[0001]The present invention is a photochromic compound and a polymerizable composition for optical material containing the ultraviolet absorber, an optical material and a plastic lens obtained from the composition.
Background technique
[0002]
　Plastic lenses, a high refractive index compared with inorganic lenses, a high Abbe number, difficult to crack lightweight, dyeing spectacle lenses because it can, it has rapidly spread as an optical material such as a camera lens. This variety of lens molded articles have so far been developed and used.
　Representative examples among them, and allyl resins obtained from diethylene glycol bis allyl carbonate and diallyl isophthalate, and (meth) obtained from acrylate (meth) acrylic resins, polythiourethane resin obtained from isocyanates and thiols.
[0003]
　In recent years, plastic lens that various functions have been granted have been developed.
　For example, development of a plastic lens having photochromic properties has been developed. The glasses having photochromic properties, and functions as an ordinary transparent color glasses indoors, the lens in response to sunlight (ultraviolet) is outdoors gray coloring in brown or the like, exhibits a function to protect the eyes from glare is the glasses. A high-performance eyeglasses corresponding to use in both indoor and outdoor, in recent years, has expanded its demand.
　As the photochromic lens material, for example, a technique described in Patent Document 1-6.
[0004]
　Patent Document 1, by radical polymerization of a specific structure as the photochromic compound (meth) polymerizable composition comprising an acrylic acid ester and divinylbenzene casting polymerization method, high refractive index, excellent photochromic properties it is disclosed that can provide a photochromic spectacle lens.
[0005]
　Patent Document 2, by radical polymerization of a composition comprising a polymerizable monomer having a photochromic compound and a di (meth) acrylate groups in casting polymerization method, and has a fast photochromic properties of photoresponsive low specific gravity, it is disclosed that can provide a photochromic optical material having physical properties such as impact resistance. Further, by curing a composition containing a polymerizable monomer having a photochromic compound and a polyol or polythiol and a polyisocyanate and di (meth) acrylate group, it has been disclosed that can provide a photochromic optical material having a high refractive index .
[0006]
　Patent Document 3, an optical material for the polymerizable composition containing a photochromic compound and a fluorene acrylate compound by radical polymerization in casting polymerization method, photochromic performance and optical properties while the high refractive excellent fluorene acrylic ability to provide a photochromic optical material is disclosed.
[0007]
　Patent Document 4, a predetermined photochromic compound, a composition containing a di (meth) acrylate compounds, lenses.
[0008]
　Patent Document 5, a coating layer comprising a composition containing a photochromic compound and a phenol compound having a chromene skeleton, a lens provided on the surface of the thiourethane plastic lens is disclosed.
[0009]
　Patent Document 6, a lens base material made of a thiourethane resin, on to the substrate, a photochromic lens having a photochromic film solution formed by applying a containing a photochromic compound and a radically polymerizable monomer There has been disclosed.
　Incidentally, Patent Document 7, compounds having photochromic properties is disclosed.
[0010]
　The ultraviolet cut function can be given as a separate function that is applied to the plastic lens. Recently, development of a plastic lens having cut function ultraviolet (UV) have been developed.
[0011]
　Patent Document 8, or more wavelength 300 nm, the average light transmittance at 400nm following range is 0.5% or less, the plastic lens containing an ultraviolet absorbing agent is disclosed.
[0012]
　Furthermore, in recent years, has been demanded further sophistication of plastic lenses, plastic lenses have been developed that combines both of the aforementioned photochromic performance and UV cut function. Patent Documents 1 to 3, it is described that may be added an ultraviolet absorber in the polymerizable composition containing a photochromic compound. However, in the embodiment, specifically, the polymerizable composition containing these compounds together is not described.
CITATION
Patent Literature
[0013]
Patent Document 1: WO 2012/141306 Pamphlet
Patent Document 2: JP 2004-78052 JP
Patent Document 3: WO 2014/208994 pamphlet
Patent Document 4: JP-A 8-272036 Patent Publication
Patent Document 5: JP 2005-23238 JP
Patent Document 6: JP 2008-30439 JP
Patent Document 7: JP 2011-144181 JP
Patent Document 8: JP-a 10-186291 JP
Patent Document 9: WO 2009/146509 pamphlet
Patent Document 10: International Publication No. 2010/20770 pamphlet
Patent Document 11: WO 2012/149599 pamphlet
Patent Document 12: WO 2012/162725 pamphlet
Non-Patent Document
[0014]
非特許文献1 : The European journal of neuroscience, vol.34, Iss.4, 548-58, (2011)
Summary of the Invention
Problems that the Invention is to Solve
[0015]
　Photochromic compound whereas those expressing effect by ultraviolet rays, the ultraviolet absorber is to absorb ultraviolet rays. Therefore, if the photochromic compound and the ultraviolet absorber in the resin molded body are mixed, the light in the wavelength range necessary for the photochromic compound develops color will absorb ultraviolet absorber, that the photochromic performance is not sufficiently exhibited there were.
　Therefore, if you want to simultaneously impart photochromic performance and UV cut function to the plastic lens, for example, by adding a UV absorber to the polymerizable composition after creating the resin lenses, the lens surface a coating agent photochromic compound included a method such as construction has been carried out normally. However, such a manufacturing method, the more the number of manufacturing processes because the process is necessary to applying a coating agent onto step and resin surface to prepare a coating agent containing a photochromic compound, the manufacturing cost of the plastic lens is increased it was a.
Means for Solving the Problems
[0016]
　The present inventors have found that such prior art As a result of intensive studies in view of the, if a certain combination of UV absorber and a specific photochromic compound, it is possible to coexist both these in the polymerizable composition, the resin obtained by curing the polymerizable composition is found that together sufficiently exhibit the photochromic performance and UV cut function, which resulted in the completion of the invention.
[0017]
　That is, the present invention can be illustrated below.
[1] (A) (meth) monomer mixture containing a polymerizable monomer having an acrylic group and
at least one selected from compounds represented by (B) the general formula (1) and general formula (2) is a species, photochromic compound
is at least one member selected from (C) the general formula (a) ~ the compounds represented by (c), an ultraviolet absorber
including, for optical materials polymerizable composition;
　PC -Chain -L
　(1) '(2) PC-L-Chain-L'-PC
(in the formula (1) or formula (2), PC and PC' from the compound of the general formula (3) to (6) .PC a PC to a monovalent group derived 'may be the same or different.
[formula 1]

(in the formula (3) ~ (6), R 1 ~ R 18 is hydrogen, halogen atom, carboxyl group, an acetyl group, a formyl group, an optionally substituted C1 ~ C20 aliphatic group, optionally substituted Alicyclic group C3 ~ C20 or substituted an aromatic organic group which may C6 ~ C20, each of which may be the same or different. These aliphatic group, alicyclic group or an aromatic organic radical and, oxygen atoms, contained in the compound represented by the nitrogen atom may contain. formula (3) to (6), one of the group is attached to L or L 'is a divalent organic group. )
　In the formula (1) or Formula (2), L and L 'are oxyethylene chain, oxypropylene chain, (thio) ester group, a divalent organic group containing one or more selected from (thio) amido group It is shown. In the formula (1) or Formula (2), Chain represents a monovalent or divalent organic group containing at least one selected polysiloxane chain, polyoxyalkylene chain. )
[Formula 2]

(In the formula (a), R 1 , R 2 is an alkyl group of C1 ~ C8 or a halogen atom, may be the same or different. R there exist a plurality of 1 s or more exist, to R 2 together is an integer of good .m 0 to be the same or different 3, n represents an integer of 0 to 3, p is an integer of 0 to 1, R 3 is a straight-chain containing an ester bond or an branched C1 ~ C15 hydrocarbon group.)
[Chemical formula 3]

(in the formula (b), Z 1 and Z 2 may be the same or different, C1 ~ C6 alkyl group, a C1 ~ C6 alkoxy group shown.)
[formula 4]

(in the formula (c), Z 3 represents an alicyclic group of the aromatic organic group, may be substituted C5 ~ C20 of which may be substituted C6 ~ have C20, Z 4 and Z 5 may be the same or different, C1 ~ C6 alkyl group, C1 ~ C6 alkoxy group Show.).
[2] (meth) monomer mixture containing a polymerizable monomer having an acrylic group (A) is,
the table in the general formula (i), general formula (ii), there may formula (iii) and formula (iv) is the at least two selected from compounds [1] for an optical material polymerizable composition.
[Chemical Formula 5]

(wherein, R represents a hydrogen atom or a methyl group, R's, which are present in plural may be the same or different .m, n represents an integer of 0 to 20, be the same or different may also be.)
[formula 6]

is (wherein, R, represents a hydrogen atom or a methyl group, R's, which are present in plural may be the same or different .p represents an integer of 0-20.)
[formula 7]

(wherein, R represents a hydrogen atom or a methyl group, q is. an integer of 0 to 20)
[formula 8]

[3] (C) an ultraviolet absorber, 2- (2-hydroxy -5-t-octylphenyl) benzotriazole, 2- (2-hydroxy -5-t-butylphenyl) benzotriazole, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2-ethyl-2'- ethoxy-oxanilide, and (p- methoxybenzylidene) dimethyl malonate It is at least one selected from the chill, [1] or an optical material for a polymerizable composition as described in [2].
[4] [1] to [3] molded body obtained by curing the optical material for the polymerizable composition according to any one of.
Optical material comprising a molded product according to [5] [4].
[6] a plastic lens composed of a molded product according to [4].
[7] and the polarizing film,
　At least one of the formed on the surface, the plastic polarized lens comprising: a base material layer made of a molded product according to [4] of the polarizing film.
[8] (A) (meth) a monomer mixture containing a polymerizable monomer having an acrylic group,
at least selected from the compounds represented by (B) the general formula (1) and general formula (2) is one, and the photochromic compound,
and is, an ultraviolet absorber at least one selected from the compounds represented by (C) the general formula (a) ~ (c)
collectively mixed, for optical materials preparing a polymerizable composition,
　wherein the optical material for the polymerizable composition comprising the step of forming a lens substrate by cast polymerization method for producing a plastic lens;
　PC-L-Chain (1)
　PC '(2) -L-Chain- L'-PC
(in the formula (1) or formula (2), PC and PC' a monovalent group derived from a compound of the general formula (3) to (6) .PC and PC 'may be the same or different indicated.
[Chem 9]

(formula (3) - During 6), R 1 ~ R 18 is hydrogen, halogen atom, carboxyl group, an acetyl group, a formyl group, an aliphatic group which may be C1 ~ C20 substituted, cycloaliphatic optionally substituted C3 ~ C20 group or an aromatic organic group which may also be C6 ~ by C20 substituted, each may be the same or different. these aliphatic group, alicyclic group or an aromatic organic group, an oxygen atom, a nitrogen atom include But contained in the compound represented by the good. formula (3) to (6), one of the group is attached to L or L 'is a divalent organic group.)
　In the formula (1) or Formula (2), L and L 'are oxyethylene chain, oxypropylene chain, (thio) ester group, a divalent organic group containing one or more selected from (thio) amido group It is shown. In the formula (1) or Formula (2), Chain represents a monovalent or divalent organic group containing at least one selected polysiloxane chain, polyoxyalkylene chain. )
[Formula 10]

(In the formula (a), R 1 , R 2 is an alkyl group of C1 ~ C8 or a halogen atom, may be the same or different. R there exist a plurality of 1 s or more exist, to R 2 together is an integer of good .m 0 to be the same or different 3, n represents an integer of 0 to 3, p is an integer of 0 to 1, R 3 is a straight-chain containing an ester bond or an branched C1 ~ C15 hydrocarbon group.)
[Chem 11]

(in the formula (b), Z 1 and Z 2 may be the same or different, C1 ~ C6 alkyl group, a C1 ~ C6 alkoxy group shown.)
[formula 12]

(in the formula (c), Z 3 represents an alicyclic group of the aromatic organic group, may be substituted C5 ~ C20 of which may be substituted C6 ~ have C20, Z 4 and Z 5 may be the same or different, C1 ~ C6 alkyl group, C1 ~ C6 alkoxy Are shown.).
[9] (A) (meth) a monomer mixture containing a polymerizable monomer having an acrylic group,
at least selected from the compounds represented by (B) the general formula (1) and general formula (2) is one, and the photochromic compound,
and is, an ultraviolet absorber at least one selected from the compounds represented by (C) the general formula (a) ~ (c)
collectively mixed, for optical materials preparing a polymerizable composition,
　a polarizing film, a step of fixing in the lens casting mold in a state of being separated from the mold,
　the polarizing film, at least one of the gap formed between the mold wherein the step of injecting an optical material for the polymerizable composition, the
　polymerized curing the optical material for the polymerizable composition, a step of laminating the base material layer on at least one surface of the polarizing film
containing, Made in plastic polarized lens Production
　method; PC-L-Chain
　(1) '(2) PC-L-Chain-L'-PC
(In the formula (1) or Formula (2), PC and PC' of the general formula (3) to (6 ) monovalent .PC and PC showing a group derived from a compound of 'may be the same or different.
[formula 13]

(in the formula (3) ~ (6), R 1 ~ R 18Is hydrogen, halogen atom, carboxyl group, an acetyl group, a formyl group, an aliphatic group optionally substituted C1 ~ C20, alicyclic group which may be substituted C3 ~ be C20 or may be substituted, C6 an aromatic organic radical of ~ C20, may be the same or different. These aliphatic groups, alicyclic group or an aromatic organic group may contain an oxygen atom, a nitrogen atom. Formula (3) contained in the compound represented by - (6), one of the group is attached to L or L 'is a divalent organic group. )
　Formula (1) or the formula (2), L and L 'are oxyethylene chain, oxypropylene chain, (thio) ester group, a divalent organic containing one or more selected from (thio) amido group a group. In the formula (1) or Formula (2), Chain represents a monovalent or divalent organic group containing at least one selected polysiloxane chain, polyoxyalkylene chain. )
[Formula 14]

(In the formula (a), R 1 , R 2 is an alkyl group of C1 ~ C8 or a halogen atom, may be the same or different. R there exist a plurality of 1 s or more exist, to R 2 together is an integer of good .m 0 to be the same or different 3, n represents an integer of 0 to 3, p is an integer of 0 to 1, R 3 is a straight-chain containing an ester bond or an branched C1 ~ C15 hydrocarbon group.)
[formula 15]

(in the formula (b), Z 1 and Z 2 may be the same or different, C1 ~ C6 alkyl group, a C1 ~ C6 alkoxy group show.)
[Formula 16]

(In the formula (c), Z 3 is an aromatic organic group which may be substituted C6 ~ have C20, shows an alicyclic group which may be substituted C5 ~ have C20, Z 4 and Z 5 may be the same or different, C1 ~ C6 alkyl group, a C1 ~ C6 alkoxy group.).
Effect of the invention
[0018]
　According to the optical material for the polymerizable composition of the present invention, even when allowed to coexist with ultraviolet absorber and photochromic compound in the same layer, together both the photoresponsive fast photochromic performance and UV cut function, that it is possible to provide an excellent plastic spectacle lenses and polarized lenses balance of these properties.
　Further, according to the optical material for the polymerizable composition of the present invention, in the same layer can be obtained optical material containing an ultraviolet absorber and a photochromic compound, and a layer and a layer containing a photochromic compound comprising a UV absorber it is not necessary to separately form, excellent manufacturing stability of the optical material.
DESCRIPTION OF THE INVENTION
[0019]
　The optical material for the polymerizable composition of the present invention will be described with reference to the following embodiments.
　The optical material for the polymerizable composition of the present embodiment,
(A) (meth) a monomer mixture containing a polymerizable monomer having an acrylic group,
(B) the general formula (1) and general formula (2) in is at least one selected from the compounds represented, a photochromic compound,
at least one selected from the compounds represented by (C) the general formula (a) ~ (c), an ultraviolet absorber ,including.
　The optical material for the polymerizable composition of the present embodiment, by using a combination of (A) ~ (C) component as described below, in the acrylic resin, that together sufficiently exhibit the photochromic performance and UV cut function can.
　Each component is explained below.
[0020]
[(A) (meth) monomer mixture containing a polymerizable monomer having an acrylic group]
　monomer mixture (A) of the general formula (i), general formula (ii), there may formula (iii) and comprising at least two selected from compounds represented by formula (iv).
[0021]
[Chemical Formula 17]

[0022]
　In the formula, R represents a hydrogen atom or a methyl radical, R that existing in plural numbers may be the same or different. m, n represents an integer of 0 to 20, it may be the same or different.
[0023]
[Chem. 18]

[0024]
　In the formula, R represents a hydrogen atom or a methyl radical, R that existing in plural numbers may be the same or different. p is an integer of 0 to 20.
[0025]
[Of 19]

[0026]
　In the formula, R represents a hydrogen atom or a methyl group, q represents an integer of 0 to 20.
[0027]
[Of 20]

[0028]
　The polymerizable monomer having a formula (meth) acrylic group in the general formula (i), bisphenol A dimethacrylate, methylene - bis - (4,1-phenylene) - bis - (2-methacrylate), bisphenol A diacrylate, methylene - bis - (4,1-phenylene) - bis - (2-acrylate), 2,2-bis - (4-methacryloyloxy) propane, 2,2-bis - (4-acryloyloxy phenyl) propane, 2- (4-methacryloyloxy phenyl) -2- (4-methacryloyloxy-ethoxyphenyl) propane, 2- (4-acryloyloxy-phenyl) -2- (4-acryloyloxy ethoxy phenyl) propane, 2, 2- bis - (4-methacryloyloxy-ethoxyphenyl) propane, 2,2-bis - (4-acryloyloxy Ethoxyphenyl) propane, 2- (4-methacryloyloxy-ethoxy) -2- (4- (methacryloyloxy ethoxy) ethoxyphenyl) propane, 2- (4-acryloyloxy ethoxy-phenyl) -2- (4- (acryloyloxy ethoxy) ethoxy) propane, 2,2-bis - (4- (methacryloyloxy ethoxy) ethoxyphenyl) propane, 2,2-bis - (4- (acryloyloxy ethoxy) can be exemplified ethoxyphenyl) propane .
[0029]
　The polymerizable monomer having a formula (meth) acrylic group in general formula (ii), there may ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate Li rate, triethylene glycol diacrylate, mention may be made of tetraethylene glycol diacrylate.
[0030]
　Represented by the general formula (iii) (meth) As the polymerizable monomer having an acrylic group, methacrylic acid, acrylic acid, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2- (2-hydroxyethoxy) ethyl methacrylate, and 2- (2-hydroxyethoxy) ethyl acrylate.
[0031]
　The polymerizable monomer having other than (meth) acrylic group above, butanediol dimethacrylate, hexamethylene dimethacrylate, 2,2-bis (4-methacryloyloxy-ethoxy-3,5-dibromophenyl) propane, 2 , 2-bis - (4-methacryloyloxy pentaethoxy phenyl) propane, pentaerythritol tree acrylate, pentaerythritol tetraacrylate, trimethylolpropane triacrylate, dipentaerythritol hexaacrylate, bisphenol A- diglycidylether acrylate, bisphenol A - diglycidyl ether dimethacrylate system, tetrabromobisphenol A- diglycidyl ether di acrylate-based, tetrabromobisphenol A- diglycidyl It can include one or more compounds selected from a group consisting of such as Gilles ether dimethacrylate.
[0032]
　(Meth) monomers other than the polymerizable monomer having an acrylic group (excluding the compound represented by formula (iv)), styrene, alpha-methyl styrene, alpha-methyl styrene dimer, benzyl methacrylate, chlorostyrene , bromostyrene, methoxystyrene, monobenzyl malic acid, dibenzyl malic acid, monobenzyl fumarate rate, dibenzyl fumarate rate, methylbenzyl malic acid, dimethyl malate, diethyl malate, Jibuchiruringo acid, dibutyl fumarate rate, monobutyl malic acid, mono-pentyl malic acid, it can be used dipentyl malic acid, monopentyl fumarate rate, dipentyl fumarate rate, one or more compounds selected from a group consisting of diethylene glycol bisaryl carbonate.
[0033]
　Monomer mixture (A) in 100% by weight, the polymerizable monomer represented by the general formula (i) is 20 to 70 wt%, preferably may comprise 30 to 60 wt%,
　the general formula ( polymerizable monomer represented by ii) is from 10 to 60 wt%, preferably may comprise 20 to 50 wt%,
　represented by the general formula (iii) a polymerizable monomer, 2-20 wt%, preferably may comprise 5 to 15% by weight,
　the compound represented by formula (iv) is 1 wt% to 20 wt%, preferably 3 wt% to 15 wt%, more preferably 5 wt% It may comprise to 10% by weight.
　Used Included component (A) in the above range, by combining (A) ~ (C) component, can be expressed together effectively photochromic performance and UV cut function. The numerical range can be appropriately combined.
　(Meth) monomer mixture containing a polymerizable monomer having an acrylic group as (A), for example under the trade names include SSS-55 monomer.
[0034]
[(B) a photochromic compound]
　In the present embodiment, it is possible to use at least one selected from the compounds represented by (B) the general formula as the photochromic compound (1) and general formula (2).
　L--PC Chain
　(1) PC-L-Chain-L'-PC '(2)
[0035]
　PC and PC 'represents a monovalent group derived from a compound of general formula (3) to (6). PC and PC 'may be the same or different.
[0036]
[Of 21]

[0037]
　Equation (3) ~ (6), R 1 ~ R 18 is hydrogen, halogen atom, carboxyl group, an acetyl group, a formyl group, an aliphatic group optionally substituted C1 ~ C20, may be substituted C3 alicyclic group ~ C20 or an aromatic organic group which may also be C6 ~ by C20 substituted, may be the same or different. These aliphatic groups, alicyclic group or an aromatic organic group may contain an oxygen atom, a nitrogen atom. Formula (3) contained in the compound represented by - (6), one of the group is attached to L or L 'is a divalent organic group.
[0038]
　The aliphatic group optionally substituted C1 ~ C20, linear or branched C1 ~ C10 alkyl group, linear or branched C1 ~ C10 alkoxy group, linear or branched C2 ~ C10 alkenyl group, C1 ~ C10 hydroxyalkyl group, C1 ~ C10 hydroxyalkoxy group, C1 ~ C10 alkyl group substituted with C1 ~ C10 alkoxy group, C1 ~ C10 C1 ~ C10 alkoxy group substituted with an alkoxy group , C1 ~ C5 haloalkyl group, C1 ~ C5 dihaloalkyl group, C1 ~ C5 trihaloalkyl group, C1 ~ C10 alkyl amino group, C1 ~ C10 aminoalkyl group, a linear or branched C1 ~ C20 alkoxycarbonyl group it can be mentioned.
[0039]
　As alicyclic group which may be substituted C3 ~ C20, can be mentioned C3 cycloalkyl group ~ C20, like bicycloalkyl group C6 ~ C20.
　The aromatic organic group which may be C6 ~ C20 substituted phenyl group, C7 ~ C16 alkoxyphenyl group, an arylamino group, a diarylamino group, an aryl C1 ~ C5 alkyl amino group, cyclic amino group, an arylcarbonyl group, mention may be made of the aroyl group, and the like.
[0040]
　R 1 and R 2 as, preferably, a hydrogen atom, a halogen atom,
a straight-chain or branched C1 ~ C10 alkyl group, linear or branched C1 ~ C10 alkoxy group, C1 ~ C10 hydroxyalkoxy group , C1 ~ C10 alkoxy group substituted with C1 ~ C10 alkoxy group, C1 ~ C5 haloalkyl group, C1 ~ C5 dihaloalkyl group, C1 ~ C5 trihaloalkyl groups, such as C1 ~ C5 alkyl amino group, may be substituted aliphatic group C1 ~ C20;
phenyl, C7 ~ C16 alkoxyphenyl group, C1 ~ C5 dialkylamino group, an arylamino group, a diarylamino group, an aryl C1 ~ C5 alkyl amino group, such as a cyclic amino group, optionally substituted and the like can be given; aromatic organic group which may C6 ~ C20. R 1 and R 2 may be the same as or different from each other.
[0041]
　R 3 As, preferably a hydrogen atom, a halogen atom, a carboxyl group, an acetyl group;
straight chain or branched chain C1 ~ C10 alkyl group, linear or branched C2 ~ C10 alkenyl group, a straight-chain or branched C1 ~ C10 alkoxy group, C1 ~ C10 hydroxyalkyl group, C1 ~ C10 C1 ~ C10 alkyl group substituted with an alkoxy group, C1 ~ C10 aminoalkyl group, C1 ~ linear or branched C20, such as alkoxycarbonyl group, an aliphatic group which may be substituted C1 ~ by
C20; cycloalkyl group C3 ~ C20, C6 bicycloalkyl groups such ~ C20, alicyclic optionally substituted C3 ~ C20 group;
and the like, and the like; arylcarbonyl group, a formyl group, such as an aroyl group, an aromatic organic group which may be substituted C6 ~ to C20 Kill.
[0042]
　R 4 as, preferably, a hydrogen atom, a halogen atom, a carboxyl group, an acetyl group, formyl group;
straight chain or branched chain C1 ~ C10 alkyl group, linear or branched C2 ~ C10 alkenyl group, linear or branched C1 ~ C10 alkoxy group, C1 ~ C10 hydroxyalkyl group, C1 ~ C10 C1 ~ C10 alkyl group substituted with an alkoxy group, C1 ~ C10 aminoalkyl group, straight or branched of C1 ~ C20 alkoxycarbonyl group, etc., aliphatic group which may be substituted C1 ~ by
C20; cycloalkyl group C3 ~ C20, C6 bicycloalkyl groups such ~ C20, C3 may be substituted ~ C20 alicyclic group;
arylcarbonyl group, an aroyl group, a phenyl group, C7 ~ C16 alkoxyphenyl group, C1 ~ C10 Gia And the like can be given; Kokishifeniru group, C1 ~ C10 alkyl phenyl group, such as C1 ~ C10 dialkyl phenyl group, an aromatic organic group which may be substituted C6 ~ to C20.
[0043]
　R 3 and R 4 may be bonded to each other. R 3 and R 4 if are combined to form a ring structure, the general formula (7) or (8) below. Dotted lines, R 3 carbon atoms and R which are attached 4 represents the bond between the carbon atom to which they are attached.
[0044]
[Formula 22]

[0045]
　R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 14 , R 15 , R 16 is, R 1 , R 2 shows a similar functional group. R presence of a plurality of 5 ~ R 7 and may be the same or different.
[0046]
　R 11 as, preferably, a hydrogen atom, a halogen atom,
a straight-chain or branched C1 ~ C20 alkyl group, C1 ~ C5 haloalkyl group, C1 ~ C5 dihaloalkyl group, such as C1 ~ C5 trihaloalkyl group, a substituted has been in or C1 ~ C20 aliphatic
group; a cycloalkyl group of C3 ~ C20, bicycloalkyl group C6 ~ C20, C1 ~ C5 cycloalkyl group C3 ~ C20 substituted with an alkyl group, C1 ~ C5 alkyl group in bicycloalkyl group of which has been C6 ~ C20 substituted, cycloaliphatic group which may be substituted C3 ~ C20;
aryl groups substituted with C1 ~ C5 alkyl group may be substituted C6 ~ C20 aromatic organic group; and the like.
[0047]
　R 12 and R 13 as, preferably, a hydrogen atom; a halogen
atom; C1 ~ C10 alkyl group, C1 ~ such as C5 alkyl alkoxycarbonyl group, an aliphatic group optionally substituted C1 ~ C20; of C5 ~ C7 cycloalkyl shows the like; such as an alkyl group, an alicyclic group which may be substituted C3 ~ C20.
[0048]
　R 17 and R 18 as, preferably, a hydrogen atom, a halogen atom,
a straight-chain or branched C1 ~ C10 alkyl group, C1 ~ such as C10 hydroxyalkyl group, an aliphatic of optionally substituted C1 ~ C20 group; and the like; a C5 ~ such cycloalkyl group C7, alicyclic group which may be substituted C3 ~ C20.
[0049]
　L and L 'are of the general formula (1) or (2), an oxyethylene chain, oxypropylene chain, (thio) ester group, a divalent organic group containing one or more selected from (thio) amido group show.
　Specifically, L and L 'is represented by the general formula (9) to (15). L and L 'may be the same or different.
[0050]
[Of 23]

[0051]
　Wherein (9) ~ (15),
　Y represents oxygen, sulfur.
R 19 represents hydrogen, a linear or branched C1 ~ C10 alkyl group.
R 20 represents a linear or branched C1 ~ C10 alkyl group.
p represents an integer of 0 to 15, r represents an integer of 0 to 10.
Q is a straight-chain or branched C1 ~ C10 alkylene group, C1 ~ C10 alkenylene group, 1,2-, 1,3-, bivalent groups derived from 1,4-position of the substituted aryl group a divalent group derived from a substituted heteroaryl group.
* 1, * 2 represents a bond, * 1 binds monovalent or divalent organic group represented by "Chain", * 2 and a monovalent organic group represented by PC or PC ' Join.
[0052]
　"Chain" in the general formula (1) or (2) shows polysiloxane chain, a monovalent or divalent organic group containing at least one selected from polyoxyalkylene chain.
The polysiloxane chain, polydimethylsiloxane chains, polymethyl phenyl siloxane chain, polymethylhydrosiloxane chain, and the like.
The polyoxyalkylene chain, a polyoxyethylene chain, polyoxypropylene chain, polyoxymethylene hexamethylene chain, and the like.
[0053]
　Specifically,
　"Chain", if the photochromic compound of general formula (1) represents a monovalent organic group of the general formula (16) or (17).
[0054]
[Of 24]

[0055]
　"Chain" when the photochromic compound is of the general formula (2) represents a divalent organic group of the general formula (18) or (19).
[0056]
[Of 25]

[0057]
　Wherein (16) ~
(19), R 21 represents a linear or branched C1 ~ C10 alkyl group.
R 22 represents a linear or branched C1 ~ C10 alkyl group.
R 23 represents hydrogen, a methyl group, an ethyl group.
n represents an integer of 4 ~ 75, m is an integer of 1-50.
q is an integer of 1-3.
* 3, * 4 represents a bond, * 3 binds to a divalent organic group represented by L, * 4 binds to the divalent organic group represented by L '.
[0058]
　The photochromic compounds of the present invention, WO2009 / 146509 publication WO2010 / 20770 Publication, WO2012 / 149599 JP, obtained by the method described in WO2012 / 162725 publication.
[0059]
　The photochromic compound of the present invention, Vivimed's Reversacol Humber Blue (polydimethylsiloxane chain, naphthopyran chromophore (Formula 3)), Reversacol Calder Blue (polydimethylsiloxane chain, naphthopyran chromophore (Formula 3)) , Reversacol Trent Blue (polydimethylsiloxane chain, naphthopyran chromophore (formula 3)), Reversacol Pennine Green (polydimethylsiloxane chain, naphthopyran chromophore (formula 3)), Reversacol Heath Green (polyoxyalkylene chain, naphthopyran chromophore (formula 3)), Reversacol Chilli Red (polydimethylsiloxane chain, naphthopyran chromophore (formula )), Reversacol Wembley Gray (polyoxyalkylene chain, naphthopyran chromophore (Formula 3)), Reversacol Cayenne Red (polyoxyalkylene chain, naphthopyran chromophore (Formula 3)) and the like.
[0060]
[(C) an ultraviolet absorber]
　In the present embodiment, as the (C) an ultraviolet absorber, at least one is used is selected from the compounds represented by the following general formula (a) ~ (c).
[0061]
[Of 26]

[0062]
　In the general formula (a), R 1 , R 2 represents an alkyl group of C1 ~ C8 or halogen atom, and may be the same or different. More existing R 1 s or more existing R, 2 to each other may be the same or different. m is an integer of 0 to 3, n represents an integer of 0 to 3, p is an integer of 0-1. R 3 represents a linear or branched C1 ~ C15 hydrocarbon group, preferably a linear or branched in the C1 ~ C8 alkyl group containing an ester bond containing an ester bond.
[0063]
　As the ultraviolet absorber represented by the general formula (a), 2- (2-hydroxy -5-t-octylphenyl) benzotriazole, 2- (2-hydroxy -5-t-butylphenyl) benzotriazole, 2 - (2-hydroxy-5-methylphenyl) benzotriazole, 2- (5-t-octyl-3- (phenyl-2-yl) -2-hydroxyphenyl) benzotriazole, 2- (5-t-butyl 3- (phenyl-2-yl) -2-hydroxyphenyl) benzotriazole, 2- (5-methyl-3- (phenyl-2-yl) -2-hydroxyphenyl) benzotriazole, 2- (5 - octyl propionate-2-hydroxyphenyl) benzotriazole, 2- (5-t- octyl-2-hydroxyphenyl) Ben Triazole, 2- (3,5-di -t- butyl-2-hydroxyphenyl) benzotriazole, 2- (3,5-di -t- pentyl-2-hydroxyphenyl) benzotriazole, 2- (3,5 - bis - (phenyl-2-yl) -2-hydroxyphenyl) benzotriazole, 2- (3,5-di -t- butyl-2-hydroxyphenyl) -5-chloro-benzotriazole, 2- (4- octyloxy-2-hydroxyphenyl) benzotriazole, 2- (5-methyl -3-n-dodecyl-2-hydroxyphenyl) benzotriazole, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- ( 5-t-butyl-2-hydroxyphenyl) this is at least one selected from the group consisting of benzotriazole It is preferred.
　More preferably, 2- (2-hydroxy -5-t-octylphenyl) benzotriazole, 2- (2-hydroxy -5-t-butylphenyl) benzotriazole, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (5-t- octyl-3 (phenyl-propan-2-yl) -2-hydroxyphenyl) benzotriazole, 2- (5-t- butyl-3- (phenyl-2-yl) 2-hydroxyphenyl) benzotriazole, 2- (5-methyl-3- (phenyl-2-yl) -2-hydroxyphenyl) benzotriazole, 2- (5-octyl propionate-2-hydroxyphenyl) benzotriazole, 2- (3,5-di -t- pentyl-2-hydroxyphenyl) benzotriazole, 2 (3,5-bis - (phenyl-2-yl) -2-hydroxyphenyl) benzotriazole, 2- (3,5-di -t- butyl-2-hydroxyphenyl) -5-chloro-benzotriazole, 2 - (4-octyloxy-2-hydroxyphenyl) benzotriazoles, more preferably 2- (2-hydroxy -5-t-octylphenyl) benzotriazole, 2- (2-hydroxy -5-t-butylphenyl) benzo triazole, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (5-t-octyl-3- (phenyl-2-yl) -2-hydroxyphenyl) benzotriazole, 2- (5- t- butyl-3- (phenyl-2-yl) -2-hydroxyphenyl) benzotriazole, 2- (5 Methyl-3- (phenyl-2-yl) -2-hydroxyphenyl) benzotriazole, particularly preferably 2- (2-hydroxy -5-t-octylphenyl) benzotriazole, 2- (2-hydroxy-5 t- butylphenyl) benzotriazole, it is to select at least one from the group consisting of 2- (2-hydroxy-5-methylphenyl) benzotriazole.
[0064]
[Of 27]

[0065]
　In the general formula (b), Z 1 and Z 2 may be the same or different, C1 ~ C6 alkyl group, and a C1 ~ C6 alkoxy group.
[0066]
[Formula 28]

[0067]
　In the general formula (c), Z 3 may be mentioned alicyclic group of aromatic organic group, may be substituted C5 ~ C20 of which may be substituted C6 ~ have C20, Z 4 and Z 5 may be the same or different, C1 ~ C6 alkyl group, and a C1 ~ C6 alkoxy group.
　The aromatic organic group of C6 ~ C20, may be mentioned a phenyl group, a benzyl group, a benzoyl group, a p- methoxybenzyl group. The C5 ~ alicyclic group C20, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclopentanyl group, and a cyclooctyl group.
　Examples of the substituent of the alicyclic group substituted group or a substituted aromatic organic group substituted C6 ~ C20 C5 ~ C20, C1 ~ C6 alkyl group, and a C1 ~ C6 alkoxy group.
[0068]
　In formula (b) or (c), as the C1 ~ C6 alkyl group, a methyl group, an ethyl group, butyl group, propyl group, pentyl group to, can be exemplified hexyl group or the like, as C1 ~ C6 alkoxy group It may include methoxy group, an ethoxy group, a butoxy group, a phenoxy group or the like.
[0069]
　Examples of the compound represented by the general formula (b), it is possible to mention 2-ethyl-2'-ethoxy-oxanilide like. Examples of the compound represented by the general formula (c), it is possible to mention (p- methoxybenzylidene) malonate and the like.
[0070]
　In the present embodiment, (C) as an ultraviolet absorber, 2- (2-hydroxy -5-t-octylphenyl) benzotriazole, 2- (2-hydroxy -5-t-butylphenyl) benzotriazole, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2-ethyl-2'-ethoxy-oxanilide, and (p- methoxybenzylidene) is particularly preferably used at least one selected from dimethyl malonate.
[0071]
　In the present embodiment, from the viewpoint of the effect of the present invention, the (B) a photochromic compound, based on the sum of (A) (meth) mixture of a polymerizable monomer having an acryl group, 10 ppm ~ 10000 ppm, preferably 50 pm~5000ppm, more preferably may comprise in the range of 100 ppm ~ 3000 ppm.
[0072]
　Further, from the viewpoint of the effect of the present invention, the (C) an ultraviolet absorber, relative to the total of the mixture of the polymerizable monomer having a (A) (meth) acryl group, 10 ppm ~ 20000 ppm, preferably 20 ppm ~ 5000 ppm, more preferably, it can include a range of 20 ppm ~ 3000 ppm.
[0073]
[Other Components]
　In the present embodiment, in addition to the (A) ~ (C) component, a polymerization catalyst, an internal mold release agent may further contain a resin modifier, and the like.
　As the polymerization catalyst, it may be mentioned as a radical polymerization initiator peroxy ester radical polymerization initiator, a peroxy ketal radical polymerization initiator or an azo-based radical polymerization initiator.
[0074]
　To cure the monomer composition for producing an optical material in the production process of the present invention, a radical polymerization initiator is added to the monomer composition, then heat curing method or an active energy ray curing method it can be obtained by curing by.
　Upon curing the monomer composition by using these radical polymerization initiators, and prevent degradation of the photochromic compound during curing, furthermore, a polyol, polythiol, when containing polyisocyanates may suppress coloring at the time of curing can do.
[0075]
　The peroxy ester radical polymerization initiator, for example, hexyl peroxyneodecanoate to t-, 1,1,3,3-tetramethylbutyl peroxycarboxylic neodecanoate, cyclohexyl peroxy-2-ethyl-to t- hexanoate, 1-cyclohexyl-1-methylethyl peroxyneodecanoate, cumyl peroxyneodecanoate, t- butyl peroxy-2-ethylhexanoate, t- butyl peroxypivalate, t-hexyl peroxypivalate Bareto, t- butyl peroxyneodecanoate, t- butyl peroxy isobutyrate, t- butyl peroxy laurate, t- butyl peroxy nonanoate and the like.
[0076]
　The peroxy ketal radical polymerization initiator, 1,1-bis (t-hexyl peroxy) cyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, di -t- butyl peroxy-2-methylcyclohexane, 1 , 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane are preferable. More preferably, by selecting the 1,1-bis (t-hexyl peroxy) cyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, at least one di -t- butyl peroxy-2-methylcyclohexane is there.
[0077]
　The azo type radical polymerization initiators, e.g., azobisisobutyronitrile, and azobis-dimethyl valeronitrile and the like.
　These may be used alone or in combination. It may be used in combination with other radical polymerization initiator if necessary.
[0078]
　In the present invention, the addition amount of the radical polymerization initiator, the monomer composition is usually 0.01 to 10% by weight, preferably 0.1 to 5 wt%. Curing is insufficient at less than 0.01 wt%, there is a tendency that the strain enters the cured product exceeds 10 wt%.
[0079]
　As the internal mold release agent, it is possible to use an acidic phosphoric acid ester. The acidic phosphoric acid esters, phosphoric acid monoesters, there may be mentioned phosphoric acid diester, can be used as a mixture either alone or two or more kinds.
[0080]
　The resin modifier, for example, an episulfide compound, an alcohol compound, amine compound, epoxy compound, organic acid and its anhydride include olefin compounds containing (meth) acrylate compounds.
[0081]

　for an optical material polymerizable composition of the present embodiment,
a monomer mixture containing a polymerizable monomer having a (A) (meth) acrylic group,
(B ) in formula (1) and at least one compound selected from compounds represented by the general formula (2), and a photochromic compound,
selected from the compounds represented by (C) the general formula (a) ~ (c) it is at least one member, and an ultraviolet absorber, collectively mixed, can be prepared.
[0082]
　Component (A) is carried out in the component (B) and component (C), the temperature in the preparation of further polymerizable composition by mixing the other additives are usually 25 ° C. or less. From the viewpoint of pot life of the polymerizable composition, it may be preferable further to a low temperature. However, catalysts, internal release agents, if solubility in monomer additive is not satisfactory, it is also possible to dissolve beforehand warmed, monomers, a resin modifier.
[0083]
　In the present embodiment, a manufacturing method of the resin molded body is not particularly limited, and a casting polymerization as a preferred production method. First, injecting the polymerizable composition between molding mold held by a gasket or tape. At this time, depending on the properties required for the plastic lens obtained, if necessary, a defoaming treatment under reduced pressure or pressurization, it is often preferable to perform the filtration treatment and the like of reduced pressure or the like.
[0084]
　The polymerization conditions, the composition of the polymerizable composition, type and amount of catalyst used, but is not limited for different conditions largely by the shape or the like of the mold, approximately, 1 to 50 at a temperature of -50 ~ 0.99 ° C. It is carried out over a period of time. Optionally, held or gradually heated in a temperature range of 10 ~ 0.99 ° C., it is preferable to cure for 1 to 48 hours.
[0085]
　Resin molding, if necessary, may be subjected to a treatment such as annealing. Although the process is carried out at a temperature usually between 50 ~ 0.99 ° C., preferably performed at 90 ~ 140 ° C., and more preferably at 100 ~ 130 ° C..
[0086]
　In the present embodiment, in molding the resin, in addition to the above "other components" in the same manner as in a known molding method depending on the purpose, chain extenders, crosslinking agents, light stabilizers, antioxidants, bluing agent, solvent dye, filler, various additives may be added, such as an adhesion improver.
[0087]

　Acrylic resin of the present embodiment can be obtained as a molded article having various shapes by changing the type of mold during casting polymerization.
　Molded body for optical material polymerizable composition is cured in this embodiment is generally 8% light transmittance at 380nm after color less, preferably 5% or less, more preferably be suppressed to 2% or less it can. The resin compact of this exemplary embodiment is provided with such excellent fast photochromic performance of photoresponsive with UV cut function has a higher refractive index and high transparency, used for various optical materials such as plastic lenses it is possible to. In particular, it can be suitably used as a plastic spectacle lens or a plastic polarized lens.
　Method of manufacturing a plastic lens of the present embodiment includes a step of forming a lens substrate by cast polymerization of the optical material for the polymerizable composition.
[0088]
[Plastic spectacle lenses]
　plastic spectacle lens using a lens substrate made of molded body of the present embodiment may optionally be used after the coating layer on one or both sides.
　Plastic spectacle lens of the present embodiment is composed of a lens substrate and the coating layer comprising a polymerizable composition described above.
[0089]
　As a coating layer, specifically, a primer layer, a hard coat layer, an antireflection layer, anti-fogging coat layer, anti-fouling layer, a water repellent layer, and the like. It may also be used in multi-layered multiple coating layers using each of these coating layers alone. When applying a coating layer on both sides, even if subjected to the same coating layer on each side may be subjected to a different coating layers.
[0090]
　Each of these coating layers, the infrared absorbing agent for the purpose of protecting the eyes from infrared rays, a light stabilizer or antioxidant for the purpose of improving the weather resistance of the lens, the photochromic compound, purpose dyes or pigments to enhance the fashion of the lens , antistatic agents, other may be used in combination known additive for increasing the performance of the lens.
　It may be used various leveling agents for the purpose of improving the coating properties with respect to the layer to perform coating by the coating.
[0091]
　The primer layer is usually formed between the hard coat layer and the lens to be described later. The primer layer is a coating layer for the purpose of improving the adhesion between the hard coat layer and the lens formed thereon, it is possible to improve impact resistance in some cases. Primers can also be used in any material as long as high adhesion to the lens obtained in the primer layer, which usually, urethane resins, epoxy resins, polyester resins, melanin resins, a main component a polyvinyl acetal such compositions are used. The primer composition may be used a suitable solvent which does not affect the lens in order to adjust the viscosity of the composition. Of course, it may be used in solvent-free.
[0092]
　The primer layer can be formed by a coating method, any method of a dry method. When using the coating method, the primer composition was applied to the lens by a known coating method such as spin coating, dip coating, a primer layer is formed by solidifying. When performing a dry method, it is formed by a known dry method such as CVD method or a vacuum evaporation method. When forming the primer layer, for the purpose of enhancing adhesion, the surface of the lens if necessary, alkali treatment, plasma treatment, may be previously subjected to pre-treatment such as UV treatment.
　The hard coat layer, the scratch resistance on the lens surface, wear resistance, moisture resistance, hot water resistance, heat resistance, a coating layer for the purpose of giving weather resistance function.
[0093]
　The hard coat layer, an organosilicon compound typically having curability and Si, Al, Sn, Sb, Ta, Ce, La, Fe, Zn, W, Zr, the element selected from the group consisting of In and Ti hardcoat composition comprising one or more particulate composed of a composite oxide of two or more elements selected from one or more and / or these elements groups oxide microparticles are used.
[0094]
　Amines other than the above components in the hard coat composition, amino acids, at least the metal acetylacetonate complexes, organic acid metal salts, perchloric acids, salts of perchloric acids, acids, metal chlorides and polyfunctional epoxy compounds it is preferable to include either. It may be used a suitable solvent which does not affect the lens in the hard coat composition may be used without a solvent.
[0095]
　The hard coat layer is usually spin coating a hard coat composition was applied by a known coating method such as dip coating, it is formed by curing. As the curing method, thermosetting, a curing method such as by energy ray irradiation such as ultraviolet or visible light and the like. To suppress the occurrence of interference fringe, the refractive index of the hard coat layer, the difference in refractive index of the lens is preferably in the range of ± 0.1.
[0096]
　Antireflection layer is usually formed on the hard coat layer as needed. The anti-reflection layer has inorganic and organic, if inorganic, SiO 2 , TiO 2 using an inorganic oxide such as a vacuum deposition method, sputtering method, ion plating method, ion beam - Muashisuto method, CVD method It is formed by a dry method such as. If organic, using an organosilicon compound, a composition comprising a silica-based fine particles having internal cavities are formed by a wet.
[0097]
　Antireflective layer has a single-layer and multilayer, it is preferable that a refractive index higher than the refractive index of the hard coat layer is lower at least 0.1 or more when used as a single layer. It is preferable that the express effectively anti-reflection function is a multi-layer film anti-reflection film, in which case, alternately laminating a low refractive index film and the high refractive index film. It is preferred in this case the refractive index difference between the low refractive index film and the high refractive index film is 0.1 or more. The high refractive index film, ZnO, TiO 2 , CeO 2 , Sb 2 O 5 , SnO 2 , ZrO 2 , Ta 2 O 5 has such a film, the low refractive index film, SiO 2 include films and the like .
[0098]
　On the antireflection layer, anti-fogging layer optionally antifouling layer, may be formed a water-repellent layer. Antifogging, antifouling layer, a method of forming a water-repellent layer, as long as they do not result in a negative effect on the anti-reflection function, a processing method thereof, and the like without particular limitation on the processing material, known anti-fogging method, antifouling treatment method, water repellent treatment method, the material can be used. For example, a method antifogging method, the anti-fouling treatment method, a method of covering the surface with a surfactant, a method of water absorption by adding a hydrophilic film on the surface, to increase the water-absorbing covering the surface with fine unevenness , a method of using a photocatalytic activity to water absorption, a method of preventing the adhesion of water droplets by subjecting the superhydrophobic treatment. Further, the method in the water-repellent treatment method, for forming a fluorine-containing silane compound or the like and a method of forming a water-repellent treatment layer by vapor deposition or sputtering, after the fluorine-containing silane compound is dissolved in a solvent, the water-repellent treatment layer by coating etc. the.
[0099]
[Plastic polarized lens]
　plastic polarized lens of the present embodiment is composed of a polarizing film, the polarizing film is formed on at least one surface of the molded article obtained by curing the optical material for the polymerizable composition of the present embodiment comprising a substrate layer.
[0100]
　Polarizing film in the present embodiment can be composed of a thermoplastic resin. As the thermoplastic resin include thermoplastic polyester, thermoplastic polycarbonate, thermoplastic polyolefin, thermoplastic polyimide. Water resistance, from the viewpoint of heat resistance and moldability, a thermoplastic polyester, thermoplastic polycarbonates are preferred, the thermoplastic polyester is more preferable.
[0101]
　As the thermoplastic polyester, polyethylene terephthalate, polyethylene naphthalate, and can be exemplified polybutylene terephthalate, water resistance, polyethylene terephthalate from the viewpoint of heat resistance and moldability preferred.
[0102]
　As the polarizing film, particularly, a dichroic dye-containing thermoplastic polyester polarizing film, iodine-containing polyvinyl alcohol polarizing film, dichroic dye-containing polyvinyl alcohol polarizing film and the like.
　Polarizing film drying, it may be used after having undergone a heat treatment for stabilization.
　Further, polarizing film, in order to improve the adhesion between the acrylic resin, a primer coating treatment, chemical treatment (gas or chemical solution treatment in an alkali and the like), a corona discharge treatment, plasma treatment, ultraviolet irradiation treatment, electron beam irradiation treatment roughening treatment, one or more preprocessing selected from such flame treatment may be used after conducting. Among such pretreatment, a primer coating treatment, chemical treatment, corona discharge treatment, one or two or more selected from plasma treatment is particularly preferred.
[0103]
　Plastic polarized lens of the present embodiment can be obtained by such on at least one surface of the polarizing film, the optical material for the polymerizable composition of the present embodiment is cured provided a substrate layer obtained by .
　Method for producing a plastic polarized lens is not particularly limited, preferably be mentioned casting polymerization method.
[0104]
　Method for producing a plastic polarized lens of the present embodiment, for example,
　a polarizing film, a step of fixing the lens casting in a mold in a state of being separated from the mold,
　is formed with the polarizing film, between the mold a step of injecting the optical material for the polymerizable composition to at least one of the air gap,
　the polymerized curing the optical material for the polymerizable composition, laminating a base layer on at least one surface of the polarizing film , it can contain.
[0105]
　Lens casting mold are those composed of two substantially disk-shaped glass mold held by the gasket is common. In the space of the lens casting mold, the polarizing film, the film surface is placed so as to be parallel to the mold inner surface of the front side facing. Between the polarized film and the mold, the void portion is formed. The polarization film may be pre Fugata.
[0106]
　The polymerization conditions of the optical material for the polymerizable composition, the composition of the polymerizable composition, type and amount of catalyst used, although conditions vary depending on the shape or the like of the mold, over a period of 1-50 hours at a temperature of 5 ~ 140 ° C. row divide. Optionally, held or gradually heated in a temperature range of 5 ~ 130 ° C., is thereby is preferably cured for 1 to 25 hours.
　The laminate was cured by polymerization by releasing from the mold, it is possible to obtain a plastic polarized lens of the present embodiment.
[0107]
　In this embodiment, the laminate after polymerization Releasing, if necessary, it may be subjected to heat treatment such as annealing. Treatment temperature, in view of the effect of the present invention is carried out at between 90 ~ 0.99 ° C., preferably performed at 110 ~ 130 ° C., and more preferably at 115 ~ 125 ° C.. Treatment time, from the viewpoint of the effect of the present invention, 1 to 10 hours, preferably 2-5 hours.
　Incidentally, the surface of the resulting substrate layer may form the coating layer similar to the plastic spectacle lens.
[0108]
　In the present embodiment has been described by a plastic spectacle lens or the like comprising a base material formed of the optical material for the polymerizable composition, the photochromic compound and on a substrate containing no ultraviolet absorber, polymerization optical material of the present embodiment it is also possible to provide a layer consisting of gender composition.
Example
[0109]
　Is specifically described below the present invention based on examples, the present invention is not limited to these examples. The evaluation of the molded body and a plastic lens comprising a cured resin was performed by the following method.
[0110]
Refractive index (ne) was Abbe number (ve): using Shimadzu Pulfrich refractometer KPR-30, measured at 20 ° C..
Specific gravity was measured by the Archimedes method at 25 ℃.
- light transmittance: light transmittance at 380nm after color: using a metal halide lamp (180 W) light source, a temperature 19 ° C., UV intensity 1.2 mW / cm was measured by integrating actinometer 2 under the condition of, 2.0 mm when allowed to develop the compact sample processed into a thickness 5 minutes, to measure the spectral in transmission measurement system.
　As this numerical value is smaller, indicating that the high performance of UV rays.
Photo black performance: light transmittance at 550nm after color: manufactured by Ushio Inc. MS-35AAF / FB xenon lamp light source device using a (illuminance 50000 lux), at a temperature 23 ° C., in integrating actinometer, 2.0 mm thick spectroscopic when processed molded body samples were developed for 5 minutes to measure at MCPD-7700 transmission measurement system.
　Because of the high light-shielding property at the time of color development as the transmittance is small, indicating that the photochromic performance is high.
[0111]
(Materials used)
　photochromic
compound: · Reversacol Calder Blue (polydimethylsiloxane chain, naphthopyran chromophore (Formula
3)) · Reversacol Trent Blue (polydimethylsiloxane chain, naphthopyran chromophore (Formula
3)) · Reversacol Heath Green (polyoxyalkylene chain, naphthopyran chromophore (formula
3)) · Reversacol Wembley Gray (polyoxyalkylene chain, naphthopyran chromophore (formula
3)) · Reversacol Chilli Red (polydimethylsiloxane chain, naphthopyran chromogenic Dan (the formula 3))
[0112]
[Example
　1] 0.02 part by weight of trade name Reversacol Calder Blue as photochromic compound in 100.0 parts by weight of SSS-55 monomer, 0.01 parts by weight of the product name Reversacol Trent Blue, a product name Reversacol Heath Green 0. 031 parts by weight of a 2-2,2'-azobis [2,4-dimethylvaleronitrile] 0.25 parts by weight, 1,1-bis (t-butylperoxy) cyclohexane 0.03 parts by weight, as an ultraviolet absorber ( 2-hydroxy -5-t-octylphenyl) benzotriazole (VIOSORB583 (product name), KYODO cHEMICAL Co., Ltd.) 0.10 parts by weight was added and dissolved stirred together. 5mmHg was degassed under 60 minutes. It was filtered through a 1μmPTFE filter made and injected into a mold composed of a glass mold and a tape. After turning the mold to an oven and polymerized by gradually heated over a period of 23 hours from 35 ° C. to 95 ° C.. After completion of the polymerization, removed mold from the oven, to obtain a 2.0mm thick resin flat plate and release. The obtained resin plates were subjected to 1 hour annealing at further 110 ° C.. The resulting resin flat refractive index (ne) 1.547, Abbe number (ve) 40, a resin and a specific gravity of 1.18.
　Molded body was colorless and transparent, and immediately colored when placed under sunlight, had a good light modulating performance that decolored when shielding light. Evaluation of the light modulating performance of the compact, light transmittance at 380nm after coloring: 1.2%, light transmittance after color development at 550nm after coloring: showed good results of 27.0%. The results are shown in Table 1.
[0113]
Example 2
　0.03 parts by weight Product name Reversacol Calder Blue as the photochromic compound, 0.015 parts by weight of the product name Reversacol Trent Blue, except for changing the product name Reversacol Heath Green to 0.0465 parts by weight Example to obtain a 2.0mm thick resin flat plate 1 and similar methods. The results, shown in Table 1.
[0114]
Example 3
　Product name Reversacol Wembley Gray 0.054 parts by weight of photochromic compound, product name Reversacol Heath Green 0.0215 parts by weight, as an ultraviolet absorber 2- (2-hydroxy -5-t-octylphenyl) benzotriazole 0.02 parts by weight, except for changing the got 2.0mm thick resin flat plate in the same manner as in example 1. The results, shown in Table 1.
[0115]
[Example 4]
　0.10 parts by weight of 2- (2-hydroxy -5-t-octylphenyl) benzotriazole as an ultraviolet absorber, 2.0 mm thick resin plate-in the same manner as in Example 3 was changed to a Obtained. The results, shown in Table 1.
[0116]
[Example 5]
　Product name Reversacol Chilli Red 0.06 parts by weight, product name Reversacol Heath Green 0.09 part by weight, as an ultraviolet absorber 2- (2-hydroxy -5-t-octylphenyl) benzotriazole as a photochromic compound 0.02 parts by weight, except for changing the got 2.0mm thick resin flat plate in the same manner as in example 1. The results, shown in Table 1.
[0117]
Example 6
　0.05 part by weight of 2- (2-hydroxy -5-t-octylphenyl) benzotriazole as an ultraviolet absorber, 2.0 mm thick resin plate-in the same manner as in Example 5 was changed to a Obtained. The results, shown in Table 1.
[0118]
Example 7
　similarly to as an ultraviolet absorber 2- (2-hydroxy-5-methylphenyl) benzotriazole (TINUVIN P (trade name), manufactured by BASF) 0.10 parts by weight, except that the Example 1 to obtain a 2.0mm thick resin flat plate in a way. The results, shown in Table 1.
[0119]
Example 8
　as a UV absorber 2- (2-hydroxy -5-t-butylphenyl) benzotriazole (TINUVIN PS (product name), manufactured by BASF) 0.15 parts by weight, except that the Example 1 to obtain a 2.0mm thick resin flat plate in a similar manner. The results, shown in Table 1.
[0120]
Example 9
　as an ultraviolet absorber (p- methoxybenzylidene) malonate (Hostavin PR-25 (product name), CLARIANT Corp.) 1.0 part by weight, in the same manner as in Example 3 was changed to to obtain a 2.0mm thick resin plates. The results, shown in Table 1.
[0121]
Example 10
　as an ultraviolet absorber 2-ethyl-2'-ethoxy-oxanilide (Hostavin VSU (trade name), CLARIANT Corp.) 1.0 part by weight, in the same manner as in Example 3 except that the to obtain a 2.0mm thick resin plates. The results, shown in Table 1.
[0122]
[Comparative Example 1]
　except for not adding the ultraviolet absorber to obtain a 2.0mm thick resin flat plate in the same manner as in Example 1. The results, shown in Table 1.
[0123]
[Comparative Example 2]
　As the ultraviolet absorber 2,2'4,4'- tetrahydroxybenzophenone (Shisorubu 106 (product name), manufactured by Cipro Chemical Co., Ltd.) 0.025 parts by weight, except for changing the same manner as in Example 1 to obtain a 2.0mm thick resin flat plate in a way. The results, shown in Table 1.
[0124]
[Comparative Example 3]
　2,2'-dihydroxy-4,4'-dimethoxy benzophenone as an ultraviolet absorber (Shisorubu 107 (product name) 2 0.020 part by weight, the in the same manner as in Example 1 except that the was obtained .0mm thickness resin plates. the results, shown in Table 1.
[0125]
[Comparative Example 4]
　The photochromic compound, Benzenamine, 4- [7,9-dimethoxy -2- (4-methoxyphenyl) -5-methyl-2H-naphtho [1,2-b] pyran-2-yl] -N , 0.0536 parts by weight of N-dimethyl-, Morpholine, 4- [ 3- (4-methoxyphenyl) -3-phenyl-3H-naphtho [2,1-b] pyran-6-yl] - a 0.0064 was changed to parts by weight to obtain a 2.0mm thick resin flat plate in the same manner as in example 1. The results, shown in Table 1.
[0126]
[Table 1]

[0127]
　Components and the like described in Table 1 are as follows.
Dye (1): Reversacol Calder Blue
Dye (2): Reversacol Trent Blue
Dye (3): Reversacol Heath Green
Dye (4): Reversacol Wembley Grey
-dye (5): Reversacol Chilli Red
* 1: Benzenamine, 4- [7,9-dimethoxy-2- ( 4-methoxyphenyl) -5-methyl-2H-naphtho [1,2-b] pyran-2-yl] -N, the N-dimethyl- 0.0536 parts by weight, Morpholine , 4- [3- (4-methoxyphenyl ) -3-phenyl-3H-naphtho [2,1-b] pyran-6-yl] - the containing 0.0064 parts by weight.
[0128]
　Also in the plastic polarized lens it was estimated that similar results are obtained.
[0129]
　This application, the basic priority based on Japanese Patent Application No. 2015-183492, filed on September 16, 2015, and the Japanese Patent Application No. 2015-240354, filed on December 9, 2015 claims priority, the entire contents of which are incorporated herein.

claims

[Claim 1](A) (meth) monomer mixture containing a polymerizable monomer having an acrylic group and
at least one selected from the compounds represented by (B) the general formula (1) and general formula (2) the photochromic compound
is at least one member selected from (C) the general formula (a) ~ the compounds represented by (c), an ultraviolet absorber
including, for optical materials polymerizable composition;
　PC-L- Chain
　(1) '(2) PC-L-Chain-L'-PC
(in the formula (1) or formula (2), PC and PC' are derived from compounds of the general formula (3) to (6) monovalent .PC and PC showing a group 'may be the same or different.
[formula 1]

(in the formula (3) ~ (6), R 1 ~ R 18 is hydrogen, halogen atom, carboxyl group, acetyl group, a formyl group, an aliphatic group optionally substituted C1 ~ C20, may be substituted C3 Shows the C20 alicyclic group or an optionally substituted C6 ~ C20 aromatic organic group, a, each of which may be the same or different. These aliphatic group, alicyclic group or an aromatic organic group, an oxygen atom , contained in the compound represented by the nitrogen atom may contain. formula (3) to (6), one of the group is attached to L or L 'is a divalent organic group.)
　formula (1) or the formula (2), L and L 'are oxyethylene chain, oxypropylene chain, (thio) ester group, a divalent organic group containing one or more selected from (thio) amido group shown in. equation (1) or formula (2), chain polysiloxane chain, a monovalent or divalent organic group containing at least one selected from polyoxyalkylene chain.)
[formula 2]

(In the formula (a), R 1 , R 2 is an alkyl group of C1 ~ C8 or a halogen atom, R is present or. More be the same or different, 1 to each other or more existing R, 2 each other may be the same or different .m is an integer of 0 to 3, n represents an integer of 0 to 3, p is an integer of 0 ~ 1, R 3 is C1 ~ linear or branched containing an ester bond C15 a hydrocarbon group.)
[Chemical formula 3]

(in the formula (b), Z 1 and Z 2 may be the same or different, C1 ~ C6 alkyl group, a C1 ~ C6 alkoxy group.)
[formula 4]

(in the formula (c), Z 3 represents an alicyclic group of the aromatic organic group, may be substituted C5 ~ C20 of which may be substituted C6 ~ have C20, Z 4 and Z 5 It may be the same or different, C1 ~ C6 alkyl group, a C1 ~ C6 alkoxy group. ).
[Claim 2]
　(Meth) monomer mixture containing a polymerizable monomer having an acrylic group (A) is
the general formula (i), general formula (ii), there may compound represented by the general formula (iii) and formula (iv) comprising at least two selected from claim 1 for an optical material polymerizable composition.
[Chemical Formula 5]

(wherein, R represents a hydrogen atom or a methyl group, R's, which are present in plural may be the same or different .m, n represents an integer of 0 to 20, be the same or different may also be.)
[formula 6]

is (wherein, R, represents a hydrogen atom or a methyl group, R's, which are present in plural may be the same or different .p represents an integer of 0-20.)
[formula 7]

(wherein, R represents a hydrogen atom or a methyl group, q is. an integer of 0 to 20)
[formula 8]

[Claim 3]
　(C) an ultraviolet absorber, 2- (2-hydroxy-5-t-octylphenyl) benzotriazole, 2- (2-hydroxy-5-t-butylphenyl) benzotriazole, 2- (2-hydroxy-5 - methylphenyl) benzotriazole, is at least one selected 2-ethyl-2'-ethoxy-oxanilide, and (from p- methoxybenzylidene) malonate, polymerization optical material according to claim 1 or 2 gender composition.
[Claim 4]
　Molded body obtained by curing the optical material for the polymerizable composition according to any one of claims 1-3.
[Claim 5]
　Optical material comprising a molded body according to claim 4.
[Claim 6]
　Plastic lenses made of molded product according to claim 4.
[Claim 7]
　A polarizing film,
　at least one of which is formed on the surface, the plastic polarized lens comprising: a base material layer made of a molded product according to claim 4 of the polarizing film.
[8.]
(A) (meth) a monomer mixture containing a polymerizable monomer having an acrylic group,
at least one selected from the compounds represented by (B) the general formula (1) and general formula (2) there, a photochromic compound,
(C) is a formula (a) at least one selected from compounds represented by ~ (c), an ultraviolet absorber,
collectively mixed, the polymerizable composition for an optical material a step of preparing an object,
　comprising the step of forming the lens substrate by the optical material for the polymerizable composition to cast polymerization method for producing a plastic lens;
　PC-L-Chain (1)
　PC-L- '(2) Chain-L'- PC
(in the formula (1) or formula (2), PC and PC' .PC showing a monovalent group derived from a compound of the general formula (3) to (6) and PC 'may be the same or different.
[Chem 9]

(equation (3) to (6 Among, R 1 ~ R 18 is hydrogen, halogen atom, carboxyl group, an acetyl group, a formyl group, an aliphatic group which may be C1 ~ C20 substituted, cycloaliphatic group which may be substituted C3 ~ C20, or an aromatic organic group which may be substituted C6 ~ by C20, each of which may be the same or different. these aliphatic group, alicyclic group or an aromatic organic group may contain an oxygen atom, a nitrogen atom . contained in the compound represented by the general formula (3) to (6), one of the group is attached to L or L 'is a divalent organic group.)
　In the formula (1) or Formula (2), L and L 'are oxyethylene chain, oxypropylene chain, (thio) ester group, a divalent organic group containing one or more selected from (thio) amido group It is shown. In the formula (1) or Formula (2), Chain represents a monovalent or divalent organic group containing at least one selected polysiloxane chain, polyoxyalkylene chain. )
[Formula 10]

(In the formula (a), R 1 , R 2 is an alkyl group of C1 ~ C8 or a halogen atom, may be the same or different. R there exist a plurality of 1 s or more exist, to R 2 together is an integer of good .m 0 to be the same or different 3, n represents an integer of 0 to 3, p is an integer of 0 to 1, R 3 is a straight-chain containing an ester bond or an branched C1 ~ C15 hydrocarbon group.)
[Chem 11]

(in the formula (b), Z 1 and Z 2 may be the same or different, C1 ~ C6 alkyl group, a C1 ~ C6 alkoxy group shown.)
[formula 12]

(in the formula (c), Z 3 represents an alicyclic group of the aromatic organic group, may be substituted C5 ~ C20 of which may be substituted C6 ~ have C20, Z 4 and Z 5 may be the same or different, C1 ~ C6 alkyl group, C1 ~ C6 alkoxy Are shown.).
[Claim 9]
(A) (meth) a monomer mixture containing a polymerizable monomer having an acrylic group,
at least one selected from the compounds represented by (B) the general formula (1) and general formula (2) there, a photochromic compound,
(C) is a formula (a) at least one selected from compounds represented by ~ (c), an ultraviolet absorber,
collectively mixed, the polymerizable composition for an optical material a step of preparing an object,
　a polarizing film, and fixing in a mold for lens casting in spaced condition from the mold,
　the said polarizing film, at least one void formed between the mold optical implanting material for the polymerizable composition,
　the polymerized curing the optical material for the polymerizable composition, a step of laminating the base material layer on at least one surface of the polarizing film
containing a plastic polarized lens of the production side ;
　PC-L-Chain
　(1) '(2) PC-L-Chain-L'-PC
(In the formula (1) or Formula (2), PC and PC' of the general formula (3) to (6) .PC a PC to a monovalent group derived from a compound 'may be the same or different.
[formula 13]

(in the formula (3) ~ (6), R 1 ~ R 18Is hydrogen, halogen atom, carboxyl group, an acetyl group, a formyl group, an aliphatic group optionally substituted C1 ~ C20, alicyclic group which may be substituted C3 ~ be C20 or may be substituted, C6 an aromatic organic radical of ~ C20, may be the same or different. These aliphatic groups, alicyclic group or an aromatic organic group may contain an oxygen atom, a nitrogen atom. Formula (3) contained in the compound represented by - (6), one of the group is attached to L or L 'is a divalent organic group. )
　Formula (1) or the formula (2), L and L 'are oxyethylene chain, oxypropylene chain, (thio) ester group, a divalent organic containing one or more selected from (thio) amido group a group. In the formula (1) or Formula (2), Chain represents a monovalent or divalent organic group containing at least one selected polysiloxane chain, polyoxyalkylene chain. )
[Formula 14]

(In the formula (a), R 1 , R 2 is an alkyl group of C1 ~ C8 or a halogen atom, may be the same or different. R there exist a plurality of 1 s or more exist, to R 2 together is an integer of good .m 0 to be the same or different 3, n represents an integer of 0 to 3, p is an integer of 0 to 1, R 3 is a straight-chain containing an ester bond or an branched C1 ~ C15 hydrocarbon group.)
[formula 15]

(in the formula (b), Z 1 and Z 2 may be the same or different, C1 ~ C6 alkyl group, a C1 ~ C6 alkoxy group show.)
[Formula 16]

(In the formula (c), Z 3 is an aromatic organic group which may be substituted C6 ~ have C20, shows an alicyclic group which may be substituted C5 ~ have C20, Z 4 and Z 5 may be the same or different, C1 ~ C6 alkyl group, a C1 ~ C6 alkoxy group.).