to environmental changes. Can do.

  In the manufacturing method of the polarizing plastic lens 11, the lens body 12 is integrally formed on both surfaces of the polarizing film 13. For this reason, after forming the pair of lens bodies 12, an adhesive is applied to the inner surfaces thereof, whereby the polarizing plastic lens 11 is easily manufactured as compared with the type in which the polarizing film 13 is sandwiched between the two lens bodies 12. be able to. In addition, since the lens body 12 is molded in a state where the polarizing film 13 is fixed by the fixing member, wrinkles and distortion of the polarizing film 13 are suppressed, and the function of the polarizing plastic lens 11 is more effective. Can be demonstrated.

  In this embodiment, as one of the main components of the polymerization raw material of the lens body 12, it is excellent in reactivity with the hydroxyl group of the resin forming the polarizing film 13, and m-xylyl having two isocyanato groups in one molecule. Range isocyanate is used. That is, a urethane bond is easily formed between the hydroxyl group and the crosslink density is increased, so that the adhesion of the polarizing film 13 to the lens body 12 can be improved.

  Furthermore, in this embodiment, a polyfunctional mercapto compound is used as one of the main components of the polymerization raw material of the lens body 12. That is, the refractive index of the lens body 12 can be increased by a plurality of sulfur atoms contained in the lens body 12, and accordingly, the lens body 12 can be thinned.

  The compounding ratio of the compound having the isocyanato group or isothiocyanato group and the compound having a hydroxyl group or a mercapto group is [(−NCO) + (− NCS)] / [(− OH) + (− SH)]. The functional group equivalent ratio is set to 0.5 to 1.5. For this reason, in parallel with the polymerization curing reaction of the polymerization raw material, a urethane bond or a thiourethane bond is reliably formed between the respective resins forming the lens body 12 and the polarizing film 13. As a result, peeling of the polarizing film 13 from the lens body 12 can be more effectively suppressed.

(Second Embodiment)
Since the second embodiment is different from the first embodiment only in the method of manufacturing the polarizing plastic lens 11, the difference will be mainly described.

  In the manufacturing method of the polarizing plastic lens 11 in the present embodiment, first, a first step of forming an intermediate molded body in which the lens body 12 is provided on one side surface of the polarizing film 13, and the lens body 12 on the other side surface of the polarizing film 13. It consists of the 2nd process to form.

  As shown in FIG. 5 (a), the molding die 21 used in the first step is a second lower mold 41 having a bottomed cylindrical shape as a molding die and a circle disposed in the opening thereof. The plate-shaped second upper mold 42 and an annular fixing member 25 disposed on the bottom surface of the second lower mold 41 are configured. The bottom of the second lower mold 41 and the second upper mold 42 are formed in a curved surface shape that gently swells upward. The fixing member 25 is inclined upward as it goes inward, and has a shape that follows the peripheral edge of the bottom surface of the second lower mold 41.

  In addition, as shown in FIG. 5B, in the second step, the third lower mold 43 as a molding die used for forming the lens body 12 on the other side surface of the polarizing film 13 is The shape is the same as that of the second lower mold 41.

  When the polarizing plastic lens 11 is manufactured, as shown in FIG. 5A, the polarizing film 13 is first disposed on the inner bottom surface of the second lower mold 41, and then the fixing member 25 is disposed on the peripheral edge of the polarizing film 13. To fix the polarizing film 13 in the second lower mold 41. Subsequently, the second upper mold 42 is fitted into the opening of the second lower mold 41, and this is clamped to the second lower mold 41. And the said lens raw material is filled in the 4th shaping | molding recessed part 45 comprised by one side surface of the polarizing film 13, and the inner surface of the 2nd upper mold 42, and this is superposed | polymerized and hardened. As a result, the intermediate molded body is obtained.

  Next, as shown in FIG. 5B, only the second lower mold 41 is released, and the intermediate molded body is used as a third lower mold as a molding die with the other side surface of the polarizing film 13. It arrange | positions so that it may have the 5th shaping | molding recessed part 46 between the inner bottom surfaces of 43. Then, in a state where the third lower mold 43 is clamped to the second upper mold 42, the fifth raw material 46 is filled with a lens material, and this is polymerized and cured. Then, the polarizing plastic lens 11 is manufactured by releasing the molds 42 and 43 and the first fixing member 25.

  Therefore, in the manufacturing method of the polarizing plastic lens 11 of this embodiment, since one side of the polarizing film 13 made of polyvinyl alcohol resin is sequentially immersed in the lens material, the entire polarizing film 13 is not immersed in the lens material. For this reason, it can suppress that the polarizing film 13 softens and flatness is impaired.

(Third embodiment)
In the third embodiment, after molding a molded body having the same shape as the polarizing plastic lens 11 by polymerizing and curing the lens raw material in the first or second embodiment, the molded body is subjected to an annealing treatment. The polarizing plastic lens 11 is manufactured by applying.

  This annealing treatment is performed at a temperature within a range from the glass transition temperature of the molded body to a temperature 20 ° C. higher than the glass transition temperature. Here, when the temperature of the annealing treatment is lower than the glass transition temperature, the residual stress of the molded body is not sufficiently removed, and there is a possibility that a suitable strength cannot be obtained. On the other hand, when the temperature of annealing treatment is higher than the said range, the distortion | strain (polymerization distortion) and deformation | transformation by superposition | polymerization of the lens body 12 may not fully be suppressed. Therefore, in the polarizing plastic lens 11 subjected to the annealing treatment in the temperature range of the present embodiment, it is possible to suppress polymerization distortion and deformation of the lens body 12 while ensuring a suitable strength.

Each embodiment can be modified and embodied as follows.
(1) You may manufacture the polarizing plastic lens 11 of 1st Embodiment with the manufacturing method shown below. That is, the polarizing film 13 is first fixed in the gasket 23, and then the molds 24 and 26 are disposed in the gasket 23. Subsequently, a lens raw material is filled in a third molding recess formed between the inner surface of the first lower mold 24 and the inner surface of the first upper mold 26, and this is polymerized and cured in the same manner as described above.

  (2) The polarizing plastic film 31 shown in FIG. 3 can be manufactured using the same manufacturing method as in the first embodiment. The polarizing plastic film 31 includes a pair of film bodies 32 having different thicknesses provided on both surfaces of the polarizing film 13. The film raw material of the film body 32 is the same as the lens raw material of the lens body 12, and the isocyanato group or isothiocyanato group and the hydroxyl group of the resin forming the polarizing film 13 are bonded by a urethane bond or a thiourethane bond. It is formed in a combined state. The thickness of the polarizing plastic film 31 is set to about 300 μm, and is used for image display bodies such as a liquid crystal display (LCD) and a plasma display (PDP). As shown in FIG. 4, both molds 24 and 26 constituting the mold 21, the annular support protrusion 22 of the gasket 23, and the locking portion 25 a of the first fixing member 25 are formed in a flat shape.

  When comprised in this way, the adhesive force of the film body 32 and the polarizing film 13 improves, As a result, peeling of the polarizing film 13 from the film body 32 can be suppressed. Moreover, since the film body 32 is integrally formed on both surfaces of the polarizing film 13, the polarizing plastic film 31 can be easily manufactured. In addition, you may manufacture this polarizing plastic film 31 using the method shown in said (1).

  (3) The said polarizing plastic film 31 can be manufactured using the manufacturing method similar to 2nd Embodiment. At this time, the bottoms of the second lower mold 41 and the third lower mold 43, the fixing member 25, and the second upper mold 42 are formed flat. When configured in this manner, one surface of the polarizing film 13 made of polyvinyl alcohol resin is sequentially immersed in the lens material, so that the entire polarizing film 13 is not immersed in the lens material. For this reason, it can suppress that the polarizing film 13 softens and flatness is impaired.

  (4) In the manufacturing method of the polarizing plastic film 31 as described in said (2) and (3), the annealing process similar to 3rd Embodiment may be employ | adopted. When comprised in this way, the superposition | polymerization distortion and deformation | transformation of the film body 32 can also be suppressed suitably, suppressing peeling of the polarizing film 13 from the film body 32. FIG.

  (5) You may change the manufacturing method of the polarizing plastic lens 11 of 2nd Embodiment as follows. That is, after the intermediate molded product is formed, the second lower mold 41, the fixing member 25, and the second upper mold 42 are released, and then another lower mold, a fixing member, and an upper mold having shapes different from these. An intermediate molded product is assembled to the polarizing plastic lens 11 as in the second embodiment. In addition, you may manufacture the said polarizing plastic film 31 using this method.

  (6) Furthermore, the manufacturing method of the polarizing plastic lens 11 of the second embodiment may be changed as follows. That is, after molding the intermediate molded body and releasing the second lower mold 41, a lens material is applied or sprayed on the other side surface of the polarizing film 13. Next, as in the second embodiment, the third lower mold 43 is disposed at a predetermined position, and the lens material is polymerized and cured. In addition, you may manufacture the said polarizing plastic film 31 using this method.

  (7) The shapes of the bottom of the first lower mold 24 and the first upper mold 26 constituting the molding die 21 of the first embodiment may be formed into a curved shape that gently bulges upward. At this time, the annular support protrusion 22 and the locking portion 25a of the first fixing member 25 are formed slightly inclined upward.

  (8) The bottoms of the second lower mold 41 and the third lower mold 43 constituting the molding die 21 of the second embodiment, and the shape of the second upper mold 42 are formed in a curved shape that gently bulges downward. Also good. At this time, the fixing member 25 is formed to be inclined downward as it goes inward.

  (9) Instead of the third lower mold 43 of the second embodiment, a lower mold obtained by polymerizing and curing the lens raw material may be used. In this case, the lens raw material used in the manufacturing process of the polarizing plastic lens 11 can be used together, and the manufacturing cost can be reduced.

(10) The fixing member in both embodiments may be changed to, for example, an adhesive tape.
(11) In addition, the lens body 12 is subjected to surface polishing treatment and antistatic treatment according to purposes such as improvement of wear resistance, improvement of anti-fogging property, provision of high strength, improvement of chemical resistance, antireflection and fashionability. You may perform a process, a hard-coat process, a non-reflective coating process, a dyeing process, a light control process, etc. At this time, the polarizing plastic lens 11 is used for protective goggles, fashion glasses, and the like in sports goggles, welding work, organic solvent handling work, and the like.

  (12) A polarizing film 13 produced by impregnating a polyvinyl alcohol resin with a dichroic dye may be used. As this type of dichroic dye, Direct Black 17, 19, 154, Direct Brown 44, 106, 195, 210, 223, Direct Red 2, 23, 28, 31, 37, 39, 79, 81, 240, 242,247, Direct Blue 1,15,22,78,90,98,151,168,202,236,249,270, Direct Violet 9,12,51,98, Direct Green 1,85, Direct Yellow 8, 12, 44, 86, 87, direct orange 26, 39, 106, 107 and the like.

Next, the present invention will be described more specifically with reference to examples and comparative examples.
(Examples 1-6, Comparative Example 1)
With respect to the polarizing plastic lens 11 obtained in each of the following examples, the physical properties shown in the following (1) to (3) were evaluated. However, regarding Example 1 and Example 2, the physical property evaluation of (3) was not performed. In each example, “part” means “part by mass”. In each of the following examples, the lens body 12 is not formed on one surface of the polarizing film 13 in order to make it easy to confirm the adhesion of the polarizing film 13 to the lens body 12. And the measurement result of each physical property evaluation is shown in Table 1 together with the refractive index, Abbe number, specific gravity, and glass transition temperature of the lens body 12 of the polarizing plastic lens 11 obtained in each example.

Example 1
43.5 parts (0.23 mol, isocyanato group 0.46 equivalent) of m-xylylene diisocyanate as a polymerization raw material and 56.5 parts (0.115 mol, mercapto) of pentaerythritol tetrakis (3-mercaptopropionate) 0.46 equivalents), 0.01% by weight of dibutyltin dichloride as a polymerization catalyst, 0.1% by weight of Zelec UN as an internal mold release agent, and 2- (2-hydroxy-5-methylphenyl) as an ultraviolet absorber A lens raw material was prepared by mixing 0.02% by mass of -2H-benzotriazole. Next, the polarizing plastic lens 11 was manufactured by the manufacturing method of the first embodiment. At this time, the functional group equivalent ratio of m-xylylene diisocyanate to pentaerythritol tetrakis (3-mercaptopropionate) is 1.0.

(Example 2)
52 parts (0.276 mol, isocyanato group 0.552 equivalent) of m-xylylene diisocyanate and 48 parts of 1,2-bis (2-mercaptoethylthio) -3-mercaptopropane (0.184 mol) as polymerization raw materials , Mercapto group 0.92 equivalent), 0.015% by weight of dibutyltin dichloride as a polymerization catalyst, 0.1% by weight of Zelec UN as an internal mold release agent, and 2- (2-hydroxy-5-methyl as an ultraviolet absorber) A lens raw material was prepared by mixing 0.024 mass% of phenyl) -2H-benzotriazole. Next, the polarizing plastic lens 11 was manufactured by the above-described manufacturing method using the mold 21 shown in FIG. 2, and the performance evaluation was performed according to the following evaluation criteria (1) and (2) in the same manner as in Example 1. . At this time, the functional group equivalent ratio of m-xylylene diisocyanate to 1,2-bis (2-mercaptoethylthio) -3-mercaptopropane is 1.0.

(Example 3)
The lens material prepared in Example 1 was sufficiently degassed and injected into the mold 21, and then the polarizing film 13 was placed at a predetermined position. Next, the mold 21 was gradually heated from 30 ° C. to 120 ° C., and the lens raw material was polymerized and cured over 24 hours. Thereafter, the mold 21 was gradually cooled to obtain a molded body. Then, the polarizing plastic lens 11 was manufactured by performing the annealing process for 1 hour at 100 degreeC with respect to this molded object.

  Here, the glass transition temperature of the lens body 12 in Example 3 is 85 ° C. (see Table 1). That is, in Example 3, the annealing treatment was performed at a temperature within a predetermined range from the glass transition temperature to a temperature 20 ° C. higher than the glass transition temperature.

Example 4
In contrast to Example 2, the ultraviolet light absorber was changed to 0.05% by mass of 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chloro-2H-benzotriazole. Prepared. Then, the lens material was sufficiently degassed and injected into the mold 21, and then the polarizing film 13 was placed at a predetermined position. Next, the mold 21 was gradually heated from 30 ° C. to 120 ° C., and the lens raw material was polymerized and cured over 24 hours. Thereafter, the mold 21 was gradually cooled to obtain a molded body. Then, the polarizing plastic lens 11 was manufactured by performing the annealing process for 1 hour at 100 degreeC with respect to this molded object. In addition, since the glass transition temperature of the lens body 12 of the fourth embodiment is 90 ° C., the annealing process is performed at a temperature within the predetermined range.

(Example 5)
1,4-bis (isocyanatomethyl) cyclohexane 96.1 parts (0.5 mol, isocyanato group 1.0 equivalent) and 1,2-bis (2-mercaptoethylthio) -3-mercaptopropane as polymerization raw materials 87 parts (0.33 mol, mercapto group 1.0 equivalent), 0.01% by weight of dibutyltin dichloride as a polymerization catalyst, 0.1% by weight of Zelec UN as an internal mold release agent, and 2- ( 2-hydroxy-5-tert-octylphenyl) -2H-benzotriazole (0.05% by mass) was mixed to prepare a lens material. Then, after sufficiently defoaming the lens material and injecting it into the mold 21, the polarizing film 13 was placed at a predetermined position. Next, the mold 21 was gradually heated from 30 ° C. to 100 ° C., and the lens raw material was polymerized and cured over 24 hours. Thereafter, the mold 21 was gradually cooled to obtain a molded body. Then, the polarizing plastic lens 11 was manufactured by performing the annealing process for 1 hour at 100 degreeC with respect to this molded object. At this time, the functional group equivalent ratio of 1,4-bis (isocyanatomethyl) cyclohexane to 1,2-bis (2-mercaptoethylthio) -3-mercaptopropane is 1.0. In addition, since the glass transition temperature of the lens body 12 of Example 5 is 95 ° C., the annealing process is performed at a temperature within the predetermined range.

(Example 6)
1,4-bis (isocyanatomethyl) cyclohexane 96.1 parts (0.5 mol, isocyanato group 1.0 equivalent) and 1,2-bis (2-mercaptoethylthio) -3-mercaptopropane as polymerization raw materials 87 parts (0.33 mol, mercapto group 1.0 equivalent), 0.02% by mass of dibutyltin dichloride as a polymerization catalyst, 0.1% by mass of Zelec UN as an internal mold release agent, and 2- ( 2-hydroxy-5-tert-octylphenyl) -2H-benzotriazole (0.05% by mass) was mixed to prepare a lens material. Then, after sufficiently defoaming the lens material and injecting it into the mold 21, the polarizing film 13 was placed at a predetermined position. Next, the mold 21 was gradually heated from 30 ° C. to 130 ° C., and the lens raw material was polymerized and cured over 24 hours. Thereafter, the mold 21 was gradually cooled to obtain a molded body. Then, the polarizing plastic lens 11 was manufactured by performing the annealing process for 1 hour at 120 degreeC with respect to this molded object. At this time, the functional group equivalent ratio of 1,4-bis (isocyanatomethyl) cyclohexane to 1,2-bis (2-mercaptoethylthio) -3-mercaptopropane is 1.0. In addition, since the glass transition temperature of the lens body 12 of Example 6 is 110 ° C., the annealing process is performed at a temperature within the predetermined range.

(Comparative Example 1)
100 parts (0.365 mol) of diethylene glycol bisallyl carbonate as a polymerization raw material, 3.0% by mass of diisopropyl peroxydicarbonate as a radical polymerization initiator, and 0.05 of 2-hydroxy-4-methoxybenzophenone as an ultraviolet absorber A lens raw material was prepared by mixing mass%. Next, the polarizing plastic lens 11 was manufactured using the mold 21 by the manufacturing method of the first embodiment.

(1) Impact resistance evaluation The polarizing plastic lens 11 obtained in each example is grasped by hand, and the polarizing plastic lens 11 is struck against a desk a plurality of times to confirm the adhesion state of the polarizing film 13 to the lens body 12. did. Here, the evaluation was made in two stages: the polarizing film 13 did not peel from the lens body 12 and adhered (◯), and the polarizing film 13 peeled from the lens body 12 (×).

(2) Water resistance evaluation After the polarizing plastic lens 11 obtained in each example was immersed in warm water at 50 ° C. for 15 hours, the polarizing film 13 was immersed in one side of the polarizing plastic lens 11 in warm water. The adhesion state of the polarizing film 13 to the lens body 12 was confirmed by rubbing the surface of the film with a fingertip. Here, there was no color fading, no peeling (◎), partial color fading but no peeling (◯), partial color fading and peeling (x).

(3) Presence or absence of polymerization distortion and deformation The presence or absence of polymerization distortion of the polarizing plastic lens 11 obtained in each example was observed using a strain gauge. Further, the polarizing plastic lens 11 was placed on a table so that the curved surface thereof was convex upward, and an external force was applied to the peripheral portion of the polarizing plastic lens 11. The degree of rocking of the polarizing plastic lens 11 at this time was visually evaluated, and the presence or absence of deformation of the polarizing plastic lens 11 was confirmed. Here, the evaluation was made in three stages: no polymerization strain and deformation (◯), slight polymerization strain and deformation (Δ), and significant polymerization strain and deformation (×).

表１に示すように、実施例１〜実施例６ではイソシアナト基とヒドロキシル基とのウレタン結合を伴って偏光膜１３とレンズ体１２とが強固に接着されているため、耐衝撃性及び耐水性について良好な結果が得られた。即ち、レンズ体１２からの偏光膜１３の剥離が好適に抑制された。また実施例３〜実施例５ではアニーリング処理によりレンズ体１２の重合歪み及び変形を十分に抑制することができた。しかしながら、実施例６では、他の実施例に比べてアニーリング処理の温度が高いため、レンズ体１２の重合歪み及び変形を十分に抑制することができなかった。このため、本発明におけるアニーリング処理の温度は、各例のガラス転移温度を考慮した結果、該ガラス転移温度より高く、１１０℃以下であるのが好ましい。

As shown in Table 1, in Examples 1 to 6, since the polarizing film 13 and the lens body 12 are firmly bonded together with a urethane bond between an isocyanato group and a hydroxyl group, impact resistance and water resistance are reduced. Good results were obtained for. That is, peeling of the polarizing film 13 from the lens body 12 was suitably suppressed. In Examples 3 to 5, the polymerization distortion and deformation of the lens body 12 could be sufficiently suppressed by the annealing process. However, in Example 6, since the temperature of the annealing process was higher than in the other examples, the polymerization distortion and deformation of the lens body 12 could not be sufficiently suppressed. For this reason, as a result of considering the glass transition temperature of each example, the temperature of the annealing treatment in the present invention is preferably higher than the glass transition temperature and 110 ° C. or lower.

  On the other hand, in Comparative Example 1, since no chemical bond is particularly formed between the diethylene glycol bisallyl carbonate resin forming the lens body 12 and the polyvinyl alcohol resin forming the polarizing film 13, the adhesion between the polarizing film 13 and the lens body 12 is not caused. As a result, the polarizing film 13 is easily peeled off. Therefore, in the comparative example 1, the impact resistance and water resistance of the polarizing plastic lens 11 were not sufficiently obtained.

Further, the technical idea that can be grasped from the embodiment will be described below.
(1) The compounding ratio of the compound having the isocyanato group or isothiocyanato group and the compound having a hydroxyl group or a mercapto group is 0.5 to 1 as a functional group equivalent ratio of the isocyanato group and the isothiocyanato group to the hydroxyl group and the mercapto group. The polarizing plastic lens according to claim 1, which is set to .5. When comprised in this way, a urethane bond or a thiourethane bond can be formed reliably.

  (2) The compounding ratio of the compound having the isocyanato group or isothiocyanato group and the compound having a hydroxyl group or a mercapto group is 0.5 to 1 as a functional group equivalent ratio of the isocyanato group and the isothiocyanato group to the hydroxyl group and the mercapto group. The polarizing plastic film according to claim 2, which is set to .5. When comprised in this way, a urethane bond or a thiourethane bond can be formed reliably.

  (3) The polarizing plastic lens according to claim 1, wherein the compound having an isocyanato group and the compound having a mercapto group are main components of a polymerization raw material of the lens body. When comprised in this way, the adhesiveness of the polarizing film to a lens body can be improved.

  (4) The polarizing plastic lens according to (3), wherein the compound having an isocyanato group is an aromatic isocyanate. When comprised in this way, the adhesiveness of the polarizing film to a lens body can further be improved.

  (5) The polarizing plastic lens according to (3), wherein the compound having a mercapto group is a polyfunctional mercapto compound having at least four mercapto groups in one molecule. When configured in this way, it is possible to increase the refractive index and the thickness of the lens body.

  (6) The polarizing plastic film according to claim 2, wherein the compound having the isocyanato group and the compound having a mercapto group are used as a main component of a polymerization raw material of the film body. When comprised in this way, the adhesiveness of the polarizing film to a film body can be improved.

  (7) The polarizing plastic film according to (6), wherein the compound having an isocyanato group is an aromatic isocyanate. When comprised in this way, the adhesiveness of the polarizing film to a film body can further be improved.

  (8) The polarizing plastic film according to (6), wherein the compound having a mercapto group is a polyfunctional mercapto compound having at least four mercapto groups in one molecule. When comprised in this way, the high refractive index and thickness reduction of a film body can be achieved.

  (9) The third forming recess is filled with a polymerization raw material, and then the polymerization raw material is polymerized and cured to form a molded body, and then the molded body is heated to 20 ° C. from the glass transition temperature to the glass transition temperature. The method for producing a polarizing plastic lens according to claim 3, wherein the annealing treatment is performed at a temperature within a range of up to. When comprised in this way, distortion and deformation | transformation of the lens body by superposition | polymerization can be suppressed.

  (10) Filling the third molding recess with a polymerization raw material, and then polymerizing and curing the polymerization raw material to form a molded body, and then forming the molded body at a temperature 20 ° C. higher than the glass transition temperature from the glass transition temperature. The method for producing a polarizing plastic film according to claim 4, wherein the annealing treatment is performed at a temperature within a range of up to. When comprised in this way, distortion and a deformation | transformation of the film body by superposition | polymerization can be suppressed.

  (11) The new forming recess is filled again with a polymerization raw material, and this is polymerized and cured to form a molded body, and then the molded body is heated from its glass transition temperature to a temperature 20 ° C. higher than the glass transition temperature. The method for producing a polarizing plastic lens according to claim 5, wherein the annealing treatment is performed at a temperature within the range. When comprised in this way, distortion and deformation | transformation of the lens body by superposition | polymerization can be suppressed.

  (12) The new forming recess is filled again with a polymerization raw material, and this is polymerized and cured to form a molded body. Then, the molded body is heated from its glass transition temperature to a temperature 20 ° C. higher than the glass transition temperature. The method for producing a polarizing plastic film according to claim 6, wherein the annealing treatment is performed at a temperature within the range of 5. When comprised in this way, distortion and a deformation | transformation of the film body by superposition | polymerization can be suppressed.

The sectional side view which shows a polarizing plastic lens. FIG. 3 is a side sectional view showing a mold for forming the polarizing plastic lens of the first embodiment. The sectional side view which shows a polarizing plastic film. The sectional side view which shows the shaping | molding die of the polarizing plastic film of 1st Embodiment. (A) And (b) is a sectional side view which shows the shaping | molding die of the polarizing plastic lens of 2nd Embodiment.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 11 ... Polarized plastic lens, 12 ... Lens body, 13 ... Polarizing film, 21 ... Mold, 23 ... Gasket which comprises a lower mold, 24 ... 1st lower mold which comprises a lower mold, 25 ... Fixing member, 26: First upper mold constituting the upper mold, 27: First molding recess, 28: Second molding recess, 31: Polarized plastic film, 32: Film body, 41: Second lower side as a molding die Mold, 42: second upper mold as a molding die, 45: fourth molding recess, 46: fifth molding recess.

Claims (4)

A lens body obtained by polymerizing a polymerization raw material containing a polymerization catalyst containing a compound having an isocyanato group or an isothiocyanato group and a compound having a hydroxyl group or a mercapto group as a main component is formed from a resin having a hydroxyl group. It is provided on both surfaces of the polarizing film, and an isocyanato group or an isothiocyanato group is contained in the polymerization raw material of the lens body, and a hydroxyl group contained in the resin for forming the polarizing film is bonded by a urethane bond or thiourethane bond A method for producing a polarizing plastic lens, comprising:
A molding die comprising a pair of molding dies formed in a gently curved shape and a fixing member for fixing the polarizing film to one molding die is used. The molding die is disposed on the bottom surface and the peripheral portion thereof is fixed to one molding die by a fixing member, and then the other molding die is formed with a molding recess between the inner surface and one side surface of the polarizing film. The lens body is provided on one side surface of the polarizing film by filling the molding recess with a polymerization raw material in a state of being clamped to the one molding die, and then polymerizing and curing the polymerization raw material. Then, the intermediate molded body is molded, and then the intermediate molded body is arranged so as to have a new molding recess between the other side surface of the polarizing film and the inner surface of one molding die. It is characterized in that the polymerization raw material is filled again in the inside and this is cured by polymerization. Method of manufacturing a polarizing plastic lens that.   After polymerizing and curing the polymerization raw material on one side of the polarizing film and the polymerization raw material on the other side of the polarizing film, within a range from the glass transition point of the polymerization raw material to a temperature 20 ° C. higher than the glass transition point. The method for producing a polarizing plastic lens according to claim 1, wherein heat treatment is performed. A film body obtained by polymerizing a polymerization raw material containing a compound having an isocyanato group or an isothiocyanato group and a compound having a hydroxyl group or a mercapto group as a main component and containing a polymerization catalyst is formed from a resin having a hydroxyl group. It is provided on both surfaces of the polarizing film, and an isocyanato group or an isothiocyanato group is contained in the polymerization raw material of the film body, and a hydroxyl group contained in the resin for forming the polarizing film is bonded by a urethane bond or thiourethane bond A method for producing a polarizing plastic film comprising:
Using a molding die comprising a pair of molding dies whose inner surfaces are formed flat and a fixing member for fixing the polarizing film to one molding die, the polarizing film is The molding die is disposed on the bottom surface and the peripheral portion thereof is fixed to one molding die by a fixing member, and then the other molding die is formed with a molding recess between the inner surface and one side surface of the polarizing film. The film body is provided on one side surface of the polarizing film by filling the molding recess with a polymerization raw material in a state of being clamped to the one molding die and then polymerizing and curing the polymerization raw material. Then, the intermediate molded body is molded, and then the intermediate molded body is arranged so as to have a new molding recess between the other side surface of the polarizing film and the inner surface of one molding die. It is characterized in that the polymerization raw material is filled again in the inside and this is polymerized and cured. Method for producing a polarizing plastic film that.   After polymerizing and curing the polymerization raw material on one side of the polarizing film and the polymerization raw material on the other side of the polarizing film, within a range from the glass transition point of the polymerization raw material to a temperature 20 ° C. higher than the glass transition point. The method for producing a polarizing plastic film according to claim 3, wherein heat treatment is performed.

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