Technical field
[0001]
The present invention relates to a polymerizable composition and a molded body for optical material containing a photochromic compound.
BACKGROUND
[0002]
Plastic lenses, as compared with inorganic lenses, since hardly cracks lightweight, have rapidly spread in the optical elements such as eyeglass lenses, camera lenses. In recent years, development of a plastic lens having photochromic properties has been developed.
[0003]
　Patent Document 1, by radical polymerization of a specific structure as the photochromic compound (meth) polymerizable composition comprising an acrylate and divinylbenzene in casting polymerization method, high refractive index, excellent photochromic properties spectacles it is disclosed that can provide use photochromic lenses. The relevant literature, it is also described that may include a radical polymerization initiator in the polymerizable composition.
[0004]
　Patent Document 2, the photochromic compound and the di (meth) causing radical polymerization and polymerizable monomer having an acrylic group, one or more compositions comprising a radical polymerization initiator in a casting polymerization method Accordingly, and it has a fast photochromic properties of photoresponsive, low specific gravity, to be able to provide a photochromic optical material is disclosed having various physical properties such as impact resistance.
[0005]
　Patent Document 3, diethylene glycol bis-allyl carbonate and / or its oligomer, and 2 kinds of the radical polymerization initiator having a predetermined half-life temperature, a photochromic compound, a photochromic curable composition containing a predetermined range, It showed good photochromic action, it is disclosed that can provide excellent photochromic spectacle lenses mechanical or optical properties.
[0006]
　Patent Document 4, the polyol (allyl carbonate) from about 55 to about 90 wt%, selected terminal ethylenically unsaturated aliphatic polyurethane from about 10 to about 40 wt% with, and from the group consisting of allyl methacrylate and allyl acrylate and bifunctional monomers from about 0 to about 5 consisting wt% polyol (allyl carbonate) component that, by containing an organic photochromic material, it is disclosed that can provide a material excellent in photochromic response. The said document describes a can contain a radical polymerization initiator in the material.
[0007]
　Patent Document 5, a raw material solution containing a half-life temperature of two different radical polymerization initiator, 90 and the low-temperature polymerization step of heating at a low temperature range below ° C., 90 ° C. of ~ 100 ° C. range performed thereafter polymerization by a high temperature polymerization step of heating at a high temperature, method for producing a plastic lens is disclosed glasses.
[0008]
　Patent Document 6 discloses a method of manufacturing a plastic lens comprising a step of radically polymerizing a composition comprising a (meth) acrylate monomer and half-life two or more different organic peroxides.
　Patent Document 7, a polymerizable monomer or the like containing an allyl group, and a half-life temperature of two different aliphatic organic peroxide, the plastic lens composition is disclosed.
[0009]
　Patent Document 8, a monomer composed mainly of dimethallyl phthalate, as a polymerization initiator, and blending the half-life temperature of two different aliphatic organic peroxide at a desired lens type, method for producing a plastic lens to be polymerized forming the blend is disclosed.
CITATION
Patent Document
[0010]
Patent Document 1: WO 2012/141306
Patent Document 2: JP 2004-078052 Patent Publication
Patent Document 3: JP 2009-19157 JP
Patent Document 4: Kohyo 04-502931 JP
Patent Document 5: JP open 2013-213937 JP
Patent Document 6: JP-A 10-147609 JP
Patent Document 7: JP-A 08-127608 JP
Patent Document 8: JP 61-144601 JP
Summary of the Invention
Problems that the Invention is to Solve
[0011]
　The above technique described in the literature, there is a point to be improved in the following.
　In Patent Document 1 or 2, such as (meth) acrylic substrate, although with sufficient light modulating performance, resulting lens is soft, there may not be suitable as the intensity of the spectacle lens. As described in Patent Document 3, the photochromic cured product comprising allyl carbonate, colored there is room for improvement in the accepted light modulating performance. Furthermore, the hardness is low, there is the damaged during use, cracks during processing occurs. As in Patent Document 4, the amount ratio of allyl carbonate is large, photochromic materials consisting of allyl carbonate and acrylic have low transparency, and there is room for improvement in the light modulating performance.
[0012]
　Further, as in Patent Documents 5-8, a predetermined polymerizable monomer, if the half-life temperature using two different radical polymerization initiator, there is room for improvement in the moldability of the lens.
[0013]
　Accordingly, the present inventors have made intensive studies, as a result, by copolymerizing a particular diallyl carbonate and (meth) acrylate in a specific proportion, without impairing the transparency, it serves as an excellent surface hardness, light modulating performance obtained justification photochromic lenses for spectacles, found that further the yield of the product is excellent in moldability is improved. Additionally, than light modulating performance of diallyl carbonate and (meth) molded cured singly acrylate, found that those who copolymerized is improved more synergistically dimming performance.
Means for Solving the Problems
[0014]
　The present invention can be illustrated below.
[1] (A) represented by the general formula (1), and allyl carbonate compounds containing two or more allyloxycarbonyl group,
(B) represented by the general formula (2), a (meth) acrylic group 2 and (meth) acrylate compound containing more than
One, includes a (C) a photochromic compound, a,
　in total 100 wt% of the compound (a) and the compound (B), compound (a) below 30 wt% more than 0 wt% compound (B) in an amount of less than 70 wt% or more and 100 wt%, the optical material for the polymerizable composition.
[Formula 1]

(R 1 was also good chain or branched contain a hetero atom C3 of ~ C35 aliphatic polyols derived 2-20 bivalent group or may also C5 ~ contain a hetero atom C40 .m illustrating a 2-20 divalent group derived from a cyclic aliphatic polyol is an integer of 2-10. Note that, R 1 does not include the allyloxycarbonyl group.)
[Formula

2] (R 2 is heteroaryl .R showing a divalent to tetravalent organic group atoms or an aromatic group of carbon atoms which may contain 1 to 30 3 are, .n represents a hydrogen atom or a methyl group is an integer of 2-4.)
in total 100 wt% of [2] compound (a) and the compound (B), a compound including (a) 30 wt% 5 wt% or more or less, the compound (B) in an amount of less than 95 wt% 70 wt% or more of the optical material for the polymerizable composition according to [1].
[3] In addition, the radical polymerization initiator include (D),
　a radical polymerization initiator (D) is at
least, 50 ° C. of less than 5 hours after 100% radical remaining ratio of 20% or more after, and 70 ° C. for 5 hours after in the radical polymerization initiator is a radical residual ratio 0% or more and less than 30% and
(D1), a radical polymerization initiator is a radical residual ratio 30% or more and less than 100% after the lapse of 70 ° C. 5 hours and (D2),
including , [1] or an optical material for a polymerizable composition as described in [2].
[4] compound (A), diethylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol , neopentyl glycol, 3-methyl-1,5-pentanediol, 2-methyl-2-ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2,2,4 trimethyl-1,3-pentanediol, 1,4-dimethylolcyclohexane and 4,8-bis (hydroxymethyl) - [5.2.1.0 2, 6 ] at least one selected from tricyclodecane bis (allyl carbonate) compounds of diols,
glycerol, trimethylolpropane and tris ( Dorokishiechiru) at least one triol tris (allyl carbonate selected from isocyanurate) compounds,
pentaerythritol, at least one tetraol tetra (allyl carbonate selected from diglycerol and ditrimethylolpropane) compound,
dipenta erythritol hexa (allyl carbonate) compounds, and
the diols, the triol, is at least one said mixed poly (allyl carbonate) compound of at least two compounds selected from tetraols and said dipentaerythritol is selected from , [1] to an optical material for the polymerizable composition according to any one of [3].
[5] compound (A),
(i) diethylene glycol bis (allyl carbonate) compounds and mixtures and oligomers thereof,
(ii) bis mixture of diethylene glycol and neopentyl glycol (allyl carbonate) compounds and mixtures and oligomers thereof ,
(iii) diethylene glycol and tris poly mixture of (hydroxyethyl) isocyanurate (allyl carbonate) compounds and mixtures and oligomers thereof,
and (iv) diethylene glycol and poly (allyl carbonate) of a mixture of trimethylol propane compounds and oligomers mixture of
(v) diethylene glycol and poly (allyl carbonate) of a mixture of pentaerythritol compound and a mixture of oligomers thereof,
(vi) diethylene glycol neopentyl glycol A mixture of poly (allyl carbonate) compounds and oligomers of the mixture of pentaerythritol, and
(vii) diethylene glycol and poly (allyl carbonate) of neopentyl glycol and mixtures of pentaerythritol compound and a mixture of oligomers thereof,
diethylene glycol bis (allyl carbonate) compounds, and poly (allyl carbonate) mixture comprising a mixture of an oligomer thereof is at least one selected from [1] to the polymerizable composition for an optical material according to any one of [4] object.
[6] compound (B), the general formula (2-1), is selected from the compounds represented by the general formula (2-2), for optical material according to any one of [1] to [5] polymerizable composition.
[Formula 3]

(p represents a number of 1 ~ 100, R 3 represents a hydrogen atom or a methyl group, each may not be the same.)
[Formula 4]

(q represents one or more respective numerical , the sum of the two q is .R numerical 2-100 3 represents a hydrogen atom or a methyl group, each may not be the same .X is a substituted or unsubstituted divalent aromatic radical, a substituted or unsubstituted divalent may contain an aromatic group having 1 to 20 carbon atoms in the aliphatic group.)
[7] compound (B), in the general formula (2-1), p is is selected from the compounds represented by 2-4, for optical materials polymerizable composition according to [6].
[8] compound (B) is at least one diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, is selected from diethylene glycol diacrylate and triethylene glycol diacrylate, a polymerizable composition for optical material according to [7] object.
[9] compound (C) is represented by the general formula (5), [1] to an optical material for the polymerizable composition according to any one of [8].
[Chemical Formula 5]

(wherein, R 1 and R 2 may be the same or different, independently, hydrogen;
linear or branched alkyl group of 1 to 12 carbon atoms;
a cycloalkyl group having 3 to 12 carbon atoms ;
is a substituted or unsubstituted, as heteroaryl group (substituent of the aryl group or a C 4-24 having 6 to 24 carbon atoms, a halogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 12 carbon atoms , straight-chain or branched alkoxy group having 1 to 12 carbon atoms, at least one straight-chain or branched haloalkyl group having carbon number of 1 to 12 substituted by a halogen atom, a carbon substituted with at least one halogen atom linear or branched haloalkoxy group having 1 to 12, at least one phenoxy group or a naphthoxy group substituted by straight-chain or branched alkyl or alkoxy group having 1 to 12 carbon atoms Linear or branched alkenyl group having a carbon number of 2 ~ 12, -NH 2 group, -NHR group, -N (R) 2 is group (R is a linear or branched alkyl group having 1 to 6 carbon atoms If .R is two, the two R may be the same or different), and having at least one substituent selected from a methacryloyl group or an acryloyl group);..
aralkyl or heteroaralkyl group (carbon ) linear or branched alkyl group having 1 to 4 are replaced by the above aryl group or a heteroaryl group.
represents,
　R 3 may be the same or different, independently, a halogen atom;
the carbon number 1-12 linear or branched alkyl group;
; a cycloalkyl group having 3 to 12 carbon atoms
linear or branched alkoxy group having 1 to 12 carbon atoms;
at least one carbon atoms substituted with halogen atoms 1 2 straight chain or branched haloalkyl group, at least one halocycloalkyl group having 3 to 12 carbon atoms substituted by halogen atoms, having 1 to 12 carbon atoms which is substituted with at least one halogen atom linear or branched haloalkoxy group;
a substituted or unsubstituted, as heteroaryl group (substituent of the aryl group or a C 4-24 having 6 to 24 carbon atoms, a halogen atom, a hydroxyl group, a straight-chain or branched having 1 to 12 carbon atoms alkyl group, straight or branched alkoxy group having 1 to 12 carbon atoms, at least one straight-chain or branched haloalkyl group having 1 to 12 carbon atoms which is substituted with a halogen atom, substituted with at least one halogen atom straight or branched haloalkoxy group having 1 to 12 carbon atoms, a straight-chain or branched least one alkyl group having 1 to 12 carbon atoms or alkoxy Alkoxy phenoxy group or a naphthoxy group substituted by a radical, having at least one substituent selected straight or branched alkenyl group having 2 to 12 carbon atoms, and amino groups from. );
A linear or branched alkyl group aralkyl or heteroaralkyl group (having 1 to 4 carbon atoms are substituted with the aryl group or heteroaryl group);.
As a substituted or unsubstituted phenoxy or naphthoxy group (substituent , having at least one substituent selected from linear or branched alkyl or alkoxy group having 1 to 6 carbon
atoms);. -NH 2 , -NHR, -CONH 2 or -CONHR,
is (R, carbon atoms 1 is a linear or branched alkyl group of
6);. -OCOR 8 or -COOR 8 (wherein, R 8 is a linear or branched alkyl group having 1 to 6 carbon atoms or carbon atoms, 3 cycloalkyl group to 6 or R, 1 , R 2 in a phenyl group substituted by at least one substituent of the substituted aryl or substituted heteroaryl group Others are unsubstituted phenyl group);.
Represents,
m has an integer from 0 to 4;
is A, the following formula (A 2 ) or Formula (A 4 ) [Chemical
Formula 6]

a Aner of ring represents, in these Asnelles of rings,
the dotted line, the general formula (5) carbon C naphthopyran ring of 5 carbon C 6 represents a bond;
Aner of ring (a 4 naphthopyran of binding α) of the general formula (5) carbon C ring 5 or carbon C 6 can be coupled to;
R 4 is the same or different, independently, OH, a linear or branched alkyl group or alkoxy group having 1 to 6 carbon atoms It represents, or two R 4 may form a carbonyl (CO);
R 5 is halogen;
alkyl group, straight or branched having 1 to 12 carbon atoms;
substituted by at least one halogen atom, C 1 -C linear or branched haloalkyl group having 1-6;
Shikuroa 3 to 12 carbon atoms Kill group;
a straight-chain or branched alkoxy group having 1 to 6 carbon atoms;
a substituted or unsubstituted phenyl or benzyl group (the substituent of the general formula (5) R 1 , R 2 and groups independently aryl or If corresponding to a heteroaryl group, R 1 , R 2 has at least one of the substituents mentioned above in the definition of
groups);. -NH 2 , -NHR
(wherein, R is a linear 1 to 6 carbon atoms is a chain or branched alkyl group);.
as a substituted or unsubstituted a is phenoxy or naphthoxy group (substituent has at least straight-chain or branched alkyl or alkoxy group having 1 to 6 carbon atoms).;
-COR 9 , -COOR 9 or -CONHR 9 group (wherein, R 9 is a linear or branched alkyl group or a cycloalkyl group having 3 to 6 carbon atoms, having 1 to 6 carbon atoms or a substituted or unsubstituted, of replacement As Eniru or a benzyl group (substituent radical, R in the general formula (5) 1 , R 2 if groups independently correspond to an aryl or heteroaryl radical, R 1 , R 2 at least of the substituents described above in the definition of group having one. ));
A is (A 4 may exhibit), n is an integer from 0 to 2, p is an integer from 0 ~ 4, A is (A 2 may exhibit), n is 0-2 it is an integer of up to. )
[10] Compound (C) is represented by the general formula (a) or represented by the general formula (b), [1] ~ for optical materials polymerizable composition according to any one of [8].
　PC-L-Chain
　(a) PC-L-Chain-L'-PC
'(b) (PC and PC' of the general formula (c) .PC and PC shown - the (f) 'is either the same or different or.)
[Formula 7]

(R 1 ~ R 18 is hydrogen, halogen atom, carboxyl group, an acetyl group, a formyl group, an aliphatic group which may be substituted C1 ~ and C20, may also be C3 ~ which is substituted 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 (c) ~ (f), any one of the groups, and .L that bind to L or L 'is a divalent organic group L 'is an oxyethylene chain, oxypropylene chain, (thio) ester group, (thio) .Chain showing a divalent organic group containing one or more selected from bromide group, a monovalent or divalent organic group containing at least one selected polysiloxane chain, polyoxyalkylene chain. ) [11] [1] ~ shaped body obtained by curing the optical material for the polymerizable composition according to any one of [10]. Optical material comprising a molded product according to [12] [11]. [13] a plastic lens composed of a molded product according to [11]. [14] and a polarizing film, 　at least formed on the object plane side of the surface, the plastic polarized lens comprising: a base material layer made of a molded product according to [11] of the polarizing film.

[0015]
　In the present invention, for example, a "bis diol (allyl carbonate) compound", two hydroxyl groups of the diol is meant a compound having the replaced structure with an allyl carbonate group. Diols may be combined one or two or more kinds.
　Further, in the present invention, for example, a "diethylene glycol bis (allyl carbonate) compounds in the mixture of neopentyl glycol",
compounds having a (1) two hydroxyl groups of diethylene glycol was replaced with an allyl carbonate group structure,
(2 ) neopentyl two hydroxyl groups in glycol is meant a compound having a structure which is replaced by an allyl carbonate group.
　Further, in the present invention, for example, a "bis mixture of diethylene glycol and neopentyl glycol oligomers (allyl carbonate) compound"
selected below (3), either, or from those (4), or (5) It means two or more of the mixture.
(3) diethylene glycol bis (allyl carbonate) oligomer compounds
　2 molecules or more diethylene glycol oligomerized via carbonate bond, a compound having a hydroxyl group terminal is replaced with an allyl carbonate group structure.
(4) neopentyl glycol bis (allyl carbonate) oligomer compounds
　neopentyl glycol or 2 molecules oligomerize via carbonate bond, a compound having a hydroxyl group terminal is replaced with an allyl carbonate group structure.
(5) of diethylene glycol and neopentyl glycol, bis (allyl carbonate) oligomer compounds
　with one or more molecules of diethylene glycol and one or more molecules of neopentyl glycol, via carbonate linkages, was oligomerized in the same molecule in random combination, compounds with a terminal hydroxyl group is replaced with an allyl carbonate group structure.
　"Bis trifunctional or higher polyols (allyl carbonate) compounds," "the diol and tri- or higher functional polyol, two or more reference bis (allyl carbonate) compound" is the same case.
　"Bis trifunctional or higher polyols oligomers (allyl carbonate) compound", if "the diol and tri- or higher functional polyol, two or more reference bis oligomer (allyl carbonate) compounds", all of the hydroxyl groups of terminal including structure was replaced by allyloxy carbonate group, a part of the hydroxyl end is replaced by allyloxy carbonate group structure.
　Further, in the present invention, for example, "1 to 10" means "one or more, 10 or less".
　In the present invention, the hetero atom means C, and atoms other than H.
Effect of the invention
[0016]
　According to the optical material for the polymerizable composition of the present invention, without impairing the transparency, it is possible to provide an excellent surface hardness, also serves as a light modulating performance aligned photochromic lenses for spectacles. Furthermore, the yield of photochromic lenses are improved and excellent moldability.
DESCRIPTION OF THE INVENTION
[0017]
　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) represented by the general formula (1), and allyl carbonate compounds containing two or more allyloxycarbonyl group,
the table in (B) formula (2) is the (meth) acrylic group containing two or more (meth) acrylate
compound, comprising a (C) a photochromic compound, a,
　in total 100 wt% of the compound (a) and the compound (B), compound (a) the following 30 wt% more than 0 wt%, including the compound (B) in an amount of less than 70 wt% or more and 100 wt%.
[0018]
[Formula 8]

[0019]
　R 1 is derived from cycloaliphatic polyol of an aliphatic polyol derived 2-20 divalent group or heteroatom may contain C5 ~ C40 of C3 ~ was also good chain or branched contain a hetero atom C35 It shows a 2-20 monovalent group. m represents an integer of 2-10. Incidentally, R 1 does not include the allyloxycarbonyl group.
[0020]
[Formula 9]

[0021]
　R 2 represents a divalent to tetravalent organic radical heteroatom or aromatic carbon atoms which may contain a group 1-30. R 3 represents a hydrogen atom or a methyl group. n is an integer of 2-4.
　According to such an optical material for a polymerizable composition of the present embodiment, without impairing the transparency, it is possible to obtain an excellent surface hardness, also serves as a light modulating performance aligned photochromic lenses for spectacles, moldability yield of photochromic lenses are improved and excellent.
　Each component is explained below.
[0022]
[(A) allyl carbonate compound]
　in the present embodiment, allyl carbonate compound (A) can be expressed by the following equation.
[0023]
[Formula 10]

[0024]
　R 1 is derived from cycloaliphatic polyol of an aliphatic polyol derived 2-20 divalent group or heteroatom may contain C5 ~ C40 of C3 ~ was also good chain or branched contain a hetero atom C35 It shows a 2-20 monovalent group. m represents an integer of 2-10. Incidentally, R 1 does not include the allyloxycarbonyl group.
[0025]
　Allyl carbonate compound (A) may contain the oligomer. Oligomer, for example, be produced by transesterification of diallyl carbonate with a polyol, a poly bimolecular more polyols via carbonate linkages and ligated (allyl carbonate). The allyl carbonate compound is a linear or branched aliphatic polyol having 3 to 35 carbon atoms poly (allyl carbonate). In a molecule of poly (allyl carbonates) of cycloaliphatic polyols having 5 to 40 carbon atoms are also suitable for this purpose. These polyols, 2-6 in the normal molecule, preferably having 2 to 4 hydroxyl groups. Mixed poly (allyl carbonate), i.e. derived from two or more polyols, one can be obtained by mixing poly single polyol (allyl carbonate), or by chemical reaction starting from mixtures with diallyl carbonate polyol it is also possible to use those which can be obtained directly. Finally, all these poly (allyl carbonate) may be in the form of a mixture of monomer or monomers and oligomers.
[0026]
R 　in the general formula (1) 1 polyol constituting the, as a specific example, diethylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5 - pentanediol, 1,6-hexanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-methyl-2-ethyl-1,3-propanediol, 2,2-diethyl-1,3 - propanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,4-dimethylolcyclohexane, 4,8-bis (hydroxymethyl) - [5.2.1.0 2, 6 ] tri cyclodecane, glycerol, trimethylolpropane, tris (hydroxyethyl) isocyanurate, Pentae Suritoru, diglycerol, ditrimethylolpropane, and di pentaerythritol.
[0027]
　Accordingly, examples of the allyl carbonate compound (A), for example, diethylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1 , 6-hexanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-methyl-2-ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2 , 2,4-trimethyl-1,3-pentanediol, 1,4-dimethylolcyclohexane and 4,8-bis (hydroxymethyl) - [5.2.1.0 2, 6 ] is selected from tricyclodecane at least one diol bis (allyl carbonate) compounds that, glycerol, Trimethylolpropane and tris (hydroxyethyl) at least one triol tris (allyl carbonate) is selected from the isocyanurate compound, pentaerythritol, of at least one tetraol selected from diglycerol and ditrimethylolpropane tetra ( allyl carbonate) compounds, hexa dipentaerythritol (allyl carbonate) compounds, and the diols, mixed poly (allyl carbonate) compounds of the triol, at least two kinds selected from the tetraols and the dipentaerythritol compounds, from comprising at least one selected.
[0028]
　Note that "at least two bis mixture of diol (allyl carbonate)", for example, if the diol is diethylene glycol and neopentyl glycol is obtained as a mixture of monomer component and oligomer component follows.
Monomer component
(1) diethylene glycol bis (allyl carbonate)
(2) neopentyl glycol bis (allyl carbonate)
oligomer component
(3) an oligomer that contains only diethylene glycol-derived hydrocarbons (and ether)
(4) neopentyl glycol-derived hydrocarbons oligomers containing only
composite oligomer containing a (5) a hydrocarbon (or ethers) derived from diethylene both hydrocarbons from neopentyl glycol
[0029]
　The following are preferred examples of suitable allyl carbonate polymer compound for the purposes of the present invention.
(i) diethylene glycol bis (allyl carbonate) compounds and mixtures thereof with oligomers
　of diethylene glycol bis (allyl carbonate) can be defined by the formula (1-1).
[0030]
[Of 11]

[0031]
　Also, oligomers of diethylene glycol bis (allyl carbonate) can be defined by the formula (1-2).
[0032]
[Chem. 12]

[0033]
　In the formula, r is 2 or more.
　Compound (1-1) may, for example, "Encyclopedia of Chemical Technology", Kirk-Othmer, III Edition, Volume 2, as described in 111-112 pages, reaction with allyl alcohol diethylene glycol bis (chloroformate) it can be prepared by. Mixtures of diethylene glyceryl Corbis (allyl carbonate) (Formula (1-1)) and oligomers thereof (formula (1-2)), for example, as described in European patent 35.304, base by operating in the presence of sexual catalyst, it can be conveniently prepared by transesterification of diallyl carbonate and diethylene glycol. These mixtures usually contain up to about 80 wt% oligomers.
[0034]
(ii) diethylene glycol bis (allyl carbonate) of a mixture of neopentyl glycol compounds and mixtures and oligomers thereof
　The bis (allyl carbonate) compounds, except for replacing diethylene glycol with a mixture of diethylene glycol and neopentyl glycol, wherein is the same as the bis of (i) (allyl carbonate).
[0035]
(iii) diethylene glycol and tris poly (allyl carbonate) of a mixture of (hydroxyethyl) isocyanurate compounds and mixtures and oligomers thereof
　The poly (allyl carbonate) compounds, for example, is described in U.S. Patent No. 4,812,545 and as can be obtained by transesterification of diethylene glycol and tris diallyl carbonate of a mixture of (hydroxyethyl) isocyanurate.
[0036]
(iv) diethylene glycol and poly (allyl carbonate) of a mixture of trimethylol propane compounds and mixtures and oligomers thereof
　The poly (allyl carbonate) compounds, except for replacing tris (hydroxyethyl) isocyanurate with trimethylolpropane, it is similar to the poly (allyl carbonate) of said (iii).
[0037]
(v) diethylene glycol and poly (allyl carbonate) of a mixture of pentaerythritol compound and a mixture of oligomers thereof
　The poly (allyl carbonate) compounds, except for replacing tris (hydroxyethyl) isocyanurate with pentaerythritol, of the poly (iii) it is the same as (allyl carbonate) compounds.
[0038]
(vi) diethylene glycol and poly (allyl carbonate) of neopentyl glycol and mixtures of pentaerythritol compound and a mixture of oligomers thereof
　The poly (allyl carbonate) compounds, the diethylene glycol being substituted by two diols diethylene glycol neopentyl glycol it addition, the poly (allyl carbonate) of said (v) is the same as compound.
[0039]
(vii) diethylene glycol and neopentyl glycol and poly (allyl carbonate) of a mixture of pentaerythritol compound and a mixture of oligomers thereof,
poly comprising a mixture of diethylene glycol bis (allyl carbonate) compound and its oligomer, a (allyl carbonate) blend
[0040]
[(B) (meth) acrylate compound]
　In the present invention, (meth) acrylate compound (B) can be represented by the following formula.
[0041]
[Formula 13]

[0042]
　R 2 represents a divalent to tetravalent organic radical heteroatom or aromatic carbon atoms which may contain a group 1-30. R 3 represents a hydrogen atom or a methyl group. n is an integer of 2-4.
　Further, (meth) acrylate compound (B), general formula (2-1), represented by may be mentioned compounds with the general formula (2-2).
[0043]
[Formula 14]

[0044]
　p represents a number of 1 ~ 100, R 3 represents a hydrogen atom or a methyl group, may not be respectively identical. p is preferably a number from 1 to 50, more preferably a number from 1 to 20, more preferably numerical values of 2-10, it figures 2-4 are particularly preferred.
[0045]
　It is represented by (meth) acrylate compound of the general formula (2-1), ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, propylene glycol dimethacrylate, dipropylene glycol dimethacrylate, tripropylene glycol dimethacrylate, tetrapropylene glycol dimethacrylate, propylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, tetrapropylene glycol di It can include at least one selected from acrylate.
[0046]
[Formula 15]

[0047]
　q each represent one or more numbers, the sum of the two q is a number from 2 to 100. R 3 represents a hydrogen atom or a methyl group, may not be respectively identical. X represents a substituted or unsubstituted divalent aromatic group, a substituted or unsubstituted divalent may contain an aromatic group having 1 to 20 carbon atoms in the aliphatic group.
[0048]
　As is represented by the general formula (2-2) (meth) acrylate compounds, 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-methacryloyloxyethoxy) propane, 2,2-bis - (4- Methacryloyloxy) propane, 2- (4-methacryloyloxy-ethoxy) -2- (4- (methacryloyloxy ethoxy) ethoxyphenyl) propane, 2- (4-acryloyloxy ethoxy) -2- (4- (acryloyloxy) ethoxy phenyl) propane, 2,2-bis - (4- (methacryloyloxy ethoxy) ethoxyphenyl) propane, 2,2-bis - (4- (acryloyloxy ethoxy) selected from ethoxy phenyl) propane at least one can be mentioned that.
[0049]
　The (meth) acrylate compound other than the above, butanediol dimethacrylate, hexamethylene dimethacrylate, 2,2-bis (4-methacryloyloxy-ethoxy-3,5-dibromophenyl) propane, 2,2-bis - (4 - methacryloyloxy pentaethoxy phenyl) propane, pentaerythritol triacrylate, pentaerythritol tetraacrylate, trimethylolpropane triacrylate, dipentaerythritol hexaacrylate, bisphenol A- diglycidyl ether diacrylate based, bisphenol A- diglycidyl ether dimethacrylate system, tetrabromobisphenol A- diglycidylether acrylate-based, tetrabromobisphenol A- diglycidylether It can include at least one selected from the group consisting of data acrylate.
[0050]
　(Meth) acrylate compound (B), among these exemplified compounds, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, dipropylene glycol dimethacrylate, tripropylene glycol dimethacrylate, di propylene glycol diacrylate, at least one is preferably selected from tripropylene glycol diacrylate,
　more that is at least one diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, is selected from diethylene glycol diacrylate and triethylene glycol diacrylate, preferably,
diethylene glycol dimethacrylate, triethylene At least one member selected from glycol dimethacrylate are especially preferred.
[0051]
　Total of 100% by weight of the compound (A) and the compound (B), allyl carbonate compound (A), 0 wt% to greater than 30 wt% or less, preferably 30 wt% 5 wt% or more or less, more preferably 5 wt % or more 28 wt% or less, particularly preferably comprises 25 wt% 5 wt% or more or less, (meth) acrylate compound (B) is less than 70 wt% or more and 100 wt%, preferably 95 wt% 70 wt% or more or less, more preferably 72 wt% to 95 wt% or less, particularly preferably it can include 75 wt% to 95 wt% or less.
　Allyl carbonate compound (A) faster and fading rate is included, color density superior in terms of light modulating performance dark and mechanical strength of the lens is increased. Also If it is 30 wt% or less, excellent transparency. In other words, by comprising a compound (A) and the compound (B) in the range, the resulting resin molded article can exhibit sufficient light modulating performance and mechanical strength, clouding is suppressed is excellent in transparency. Furthermore, the yield of the photochromic lens is excellent in moldability is improved.
[0052]
[(C) a photochromic compound]
　In the present embodiment, as the photochromic compound (C), it is not particularly limited, from known compounds which may be used in the photochromic lens, be appropriately selected and used any of it can. For example, spiropyran compounds, spirooxazine compounds, fulgide compounds, naphthopyran compounds, bisimidazole compounds, from depending on the desired coloration, can be used alone or in combination, described below in general formula (a) and it is selected from the general formula (b) can also be at least one.
[0053]
　Examples of the spiropyran compound, India Linus indole ring and benzene ring are halogen pyrophosphoric benzopyran, methyl, ethyl, methylene, ethylene, substitution products, which are substituted by hydroxyl group, and the indole ring of India Linus pyro naphthopyran naphthalene ring is halogen, methyl, ethyl, methylene, ethylene, substitution products, which are substituted by hydroxyl group, India Linus Piroki Norino indole ring halogen pyran, methyl, ethyl, methylene, ethylene, each substituted substituted with hydroxyl group body, indole ring India Linus Piropi chloride pyran halogen, methyl, ethyl, methylene, ethylene, substitution products substituted by a hydroxyl group or the like, and the like.
[0054]
　Examples of the spiro-oxazine compounds, halogen India Linus pyromellitic benzoxazines substituted by an indole ring and benzene ring, methyl, ethyl, methylene, ethylene, substitution products, which are substituted by hydroxyl group, India Linus pyro naphthoxazole Gin of the indole ring and naphthalene ring are halogen, methyl, ethyl, methylene, ethylene, substitution products, which are substituted by hydroxyl group, India Linus pyro phenanthrolato benzoxazine of the indole ring is halogen, methyl, ethyl, methylene, ethylene, and a hydroxyl substitution products substituted in India Linus Piroki Norino benzoxazine of the indole ring is halogen, methyl, ethyl, methylene, ethylene, substitution products, which are substituted by hydroxyl group, a piperidine ring and naphthalene ring piperidinocarbonyl spironaphthoxazine is halogen, methyl Ethyl, methylene, ethylene, substitution products substituted by a hydroxyl group or the like, and the like.
[0055]
　Examples of the fulgide compound, -7,2'- N- cyanomethyl-6,7-dihydro-4-methyl-2-phenyl-spiro (5,6-benzo [b] thiophene-dicarboximide tricyclo [3. 3.1.1 3,7 ] decane], N- cyanomethyl-6,7-dihydro-2-(p-methoxyphenyl) -4-methylspiro (5,6-benzo [b] thiophene-dicarboximide -7, 2'tricyclo [3.3.1.1 3, 7 ] decane), 6,7 dihydro -N- methoxycarbonylmethyl-4-methyl-2-phenyl-spiro (5,6-benzo [b] Chiofenji carboxyimide -7,2'- tricyclo [3.3.1.1 3, 7 ] decane), 6,7 dihydro-4-methyl-2-(p-methylphenyl) -N- nitro methyl spiro (5 , 6-benzo [b Thiophene-dicarboximide -7,2'- tricyclo [3.3.1.1 3, 7 ] decane), N- cyanomethyl-6,7-dihydro-4-cyclopropyl-3- methylspiro (5,6-benzo [b] thiophene-dicarboximide -7,2'- tricyclo [3.3.1.1 3, 7 ] decane), N- cyanomethyl-6,7-dihydro-4-cyclopropyl-spiro (5,6-benzo [b] thiophene-dicarboximide -7,2'- tricyclo [3.3.1.1 3, 7 ] decane), N- cyanomethyl-6,7-dihydro-2-(p-methoxyphenyl) -4- cyclopropyl spiro (5,6-benzo [b] thiophene-dicarboximide -7,2'- tricyclo [3.3.1.1 3, 7 ] decane), and the like.
[0056]
　Examples of the naphthopyran compounds, spiro [norbornane-2,2 '- [2H] benzo [h] chromene], spiro [bicyclo [3.3.1] nonane -9,2' - [2H] benzo [ h] chromene], 7'-methoxy spiro [bicyclo [3.3.1] nonane -9,2 '- [2H] benzo [h] chromene], 7'Metokishisupi [norbornane-2,2' - [2H ] benzo [f] chromene], 2,2-dimethyl-7-octoxy [2H] benzo [h] chromene, spiro [2-bicyclo [3.3.1] nonene -9,2 '- [2H] benzo [ h] chromene], spiro [2-bicyclo [3.3.1] nonene -9,2 '- [2H] benzo [f] chromene], 6-morpholino-3,3-bis (3-fluoro-4- methoxyphenyl) -3H- benzo (f) chromene 5-isopropyl-2,2-diphenyl -2H- benzo (h) chromene, etc. and include compounds represented by the compound represented by and the following formula by the following general formula (3) (4).
[0057]
[Chemical Formula 16]

[0058]
[Chemical Formula 17]

[0059]
　Formula (3) and general formula (4), R 1 and R 2 may be the same or different, independently, hydrogen;
linear or branched alkyl group having 1 to 12 carbon atoms;
C 3 -C 12 cycloalkyl group;
a substituted or unsubstituted heteroaryl group an aryl group or a C 4-24 having 6 to 24 carbon atoms;
aralkyl or heteroaralkyl group (linear or branched alkyl group having 1 to 4 carbon atoms There has been substituted with an aryl group or a heteroaryl group.) shows a.
[0060]
　Substituent of the aryl group or substituted heteroaryl group having a carbon number of 4-24 substituted carbon number of 6 to 24, a halogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 12 carbon atoms, carbon linear or branched alkoxy group having 1 to 12, at least one straight-chain or branched haloalkyl group having 1 to 12 carbon atoms which is substituted by halogen atom, carbon substituted with at least one halogen atom 1 linear or branched haloalkoxy group having 1-12, and at least one linear or phenoxy group or a naphthoxy group substituted by an alkyl group or an alkoxy group branched having 1 to 12 carbon atoms, a straight C 2 -C 12 chain or branched alkenyl group, -NH 2 group, -NHR group, -N (R) 2 group (R is present two 2 .R is a linear or branched alkyl group having 1 to 6 carbon atoms case The two R may be the same or different.), And is at least one selected from a methacryloyl group or an acryloyl group.
[0061]
　R 3 may be the same or different, independently, a halogen atom;
; a linear or branched alkyl group having 1 to 12 carbon atoms
a cycloalkyl group having 3 to 12 carbon atoms;
straight chain of 1 to 12 carbon atoms or branched alkoxy group;
at least one straight-chain or branched haloalkyl group having 1 to 12 carbon atoms which is substituted with a halogen atom, at least one of carbon atoms which is substituted by halogen atoms 3-12 halocycloalkyl group, at least one One of the straight-chain or branched haloalkoxy group having carbon number of 1 to 12 substituted by a halogen atom;
a substituted or unsubstituted, as heteroaryl group (substituent of the aryl group or a C 4-24 having 6 to 24 carbon atoms a halogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 12 carbon atoms, straight-chain or branched alkoxy group having 1 to 12 carbon atoms, at least one tooth tips Linear or branched haloalkyl group having carbon number of 1 to 12 substituted by androgenic atoms, at least one straight-chain or branched haloalkoxy group having carbon number of 1 to 12 substituted by a halogen atom, at least one carbon linear or branched alkyl group or a phenoxy group or a naphthoxy group substituted by an alkoxy group having 1 to 12 linear or branched alkenyl group having 2 to 12 carbon atoms, and amino groups, at least is selected from having one substituent);.
a linear or branched alkyl group aralkyl or heteroaralkyl group (having 1 to 4 carbon atoms are substituted with the aryl group or heteroaryl group);.
a substituted or unsubstituted phenoxy or as a naphthoxy group (substituent, small is selected from linear or branched alkyl or alkoxy group having 1 to 6 carbon atoms Kutomo having one substituent);.
-NH 2 , -NHR, -CONH 2 or -CONHR,
(R is a linear or branched alkyl group having 1 to 6 carbon
atoms);. -OCOR 8 or -COOR 8 (wherein, R 8 is a linear or branched alkyl group or a cycloalkyl group having 3 to 6 carbon atoms, having 1 to 6 carbon atoms, or R, 1 , R 2 in, substituted aryl, or at least one by a phenyl group substituted or unsubstituted phenyl group substituents of the substituted heteroaryl group);.
represents a.
[0062]
　At least two adjacent R 3 bonded to each other, R 3 contains a carbon atom which is attached, can form one or more aromatic ring group or non-aromatic ring group. Aromatic group or a non-aromatic ring include oxygen, sulfur, and one which may contain a hetero atom selected from the group consisting of nitrogen a ring or two Aner reduction has been ring.
[0063]
　l is an integer from 0 to 2. m is an integer from 0 to 4.
　Also, the other, as naphthopyran compounds, WO2013 / 78086 Publication, WO2012 / 149599 publication, WO2010 / 020 770 JP polysiloxane oligomer according to WO2009 / 146509 publication, polyalkylene oxide, at least one end of each polyalkyl ester and compounds in which the dimming dye molecules were added, the structure represented by the general formula of the described (3) or general formula (4) are joined by a linking group, include compounds having two or more naphthopyran rings per molecule It is.
[0064]
　In naphthopyran compound represented by the general formula (3), a compound represented by the following general formula (5) (hereinafter, also the compound (5) referred to.) Are preferred examples.
[0065]
[Chem. 18]

[0066]
　R 1 , R 2 , R 3 , m is the same as defined above, A is the following formula (A 1 ) ~ (A 5 represents a Asnelles reduction ring).
[0067]
[Of 19]

[0068]
　These Asnelles of rings (A 1 ) ~ (A 5 in), and a dotted line, carbon C naphthopyran ring in the general formula (5) 5 carbon C 6 represents a bond. Asnelles of ring (A 4 ) or (A 5 binding α) of the carbon C naphthopyran ring in the general formula (5) 5 or carbon C 6 is coupled to.
[0069]
　R 4 is the same or different, independently, OH, a straight-chain or branched alkyl or alkoxy group having 1 to 6 carbon atoms, or two R 4 may form a carbonyl (CO).
[0070]
　R 5 , R 6 and R 7 are, independently, a halogen atom (preferably fluorine, chlorine or bromine);
a carbon number of 1 to 12 linear or branched alkyl group (preferably having 1 to 6 carbon atoms straight or branched alkyl group);
substituted by at least one halogen atom, a linear or branched haloalkyl group (preferably having 1 to 6 carbon atoms, a fluoroalkyl group);
a cycloalkyl having from 3 to 12 carbon atoms alkyl group;
a straight-chain or branched alkoxy group having 1 to 6 carbon atoms;
a substituted or unsubstituted phenyl or benzyl group (the substituent of the general formula (5) R 1 , R 2 and groups independently aryl or If corresponding to a heteroaryl group, R 1 , R 2 has at least one of the substituents mentioned above in the definition of
groups);. -NH 2 , -NHR
(wherein, R is a linear 1 to 6 carbon atoms chain or branched . Alkyl a group);
a substituted or unsubstituted a is phenoxy or naphthoxy group (substituent has at least straight-chain or branched alkyl or alkoxy group having a carbon number of 1 ~ 6);.
-COR 9 , - COOR 9 or -CONHR 9 group (wherein, R 9 is a linear or branched alkyl group or a cycloalkyl group having 3 to 6 carbon atoms, having 1 to 6 carbon atoms or a substituted or unsubstituted phenyl or benzyl, as group (substituent radical, R in the general formula (5) 1 , R 2 if groups independently correspond to an aryl or heteroaryl radical, R 1 , R 2 at least one of the substituents mentioned above in the definition of group with) represents a.) represents the.
[0071]
　n is an integer from 0 to 6, o is an integer from 0 to 2, p is an integer from 0 to 4, q is an integer from 0 to 3.
　Incidentally, A is (A 4 may exhibit), n is an integer from 0 to 2, p is an integer of from 0 to 4, A is (A 2 may exhibit), n is up to 0-2 of an integer.
[0072]
　The photochromic compounds of the general formula (5) (C) is combined with the sought-after color change reaction rates to be applied to applications, high color suitability even at high temperatures of more than 40 ° C.. Colors that can be easily achieved, ranging from orange to blue.
[0073]
　In the present embodiment, A = (A 1 ), compound (5), A = (A 2 ), compound (5), A = (A 3 ), compound (5), A = (A 4 ) a compound (5), and a = (a 5 also encompasses mixtures of) a compound (5) at least one different type belonging compound selected from the group consisting of (5).
[0074]
　In the present embodiment, as the compound (5) can be preferably used a compound represented by the following general formula (6).
[0075]
[Of 20]

[0076]
　Ar 1 , Ar 2 is an aromatic group, which may be the same or different, represent a benzene ring or a thiophene ring which may be substituted. Examples of the substituent of the benzene ring or a thiophene ring, a straight-chain or branched alkyl group having 1 to 10 carbon atoms, straight-chain or branched alkoxy group having 1 to 10 carbon atoms, having 1 to 6 carbon atoms straight-chain or branched it can be mentioned alkyl mono- (or di-) substituted amino group. R 3 , R 4 , R 5 , m, n, p are as defined above.
[0077]
　As the compound (5), can be used more preferably a compound represented by the following general formula (7).
[0078]
[Of 21]

[0079]
　Wherein (7), R 10 , R 11 may be the same or different from each other, a linear or branched alkyl group, a linear or branched alkoxy group having 1 to 10 carbon atoms having 1 to 10 carbon atoms, It represents a linear or branched alkyl mono- (or di-) substituted amino group having 1 to 6 carbon atoms. when m is 2, adjacent R 3 bonded to each other, R 3 can form a ring structure containing a carbon atom is bonded. r, s is an integer of 0 to 4. The ring structure is a substituted or unsubstituted, heteroaryl group an aryl group or a C 3 to 24 6 to 24 carbon atoms.
　R 3 , R 4 , R 5 , m, n, p are as defined above.
[0080]
　Specific examples of the compound represented by the general formula (7) include compounds represented by the following formula (8) or the following formula (9). In this embodiment, the compound of formula (8) and (9) are preferred.
[0081]
[Formula 22]

[0082]
[Of 23]

[0083]
　Compounds represented by the photochromic compound (C) is a general formula (5) can be synthesized by a known method. For example, it can also be synthesized by the method described in JP-T-2004-500319.
　Also, More specific examples of the naphthopyran compound represented by the general formula (3) may be mentioned as preferred examples of the compound represented by the following formula (10).
[0084]
[Of 24]

[0085]
　The naphthopyran compounds, may be used one or more compounds selected from the compounds described above.
　The optical material for the polymerizable composition of the present embodiment, the total 100% by weight of the compound (A) and the compound (B), 100 ~ 3000 ppm of naphthopyran compounds may preferably comprise 100 ~ 2000 ppm.
[0086]
　As the photochromic compound (C) in the present embodiment, it is also possible to use at least one selected from the general formulas (a) and the general formula (b).
　PC-L-Chain
　(a) PC-L-Chain-L'-PC
　'(b) represents a monovalent group derived from a compound of PC and PC' of the general formula (c) ~ (f). PC and PC 'may be the same or different.
[0087]
[Of 25]

[0088]
　Wherein (c) ~ (f), 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 contained in the compound represented by (c) ~ (f), any one of the group is attached to L or L 'is a divalent organic group.
[0089]
　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.
[0090]
　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.
[0091]
　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.
[0092]
　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, substituted with C1 ~ C10 alkoxy group a C1 ~ C10 alkyl group, C1 ~ C10 aminoalkyl group, a straight chain or branched chain C1 such ~ C20 alkoxycarbonyl group, an aliphatic group which may be substituted C1 ~ by
C20; cycloalkyl group C3 ~ C20, C6 bicycloalkyl groups such ~ C20, fat optionally substituted C3 ~ C20 ring 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.
[0093]
　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, straight or branched C1 ~ C10 alkoxy group, C1 ~ C10 hydroxyalkyl group, C1 ~ C10 C1 ~ C10 alkyl group substituted with an alkoxy, C1 ~ C10 aminoalkyl group, a straight chain or branched chain Jo of C1 ~ C20 alkoxycarbonyl group, etc., aliphatic group which may be substituted C1 ~ by
C20; cycloalkyl group C3 ~ C20, such as bicycloalkyl group C6 ~ C20, optionally substituted C3 ~ C20 alicyclic group;
arylcarbonyl group, an aroyl group, a phenyl group, C7 ~ C16 alkoxyphenyl group, C1 ~ C10 dialkyl And the like can be given; Kishifeniru group, C1 ~ C10 alkyl phenyl group, such as C1 ~ C10 dialkyl phenyl group, an aromatic organic group which may be substituted C6 ~ to C20.
[0094]
　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 (g) or (h) and the like. The dotted lines R 3 carbon atoms and R which are bonded 4 represents a bond between the carbon atom to which they are attached.
[0095]
[Of 26]

[0096]
　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.
[0097]
　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.
[0098]
　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.
[0099]
　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.
[0100]
　L and L 'are of the general formula (a) or (b), 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 (i) ~ (o). L and L 'may be the same or different.
[0101]
[Of 27]

[0102]
　Wherein (i) ~ (o),
　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.
[0103]
　"Chain" in the general formula (a) or (b) 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.
[0104]
　Specifically,
　"Chain", if the photochromic compound of general formula (a), a monovalent organic group of the general formula (p) or (q).
[0105]
[Formula 28]

[0106]
　"Chain" when the photochromic compound is formula (b), represents a divalent organic group of the general formula (r) or (s).
[0107]
[Of 29]

[0108]
　Wherein (p) ~
(s), 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 '.
[0109]
　The photochromic compound (C), improvement in color development rate, in terms of lowering the color development time transmission, for example, be produced a better lens that is light modulating performance of selecting compounds of the general formula (b) it can.
　As the photochromic compound (C), the photochromic combination between the photochromic compound of the general formula (a), the combination of the photochromic compound with each other in the general formula (b), the photochromic compounds and of the general formula (a) (b) it is also preferred that a combination of a compound, more preferably a combination of each other photochromic compound of general formula (b), PC and PC 'general formula (c), Chain general formula (r) or (s), L and L 'general formula (i) is, (j), and more preferably a combination of each other photochromic compound of general formula is either (o) (b). Two photochromic compounds, 1: 9 to 9: 1, preferably 2: 8 to 8: may be combined so that the second ratio.
[0110]
　The optical material for the polymerizable composition of the present embodiment, the total 100% by weight of the compound (A) and the compound (B), the general formula (a) or the photochromic compound represented by general formula (b) 100 ~ 3000 ppm, preferably may comprise 100 ~ 2000 ppm.
　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.
[0111]
　The photochromic compound (C) in the present embodiment, Vivimed's Reversacol Humber Blue (polydimethylsiloxane chain, naphthopyran chromophore (Formula (c)), Reversacol Calder Blue ( polydimethylsiloxane chain, naphthopyran chromophore ( formula (c)), Reversacol Trent Blue ( polydimethylsiloxane chain, naphthopyran chromophore (formula (c)), Reversacol Pennine Green ( polydimethylsiloxane chain, naphthopyran chromophore (formula (c)), Reversacol Heath Green (polyoxyalkylene chain, naphthopyran chromophore (formula (c)), Reversacol Chilli Red ( polydimethylsiloxane chain, Na Topiran based chromophore (Formula (c)), Reversacol Wembley Grey ( polyoxyalkylene chain, naphthopyran chromophore (Formula (c)), Reversacol Cayenne Red ( polyoxyalkylene chain, naphthopyran chromophore (Formula ( c))), Reversacol Wilson Blue ( polyoxyalkylene chain, naphthopyran chromophore (formula (c))) and the like.
　Examples of the photochromic compound (C), from the viewpoint of color development rate, these compounds are preferred used.
[0112]
[(D) a radical polymerization initiator]
　The optical material for the polymerizable composition of the present embodiment may further comprise a radical polymerization initiator (D). In the present embodiment, as the radical polymerization initiator (D), it may include at least one selected from the following radical polymerization initiator (D1) and the following radical polymerization initiator (D2).
　Radical polymerization initiator (D1) is less than the radical residual ratio after the lapse of 50 ° C. 5 hours 20% to 100% and the radical remaining rate after the lapse of 70 ° C. 5 hours is 30% or more and less than 0%. Radical polymerization initiator (D2), it is less than 100% 30% or more radicals remaining rate after the lapse of 70 ° C. 5 hours.
[0113]
　Radical residual ratio of the radical polymerization initiator can be calculated as follows.
　By the following equation, thermal decomposition rate k of the radical polymerization initiator at a given temperature T d is calculated.
　k d = Aexp (-DerutaE /
　　　RT) A: frequency factor
　　　Delta] E: activation energy
　　　R: gas constant (8.314 J / mol · K)
　　　T: absolute temperature (T)
　above the thermal decomposition rate k d , a predetermined temperature it can be calculated radicals residual ratio of the radical polymerization initiator after t time response in T.
Radical remaining ratio (%) = exp (-k d t) × 100
　　t: time (hr)
[0114]
　Radical polymerization initiator (D1) is less than 100% radical remaining ratio is 20% or more after the lapse of 50 ° C. 5 hours, preferably 90% or more and 20% or less, more preferably up to 85% more than 40%, and 70 ℃ radical remaining rate after 5 hours have passed is less than 30% 0% or more, preferably 20% or more 0% or less, more preferably 10% or more 0% or less.
　Radical polymerization initiator (D2) is, 70 ° C. radical remaining rate after 5 hours have passed is less than 30% to 100%, preferably less than 100% to 40%.
　The above range can be appropriately combined.
[0115]
　As the radical polymerization initiator (D1), peroxyester polymerization initiator, peroxydicarbonate-based polymerization initiator, and the like can be mentioned azo radical polymerization initiators may be used at least one kind. In the following, values ​​in parentheses, turn "radical remaining ratio after the lapse of 50 ° C. 5 hours", indicating a "radical remaining ratio after the lapse of 70 ° C. 5 hours."
[0116]
　The peroxyester polymerization initiator, for example, t- butyl - peroxy neodecanoate (57.6% 0.2%), t-hexyl peroxypivalate (80.2%, 5. 5%), hexyl peroxyneodecanoate to t-, 1,1,3,3-tetramethylbutyl peroxyneodecanoate (27.9%, 0.0%), t-butyl peroxypivalate Bareto (82.6%, 7.9%), and the like.
[0117]
　The peroxydicarbonate-based polymerization initiator, e.g., diisopropyl peroxydicarbonate (24.8%, 0%), di -n- propyl peroxydicarbonate (28.7%, 0%), bis ( 4-t-butylcyclohexyl) peroxydicarbonate (28.2%, 0%), di-2-ethylhexyl peroxydicarbonate (40.4%, 0%), di -sec- butyl peroxydicarbonate ( 29.4 percent, and 0%), and the like.
　The (azo) based radical polymerization initiator, for example, 2-2'-azobis (2,4-dimethylvaleronitrile) (73.8%, 2.0%) and the like.
[0118]
　As the radical polymerization initiator (D2), peroxyester polymerization initiator, peroxy ketal radical polymerization initiator, peroxy carbonate-based radical polymerization initiator, or the like can be mentioned azo radical polymerization initiator, it can be used at least one kind. In the following, numerical values ​​in parentheses indicate the "radical remaining ratio after the lapse of 70 ° C. 5 hours."
[0119]
　The peroxyester polymerization initiator, for example, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate (53.8%), t-butyl peroxy 2 Echiruhekisano benzoate (76.8%), t-amyl peroxy-2-ethylhexanoate (78.5%), hexyl t-butylperoxy 2-ethylhexanoate (70.9%), 1-cyclohexyl - 1-methylethyl peroxyneodecanoate, t- butyl peroxy laurate (99.2%), t- butyl peroxy nonanoate, t- butyl peroxy isobutyrate (92.4%), t- butyl peroxy 3,3,5 trimethyl hexanoate (98.7%), t- butyl peroxy acetate (99.6%), t- butyl peroxy isononanoate Benzoate (99.4%), t- butyl peroxy benzoate (99.6%), t- amyl peroxy-n-octoate (98.9%), t- amyl peroxy acetate (99.3%), t - amyl peroxy isononanoate Na benzoate (98.9%), t-amyl peroxybenzoate (99.2%), t-hexyl peroxybenzoate (99.3%), and the like.
[0120]
　The peroxy ketal radical polymerization initiator, for example, 1,1-di (t-amyl peroxy) cyclohexane (98.6%), 1,1-di (t-hexyl peroxy) cyclohexane (96.2 %), 1,1-di (t-butylperoxy) cyclohexane (97.5%), n-butyl-4,4-di (t-butylperoxy) valerate (99.8%), 2,2 - bis (4,4-di -t- butyl peroxy cyclohexyl) propane, 2,2-di (t-butylperoxy) butane (99.7%), ethyl-3,3-di (t-Buchirupa oxy) butyrate (99.9%), and the like.
　The peroxy carbonate-based radical polymerization initiator, t- butyl peroxy isopropyl carbonate (99.3%), t- butyl peroxy-2-ethylhexyl carbonate (99.2%), t-amyl peroxy isopropyl carbonate ( 99.1%), t-amyl peroxy-2-ethylhexyl carbonate (99.2%), and the like.
　The (azo) based radical polymerization initiator, for example, 2-2'-azobis (isobutyronitrile) (50.2%), 2-2'-azobis (2-methylbutyronitrile) (60.0 %), 1,1'-azobis (cyclohexane-1-carbonitrile) (97.7%), and the like.
[0121]
　The addition amount of the radical polymerization initiator (D), the type of polymerization conditions and initiator differs depending on the composition of the monomer and is variable. The polymerizable composition 100 parts by weight, 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight. Curing is insufficient at less than 0.01 part by weight, there is a tendency that the strain enters the shaped body and more than 10 parts by weight.
　Radical polymerization initiator (D) a radical polymerization initiator (D1), or (D2) be used alone, respectively, may be used in combination with (D1) (D2). When using a radical polymerization initiator (D1) or (D2) alone, 10 parts by weight or less than 0.01 part by weight of the polymerizable composition 100 parts by weight, preferably not more than 5 parts by weight or more 0.1 part by weight it can be included. If a combination of the radical polymerization initiator (D1) and (D2), from the viewpoint of the effect of the present invention, the polymerizable composition 100 parts by weight, the polymerization initiator (D1) 0.1 parts by weight or more 5.0 parts by weight or less, preferably comprises less 3.0 parts by weight or more, 0.2 parts by weight polymerization initiator (D2) 1.0 parts by weight or less than 0 parts by weight, preferably 0.001 part by weight It may include 0.5 parts by weight or more. The above range can be appropriately combined.
[0122]
　Upon curing the monomer composition by using these radical polymerization initiator (D1) and / or (D2), to prevent decomposition of additives such as photochromic compound and an ultraviolet absorber at the time of curing, coloration during curing it is possible to suppress.
[0123]
　In the present embodiment, a radical polymerization initiator (D) is, (D1) alone or (D1) and preferably comprises a combination of (D2),, comprise a combination of (D1) and (D2) It is more preferable.
　In the present embodiment, by including a radical polymerization initiator (D1) and the radical polymerization initiator (D2), (D1) is more radicals generated in the low temperature side, (D2) and more generating radicals at high temperature side since easy, during the polymerization, since the remaining above a certain concentration there is a radical in the system, cracking and polymerization peeling the lens is particularly suppressed, since the more excellent moldability, the yield of the product is improved greatly.
[0124]
　In this embodiment, allyl carbonate compound (A), and (meth) acrylate compound (B), the photochromic compound (C), and a combination of the radical polymerization initiator (D1) and (D2), by using without impairing the transparency, excellent surface hardness, it is possible to provide a doubles aligned photochromic lenses for spectacles of the light modulating performance, lens cracking and polymerization peeling has moldability is particularly suppressed at the time of polymerization is excellent, the yield of the product is greatly improved.
[0125]
　Polymerization initiator (D) is preferably a combination of the following compound is the following compound which is a radical polymerization initiator (D1) and a radical polymerization initiator (D2).
(1) t-butyl peroxyneodecanoate combination of benzoate and 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate
(2) t-butyl peroxyneodecanoate and t - combination of amyl peroxy-2-ethylhexanoate
　to cure the optical material for the polymerizable composition of the present embodiment, the monomer composition was added a radical polymerization initiator (D), the following it can be obtained by curing by heating curing method or an active energy ray curable method.
[0126]
[Other Components]
　In the present embodiment, in addition to the (A) ~ (D) component, an ultraviolet absorber, a resin modifier may further comprise an internal mold release agent.
[0127]
　As the ultraviolet absorber, benzotriazole ultraviolet absorbers, triazine ultraviolet absorbers, benzophenone ultraviolet absorbers, cyanoacrylate ultraviolet absorbers, diphenyl acrylate UV absorbers, phenol-based ultraviolet absorbers, Okisaanirido based ultraviolet absorber , and malonic acid ester type ultraviolet absorbing agents.
[0128]
　The addition amount of the ultraviolet absorber, ultraviolet radiation region absorbed by the type of ultraviolet absorber can not differ unconditionally limited, the polymerizable composition 100 parts by weight, 0.01 to 5 parts by weight, preferably 0 in the range of .02 to 2 parts by weight.
　As a resin modifier, without impairing the effect of the present invention may be added a radical polymerizable monomer other than (meth) acrylate compound (B).
[0129]
　(Meth) Examples of the radical polymerizable monomer other than the acrylate compound (B), styrene, alpha-methyl styrene, alpha-methyl styrene dimer, benzyl methacrylate, chlorostyrene, bromostyrene, methoxystyrene, monobenzyl fumarate, Jibenjirufuma possible rates, dibutyl fumarate, monopentyl fumarate, be used either individually or in combination of two or more compounds selected from a group consisting of dipentyl fumarate.
[0130]

　for an optical material polymerizable composition of the present embodiment, allyl carbonate compound (A), (meth) acrylate compound (B), the photochromic compound (C), to need depending radical polymerization initiator (D) are mixed, it is obtained.
　Mixing method of temporarily prepared compound containing a radical polymerization initiator (D) in a high concentration (A) and the compound (B) (masterbatch) optionally together mixed, or photochromic compound (C) and, It may also be prepared masterbatch compound (a) and the compound (B) in the diluted mixture. When using the master batch, the dilution ratio of the master batch varies depending photochromic compound, usually 2 times 50 times or less, preferably 20 times or more than four times, more preferably 15 times or less 5 times. Since the photochromic compound is in this range (C) is homogeneously dispersed can be suitably adopted.
[0131]
　Compound (A), compound (B) and compound (C), the temperature is usually preferably 40 ° C. or less in the case of further preparing a radical polymerization initiator (D) were mixed and ultraviolet absorber polymerizable composition 30 ° C. It is performed in the following. From the viewpoint of pot life of the polymerizable composition, it may be preferable further to a low temperature. However, the catalyst, if solubility in monomer additive is not satisfactory, it is also possible to dissolve beforehand warmed, monomers, a resin modifier.
[0132]
　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.
[0133]
　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.
[0134]
　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..
[0135]
　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, radical scavengers, light stabilizers, UV stabilizers, antioxidants, bluing agent, solvent dye, filler, adhesion-improving agents, antimicrobial agents, various additives may be added, such as antistatic agents.
[0136]

　resin of the present embodiment can be obtained as a molded article having various shapes by changing the type of mold during casting polymerization.
[0137]
　Molded body obtained from the optical material for the polymerizable composition of the present embodiment, without impairing the transparency, it is possible to obtain an excellent surface hardness, material stocked also serves as a light modulating performance, such as a plastic lens It can be used for various optical materials. In particular, it can be suitably used as a plastic spectacle lens or a plastic polarized lens.
[0138]
[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.
[0139]
　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.
[0140]
　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.
[0141]
　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.
[0142]
　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.
[0143]
　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.
[0144]
　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.
[0145]
　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.
[0146]
　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.
[0147]
　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 .
[0148]
　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.
[0149]
[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.
[0150]
　Polarizing film in the present embodiment can be composed of a thermoplastic resin. As the thermoplastic resin, polyester resin, polycarbonate resin, polyolefin resins, polyimide resins, polyvinyl alcohol resins, polyvinyl chloride resins and the like. Water resistance, from the viewpoint of heat resistance and moldability, a polyester resin, a polycarbonate resin is preferably a polyester resin is more preferable.
[0151]
　The polyester resin, polyethylene terephthalate, polyethylene naphthalate, and can be exemplified polybutylene terephthalate, water resistance, polyethylene terephthalate from the viewpoint of heat resistance and moldability preferred.
[0152]
　As the polarizing film, particularly, a dichroic dye-containing 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.
[0153]
　Plastic polarized lens of the present embodiment, such an objective side surface or the ocular surface on one surface side of the polarizing film, or on both sides of the plane of the surface and the ocular side of the object plane side , base layer obtained by curing the optical material for the polymerizable composition of the present embodiment are laminated.
[0154]
　From the viewpoint of the light modulating performance, on at least the object plane side surface of the polarizing film, it is preferable that the base layer obtained by curing the optical material for the polymerizable composition of the present embodiment are laminated. Base layer in the present embodiment, when it is formed only on the surface of the object plane side of the polarizing film, the base material layer formed on the other surface of the polarizing film, (C) component or (C) and (D) can be formed from an optical material for the polymerizable composition of the present embodiment does not include a component, an acrylic resin, an allyl carbonate resin, polycarbonate resin, polyurethane resin, a polythiourethane resin, a plastic material, such as polysulfide resin form can also be.
[0155]
　Plastic polarized lens of the present embodiment is not particularly limited, a method of bonding the both surfaces on the lens substrate of the polarizing film, a polymerizable composition on both sides of the polarizing film can be exemplified cast polymerization methods and the like. In the present embodiment, examples will be described which is formed by a cast polymerization method.
[0156]
　Method for producing a plastic polarized lens of the present embodiment, for example,
　in a mold, the first polymerizable composition layer formed on the surface of the object plane side of the polarizing film, the second polymer on the other surface of the polarizing film forming a sexual composition layer,
　the polymerizable composition layer polymerization curing to a step of laminating the base material layer on both surfaces of the polarizing film may include.
　The first polymerizable composition layer is formed from an optical material for the polymerizable composition of the present embodiment. If a layer of first polymerizable composition and the layer of the second polymerizable composition is the same resin composition, since the temperature management of the polymerization process is facilitated, the layer of the second polymerizable composition ( C) and (D) is formed of an optical material for the polymerizable composition of the present embodiment does not include a component.
[0157]
　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.
　Then, the layer is formed of a first polymerizable composition was injected first polymerizable composition between the object plane side surface of the mold and the polarized film and then, the eyepiece side of the polarizing film surface and the mold in the gap between, and implanting second polymerizable composition can form a layer of a second polymerizable composition.
[0158]
　Moreover, the process is the first polymerizable composition, placed on the forming surface for forming the object surface of the mold of the lens, the first polymerizable composition over the entire surface of the forming surface in the polarizing film press spread, and a surface of the object side by a predetermined distance apart from the mold and the polarizing film through the layer of first polymerizable composition formed, then, in order to form a polarizing film, an eyepiece surface of the mold of the lens possible in a gap between forming surface of, injecting a second polymerizable composition, also it is carried out by forming a layer of a second polymerizable composition.
[0159]
　The polymerization conditions of 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, is carried out over 1 to 50 hours at a temperature of 5 ~ 140 ° C.. 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.
[0160]
　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.
Example
[0161]
　Next, the present invention embodiment will be described in more detail, the present invention is not intended to restrict the scope. In Examples and Comparative Examples, equipment used and method used for the evaluation are as follows.
[0162]
Refractive index (ne) was Abbe number (ve): using a refractometer KPR-20 (Kalnew manufactured Optical Industry Co., Ltd.) was measured at 20 ° C..
Transparency: 9 mm processed molded body to a thickness of irradiated projector in the dark cloudy and determines the presence or absence of foreign matter by visual inspection. Cloudy, (with transparency) "good" things that foreign matter is not confirmed, and the ones that have been identified as "bad" (no transparency).
Rockwell hardness: ISO2039-2 in compliance with, was measured by the M scale.
[0163]
Formability
lens cracking: The "lens cracking", the lens is a phenomenon in which crack during polymerization. Plano 4C to create five lenses (2mm thick), polymerization "There lens crack" what was broken more than one after the end of the (productivity bad), "no lens cracking" the ones that did not crack at all (productivity It was good).
Polymerization peeling: The "polymerization peeling", during the polymerization in a glass mold, the molded body is a phenomenon that peel off from the glass mold. Those were not peeled off during the polymerization ◎, was peeled off during polymerization peeling those circular pattern is not confirmed 〇, during the polymerization, was × what circular pattern has been confirmed. The circular pattern, for example molded into the polymerization can unpolymerized portions for peeled from the glass mold, it means a phenomenon that appears as a circular pattern in mainly the lens surface.
· Striae: the "striae" is a phenomenon that is different from the locally normal refractive index of the surrounding including differences in composition, are observed as stripes. High pressure mercury lamp samples were created: projecting by (source model OPM-252HEG manufactured by Ushio Inc.) to observe the presence or absence of striae the transmitted image visually. Those ones striped not observed ○, and as × that observed.
Releasing cracks: Create five lenses Plano 4C (2 mm thick), after completion of the polymerization, at the time of separating the mold and the lens, "○" and those that did not crack at all, cracked or one "△" things, was evaluated as "×" what was broken four or more.
[0164]
· Color when transmittance: 2 mm in processed molded article thickness, at a temperature 23 ° C., Ushio MS-35AAF / FB xenon lamp light source device using a (illuminance 50000 lux), the transmittance at 550nm after irradiation for 15 minutes It was measured. It indicates a higher light-shielding property at the time of color development as the transmittance is small.
Fading rate: After color development during Similarly shaped body 15 min light irradiation and transmittance measurement, time required for the absorbance at 550nm of the molding samples after stopping the light irradiation is restored to an intermediate value of the absorbance before and after the color development It was measured. This time was fading rate. Color when the transmittance is low, fading speed is high compacts dimming performance is determined to be good.
[0165]
(Materials used)
allyl carbonate compound
(A) · RAV 7AT (diethylene glycol and pentaerythritol poly (allyl carbonate) compounds, and their oligomers, manufactured ACOMON
Ltd.) · RAV 7 ng (diethylene glycol and pentaerythritol poly (allyl carbonate) compounds, and oligomers thereof, made by ACOMON Co., Ltd.)
[0166]
(Meth) acrylate compound (B)
, diethylene glycol dimethacrylate (NK ester 2G, manufactured by Shin-Nakamura Chemical Co., Ltd.)
Triethylene glycol dimethacrylate (NK ester 3G, manufactured by Shin-Nakamura Chemical Co., Ltd.)
[0167]
Photochromic compound
(C) · Reversacol Heath Green (polyoxyalkylene chain, naphthopyran chromophore (Formula
(c))) · Reversacol Wembley Gray (polyoxyalkylene chain, naphthopyran chromophore (Formula (c)))
· Reversacol Wilson Blue (polyoxyalkylene chain, naphthopyran chromophore (formula
(c))) · Reversacol Cayenne Red (polyoxyalkylene chain, naphthopyran chromophore (formula (c)))
[0168]
Radical polymerization initiator
(D) D11: t-butyl - peroxy neodecanoate (Perbutyl ND, manufactured by NOF
　　　CORPORATION) Radical residual ratio after the lapse of 50 ° C. 5 hours:
　　　57.6% at 70 ° C. 5 hours after radical residual ratio: 0.2% D12:
1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate (PerOcta O, manufactured by NOF Corporation)
　　　radical residual ratio after the lapse of 70 ° C. 5 hours:
53.8% D21: t-amyl peroxy-2-ethylhexanoate (TRIGONOX 121, manufactured by Kayaku Akzo
　　　Corporation) radical residual ratio after the lapse of 70 ° C. 5 hours:
78.5% D22: 1,1-di (t-amyl peroxy) cyclohexane (LUPEROX 531, manufactured by Arkema)
　　　radical remaining rate after the lapse of 70 ° C. 5 hours: 98.6%
[0169]
Example 1
　polyallyl carbonate RAV 7 ng (manufactured Acomon Ltd.) 14.0 parts by weight (manufactured by Shin-Nakamura Chemical Co., Ltd.) Diethylene glycol dimethacrylate NK ester 2G 66.0 parts by weight of triethylene glycol dimethacrylate NK ester 3G (Shin-Nakamura Chemical Co., Ltd. ) 20.0 parts by weight, Reversacol Heath Green0.0215 parts by weight photochromic compound, Reversacol Wembley Grey0.054 parts by weight as a catalyst, t- butyl - peroxy neodecanoate 2.0 parts by weight, 1,1-di (t- amyl peroxy) cyclohexane 0.2 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 24 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 evaluation results of the moldability shown in Table 1. The obtained resin plates were subjected to 1 hour annealing at further 100 ° C.. The resulting resin flat refractive index (ne) 1.51, was Abbe number (ve) 56. The resulting molded body was colorless and transparent. A Rockwell hardness 96, was confirmed to show a good hardness. The color at the time the transmittance is 16%, fade rate and 71s, were confirmed to have excellent dimming performance. The results obtained are shown in Table 1.
[0170]
[Examples 2-6, Comparative Examples 1-4]
　As shown in Table 1, except for changing the kind and amount of each monomer, the same polymerization as in Example 1 to obtain a molded body. The results obtained are shown in Table 1.
[0171]
Example 7
　polyallyl carbonate RAV 7AT (manufactured Acomon Ltd.) 12.0 parts by weight (manufactured by Shin-Nakamura Chemical Co., Ltd.) Triethylene glycol dimethacrylate NK ester 3G 88.0 parts by weight, 2.0 parts by weight of α- methyl styrene dimer, photochromic compound Reversacol Heath Green 0.0285 parts by weight, Reversacol Wembley Gray 0.053 parts by weight, as a catalyst, t- butyl as - 0.5 part by weight of peroxy neodecanoate, 1,1-di (t-amyl peroxy) cyclohexane 0.2 parts by weight of a was 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 24 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 evaluation results of the moldability shown in Table 1. The obtained resin plates were subjected to 1 hour annealing at further 110 ° C.. The resulting resin flat refractive index (ne) 1.51, was Abbe number (ve) 54. The resulting molded body was colorless and transparent. Rockwell hardness 82 were confirmed to show a good hardness. The color at the time the transmittance is 17%, fade rate and 54s, were confirmed to have excellent dimming performance. The results obtained are shown in Table 1.
[0172]
Example 8
　polyallyl carbonate RAV 7AT (manufactured Acomon Co.) 4.0 parts by weight of triethylene glycol dimethacrylate NK ester 3G (manufactured by Shin-Nakamura Chemical Co., Ltd.) 96.0 parts by weight, 2.0 parts by weight of α- methyl styrene dimer, photochromic compound as Reversacol Heath Green 0.0285 parts by weight, Reversacol Wembley Gray 0.053 parts by weight, as a catalyst, t- butyl - 0.55 parts by weight peroxy neodecanoate, 1,1,3,3-tetramethylbutyl-2-ethyl peroxy hexa Noeto 0.15 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 24 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 evaluation results of the moldability shown in Table 1. The obtained resin plates were subjected to 1 hour annealing at further 110 ° C.. The resulting resin flat refractive index (ne) 1.50, was Abbe number (ve) 56. The resulting molded body was colorless and transparent. A Rockwell hardness 96, was confirmed to show a good hardness. The color at the time the transmittance is 18%, fade rate and 112s, were confirmed to have excellent dimming performance. The results obtained are shown in Table 1.
[0173]
Example 9
　polyallyl carbonate RAV 7AT (manufactured Acomon Ltd.) 12.0 parts by weight (manufactured by Shin-Nakamura Chemical Co., Ltd.) Triethylene glycol dimethacrylate NK ester 3G 88.0 parts by weight, 2.0 parts by weight of α- methyl styrene dimer, photochromic compound as Reversacol Heath Green 0.0323 parts by weight, Reversacol Wembley Gray 0.081 parts by weight, as a catalyst, t- butyl - peroxy neodecanoate 0.5 parts by weight, 1,1,3,3-tetramethyl-butyl-2-ethyl-butylperoxy hexa Noeto 0.2 part 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 24 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 evaluation results of the moldability shown in Table 1. The obtained resin plates were subjected to 1 hour annealing at further 110 ° C.. The resulting resin flat refractive index (ne) 1.51, was Abbe number (ve) 53. The resulting molded body was colorless and transparent. Rockwell hardness 82 were confirmed to show a good hardness. The color at the time the transmittance is 16%, fade rate and 52s, were confirmed to have excellent dimming performance. The results obtained are shown in Table 1.
[0174]
Example 10
　polyallyl carbonate RAV 7AT (manufactured Acomon Ltd.) 12.0 parts by weight (manufactured by Shin-Nakamura Chemical Co., Ltd.) Triethylene glycol dimethacrylate NK ester 3G 88.0 parts by weight, 2.0 parts by weight of α- methyl styrene dimer, photochromic compound as Reversacol Heath Green 0.0323 parts by weight, Reversacol Wilson Blue 0.081 parts by weight, as a catalyst, t- butyl - 0.55 parts by weight peroxy neodecanoate, 1,1,3,3-tetramethylbutyl-2-ethyl peroxy hexa Noeto 0.15 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 24 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 evaluation results of the moldability shown in Table 1. The obtained resin plates were subjected to 1 hour annealing at further 110 ° C.. The resulting resin flat refractive index (ne) 1.51, was Abbe number (ve) 54. The resulting molded body was colorless and transparent. Rockwell hardness 82 were confirmed to show a good hardness. The color at the time the transmittance is 16%, fade rate and 65s, were confirmed to have excellent dimming performance. The results obtained are shown in Table 1.
[0175]
Example 11
　polyallyl carbonate RAV 7AT (manufactured Acomon Ltd.) 12.0 parts by weight (manufactured by Shin-Nakamura Chemical Co., Ltd.) Triethylene glycol dimethacrylate NK ester 3G 88.0 parts by weight, 2.0 parts by weight of α- methyl styrene dimer, photochromic compound as Reversacol Heath Green 0.18 part by weight, Reversacol Cayenne Red0.080 parts by weight as a catalyst, t- butyl - 0.55 parts by weight peroxy neodecanoate, 1,1,3,3-tetramethylbutyl-2-ethyl peroxydicarbonate hexanoate 0.15 part 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 24 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 evaluation results of the moldability shown in Table 1. The obtained resin plates were subjected to 1 hour annealing at further 110 ° C.. The resulting resin flat refractive index (ne) 1.51, was Abbe number (ve) 54. The resulting molded body was colorless and transparent. Rockwell hardness 82 were confirmed to show a good hardness. The color at the time the transmittance is 18%, fade rate and 61s, were confirmed to have excellent dimming performance. The results obtained are shown in Table 1.
[0176]
Example 12
　polyallyl carbonate RAV 7AT (manufactured Acomon Ltd.) 29.0 parts by weight (manufactured by Shin-Nakamura Chemical Co., Ltd.) Triethylene glycol dimethacrylate NK ester 3G 71.0 parts by weight, 2.0 parts by weight of α- methyl styrene dimer, photochromic compound as Reversacol Heath Green 0.0285 parts by weight, Reversacol Wembley Gray 0.053 parts by weight, as a catalyst, t- butyl - 0.55 parts by weight peroxy neodecanoate, 1,1,3,3-tetramethylbutyl-2-ethyl peroxy hexa Noeto 0.15 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 24 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 evaluation results of the moldability shown in Table 1. The obtained resin plates were subjected to 1 hour annealing at further 110 ° C.. The resulting resin flat refractive index (ne) 1.51, was Abbe number (ve) 55. The resulting molded body was colorless and transparent. Rockwell hardness 78 were confirmed to show a good hardness. The color at the time the transmittance is 19%, fade rate and 46s, were confirmed to have excellent dimming performance. The results obtained are shown in Table 1.
[0177]
Example 13
　polyallyl carbonate RAV 7AT (manufactured Acomon Ltd.) 12.0 parts by weight (manufactured by Shin-Nakamura Chemical Co., Ltd.) Triethylene glycol dimethacrylate NK ester 3G 88.0 parts by weight, 2.0 parts by weight of α- methyl styrene dimer, photochromic compound Reversacol Heath Green 0.0285 parts by weight, Reversacol Wembley Gray 0.053 parts by weight, as a catalyst, t- butyl as - peroxyneodecanoate 0.55 parts by weight, 0.13 parts by weight t-amyl peroxy-2-ethylhexanoate was added, They are stirred together to dissolve. 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 24 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 evaluation results of the moldability shown in Table 1. The obtained resin plates were subjected to 1 hour annealing at further 110 ° C.. The resulting resin flat refractive index (ne) 1.51, was Abbe number (ve) 54. The resulting molded body was colorless and transparent. Rockwell hardness 82 were confirmed to show a good hardness. The color at the time the transmittance is 17%, fade rate and 53s, were confirmed to have excellent dimming performance. The results obtained are shown in Table 1.
[0178]
Example 14
　polyallyl carbonate RAV 7AT (manufactured Acomon Ltd.) 12.0 parts by weight (manufactured by Shin-Nakamura Chemical Co., Ltd.) Diethylene glycol dimethacrylate NK ester 2G 68.0 parts by weight of triethylene glycol dimethacrylate NK ester 3G (Shin-Nakamura Chemical Co., Ltd. ) 20.0 parts by weight, 2.0 parts by weight of α- methyl styrene dimer, Reversacol Heath Green .0323 parts by weight of photochromic compound, Reversacol Wembley Gray 0.081 parts by weight, as a catalyst, t- butyl - peroxy neodecanoate 0.55 parts by weight, 1 , 1,3,3-tetramethyl-butyl-2-ethyl-butylperoxy hexanoate 0.13 part 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 24 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 evaluation results of the moldability shown in Table 1. The obtained resin plates were subjected to 1 hour annealing at further 110 ° C.. The resulting resin flat refractive index (ne) 1.51, was Abbe number (ve) 56. The resulting molded body was colorless and transparent. Rockwell hardness and 102 were confirmed to show a good hardness. The color at the time the transmittance is 16%, fade rate and 55s, were confirmed to have excellent dimming performance. The results obtained are shown in Table 1.
[0179]
Example 15
　polyallyl carbonate RAV 7AT (manufactured Acomon Ltd.) 12.0 parts by weight (manufactured by Shin-Nakamura Chemical Co., Ltd.) Triethylene glycol dimethacrylate NK ester 3G 88.0 parts by weight, 2.0 parts by weight of α- methyl styrene dimer, ultraviolet absorbing agents as (p- methoxybenzylidene) malonate (Hostavin PR-25 (product name), manufactured by CLARIANT Corp.) 0.10 parts by weight, Reversacol Heath Green .0323 parts by weight of photochromic compound, Reversacol Wembley Gray 0.081 parts by weight, as a catalyst, t - butyl - 0.55 parts by weight peroxy neodecanoate, 1,1,3,3-tetramethylbutyl-2-ethyl peroxy hexanoate 0.15 part 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 24 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 evaluation results of the moldability shown in Table 1. The obtained resin plates were subjected to 1 hour annealing at further 110 ° C.. The resulting resin flat refractive index (ne) 1.51, was Abbe number (ve) 54. The resulting molded body was colorless and transparent. Rockwell hardness 82 were confirmed to show a good hardness. The color at the time the transmittance is 16%, fade rate and 52s, were confirmed to have excellent dimming performance. The results obtained are shown in Table 1.
[0180]
[Table 1]

[0181]
　Comparative Examples 1 to 3 As is apparent from the results of Examples, by copolymerizing A and B components in specific mixing ratios, transmittance during coloration is reduced, even faster dimming performance further fading rate it was confirmed that good molded body can be obtained. At the same time, have sufficient Rockwell hardness was also confirmed that further excellent moldability. As in Comparative Example 4, 35% by weight of component A, the molded body obtained from the optical material for the polymerizable composition comprising a B component 65 wt%, it was confirmed that white turbidity.
[0182]
　This application, filed on September filed in 30 days Japanese Patent Application No. 2016-194497 issue, in February filed in 20 days Japanese Patent Application No. 2017-029044, and July 13, 2017 2017 2016 has been on Japanese Patent application No. 2017-137029 claims priority based, the entire disclosure of which is incorporated herein.

The scope of the claims
[Requested item 1]
(A) represented by the general formula (1), and allyl carbonate compounds containing two or more allyloxycarbonyl group,
including (B) represented by the general formula (2), two or more (meth) acrylic group (meth) acrylate
compound, anda (C) a photochromic compound,
　in a total of 100% by weight of the compound (a) and the compound (B), compound (a) below 30 wt% more than 0 wt%, compound ( the B) in an amount of less than 70 wt% or more and 100 wt%, the optical material for the polymerizable composition.
[Formula 1]

(R 1 was also good chain or branched contain a hetero atom C3 of ~ C35 aliphatic polyols derived 2-20 bivalent group or may also C5 ~ contain a hetero atom C40 .m illustrating a 2-20 divalent group derived from a cyclic aliphatic polyol is an integer of 2-10. Note that, R 1 does not include the allyloxycarbonyl group.)
[Formula

2] (R 2 is heteroaryl .R showing a divalent to tetravalent organic group atoms or an aromatic group of carbon atoms which may contain 1 to 30 3 are, .n represents a hydrogen atom or a methyl group is an integer of 2-4.)
[Requested item 2]
　In total 100 wt% of the compound (A) and the compound (B), a compound including (A) 30 wt% 5 wt% or more or less, the compound (B) in an amount of less than 95 wt% 70 wt% or more, claim for an optical material composition as claimed in 1.
[Requested item 3]
　Further, the radical polymerization initiator include (D),
　a radical polymerization initiator (D) is at
least, radical residual ratio 20% or more and less than 100% after the lapse of 50 ° C. 5 hours, and the radical remaining after the lapse of 70 ° C. 5 hours rate is 0% or more and less than 30% radical polymerization initiator
(D1), a radical polymerization initiator is a radical residual ratio 30% or more and less than 100% after the lapse of 70 ° C. 5 hours and (D2),
including, claim 1 or an optical material for the polymerizable composition according to 2.
[Requested item 4]
　Compound (A), diethylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-methyl-2-ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2,2,4-trimethyl -1 , 3-pentanediol, 1,4-dimethylolcyclohexane and 4,8-bis (hydroxymethyl) - [5.2.1.0 2, 6 ] bis least one diol selected from tricyclodecane (allyl carbonate) compounds,
glycerol, trimethylolpropane and tris (hydro Shiechiru) at least one triol tris (allyl carbonate selected from isocyanurate) compounds,
pentaerythritol, at least one tetraol tetra (allyl carbonate selected from diglycerol and ditrimethylolpropane) compound,
dipenta erythritol hexa (allyl carbonate) compounds, and
the diols, the triol, is at least one said mixed poly (allyl carbonate) compound of at least two compounds selected from tetraols and said dipentaerythritol is selected from the optical material for the polymerizable composition according to any one of claims 1-3.
[Requested item 5]
　Compound (A),
(i) diethylene glycol bis (allyl carbonate) compounds and mixtures and oligomers thereof,
(ii) bis (allyl carbonate) of a mixture of diethylene glycol and neopentyl glycol compounds and mixtures and oligomers thereof,
(iii ) diethylene glycol and tris (poly (allyl carbonate of a mixture of hydroxyethyl) isocyanurate) compounds and mixtures and oligomers thereof,
(iv) diethylene glycol and poly (allyl carbonate mixture of trimethylol propane) compounds and mixtures and oligomers thereof,
(v) diethylene glycol and poly (allyl carbonate) compounds in the mixture of pentaerythritol and a mixture of oligomers thereof,
and (vi) diethylene glycol neopentyl glycol penta Poly mixture of erythritol (allyl carbonate) compounds and mixtures and oligomers thereof, and
(vii) diethylene glycol and poly (allyl carbonate) of neopentyl glycol and mixtures of pentaerythritol compound and a mixture of oligomers thereof,
diethylene glycol bis ( allyl carbonate) compounds, and poly (allyl carbonate) mixture comprising a mixture of oligomers thereof, a is at least one selected from, for optical materials polymerizable composition according to any one of claims 1 to 4.
[Requested item 6]
　Compound (B), the general formula (2-1), the general formula is selected from compounds represented by (2-2), the optical material for the polymerizable composition according to any one of claims 1 to 5.
[Formula 3]

(p represents a number of 1 ~ 100, R 3 represents a hydrogen atom or a methyl group, each may not be the same.)
[Formula 4]

(q represents one or more respective numerical , the sum of the two q is .R numerical 2-100 3 represents a hydrogen atom or a methyl group, each may not be the same .X is a substituted or unsubstituted divalent aromatic radical, a substituted or unsubstituted divalent may contain an aromatic group having 1 to 20 carbon atoms in the aliphatic group.)
[Requested item 7]
　Compound (B), in the general formula (2-1), p is selected from the compounds represented by 2-4, for optical materials polymerizable composition according to claim 6.
[Requested item 8]
　Compound (B), diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, is at least one selected from diethylene glycol diacrylate and triethylene glycol diacrylate, an optical material for the polymerizable composition according to claim 7.
[Requested item 9]
　Compound (C) is represented by the general formula (5), the optical material for the polymerizable composition according to any one of claims 1-8.
[Chemical Formula 5]

(wherein, R 1 and R 2 may be the same or different, independently, hydrogen;
linear or branched alkyl group of 1 to 12 carbon atoms;
a cycloalkyl group having 3 to 12 carbon atoms ;
is a substituted or unsubstituted, as heteroaryl group (substituent of the aryl group or a C 4-24 having 6 to 24 carbon atoms, a halogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 12 carbon atoms , straight-chain or branched alkoxy group having 1 to 12 carbon atoms, at least one straight-chain or branched haloalkyl group having carbon number of 1 to 12 substituted by a halogen atom, a carbon substituted with at least one halogen atom linear or branched haloalkoxy group having 1 to 12, at least one phenoxy group or a naphthoxy group substituted by straight-chain or branched alkyl or alkoxy group having 1 to 12 carbon atoms Linear or branched alkenyl group having a carbon number of 2 ~ 12, -NH 2 group, -NHR group, -N (R) 2 is group (R is a linear or branched alkyl group having 1 to 6 carbon atoms If .R is two, the two R may be the same or different), and having at least one substituent selected from a methacryloyl group or an acryloyl group);..
aralkyl or heteroaralkyl group (carbon ) linear or branched alkyl group having 1 to 4 are replaced by the above aryl group or a heteroaryl group.
represents,
　R 3 may be the same or different, independently, a halogen atom;
the carbon number 1-12 linear or branched alkyl group;
; a cycloalkyl group having 3 to 12 carbon atoms
linear or branched alkoxy group having 1 to 12 carbon atoms;
at least one carbon atoms substituted with halogen atoms 1 2 straight chain or branched haloalkyl group, at least one halocycloalkyl group having 3 to 12 carbon atoms substituted by halogen atoms, having 1 to 12 carbon atoms which is substituted with at least one halogen atom linear or branched haloalkoxy group;
a substituted or unsubstituted, as heteroaryl group (substituent of the aryl group or a C 4-24 having 6 to 24 carbon atoms, a halogen atom, a hydroxyl group, a straight-chain or branched having 1 to 12 carbon atoms alkyl group, straight or branched alkoxy group having 1 to 12 carbon atoms, at least one straight-chain or branched haloalkyl group having 1 to 12 carbon atoms which is substituted with a halogen atom, substituted with at least one halogen atom straight or branched haloalkoxy group having 1 to 12 carbon atoms, a straight-chain or branched least one alkyl group having 1 to 12 carbon atoms or alkoxy Alkoxy phenoxy group or a naphthoxy group substituted by a radical, having at least one substituent selected straight or branched alkenyl group having 2 to 12 carbon atoms, and amino groups from. );
A linear or branched alkyl group aralkyl or heteroaralkyl group (having 1 to 4 carbon atoms are substituted with the aryl group or heteroaryl group);.
As a substituted or unsubstituted phenoxy or naphthoxy group (substituent , having at least one substituent selected from linear or branched alkyl or alkoxy group having 1 to 6 carbon
atoms);. -NH 2 , -NHR, -CONH 2 or -CONHR,
is (R, carbon atoms 1 is a linear or branched alkyl group of
6);. -OCOR 8 or -COOR 8 (wherein, R 8 is a linear or branched alkyl group having 1 to 6 carbon atoms or carbon atoms, 3 cycloalkyl group to 6 or R, 1 , R 2 in a phenyl group substituted by at least one substituent of the substituted aryl or substituted heteroaryl group Others are unsubstituted phenyl group);.
Represents,
m has an integer from 0 to 4;
is A, the following formula (A 2 ) or Formula (A 4 )
[Chemical Formula 6]

a Aner of ring represents, in these Asnelles of rings,
the dotted line, the general formula (5) carbon C naphthopyran ring of 5 carbon C 6 represents a bond;
Aner of ring (a 4 naphthopyran of binding α) of the general formula (5) carbon C ring 5 or carbon C 6 can be coupled to;
R 4 is the same or different, independently, OH, a linear or branched alkyl group or alkoxy group having 1 to 6 carbon atoms It represents, or two R 4 may form a carbonyl (CO);
R 5 is halogen;
alkyl group, straight or branched having 1 to 12 carbon atoms;
substituted by at least one halogen atom, C 1 -C linear or branched haloalkyl group having 1-6;
Shikuroa 3 to 12 carbon atoms Kill group;
a straight-chain or branched alkoxy group having 1 to 6 carbon atoms;
a substituted or unsubstituted phenyl or benzyl group (the substituent of the general formula (5) R 1 , R 2 and groups independently aryl or If corresponding to a heteroaryl group, R 1 , R 2 has at least one of the substituents mentioned above in the definition of
groups);. -NH 2 , -NHR
(wherein, R is a linear 1 to 6 carbon atoms is a chain or branched alkyl group);.
as a substituted or unsubstituted a is phenoxy or naphthoxy group (substituent has at least straight-chain or branched alkyl or alkoxy group having 1 to 6 carbon atoms).;
-COR 9 , -COOR 9 or -CONHR 9 group (wherein, R 9 is a linear or branched alkyl group or a cycloalkyl group having 3 to 6 carbon atoms, having 1 to 6 carbon atoms or a substituted or unsubstituted, of replacement As Eniru or a benzyl group (substituent radical, R in the general formula (5) 1 , R 2 if groups independently correspond to an aryl or heteroaryl radical, R 1 , R 2 at least of the substituents described above in the definition of group having one. ));
A is (A 4 may exhibit), n is an integer from 0 to 2, p is an integer from 0 ~ 4, A is (A 2 may exhibit), n is 0-2 it is an integer of up to. )
[Requested item 10]
　Compound (C) is represented by the general formula (a) or represented by the general formula (b), the optical material for the polymerizable composition according to any one of claims 1-8.
　PC-L-Chain
　(a) PC-L-Chain-L'-PC
'(b) (PC and PC' of the general formula (c) .PC and PC shown - the (f) 'is either the same or different or.)
[Formula 7]

(R 1 ~ R 18 is hydrogen, halogen atom, carboxyl group, an acetyl group, a formyl group, an aliphatic group which may be substituted C1 ~ and C20, may also be C3 ~ which is substituted 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 (c) ~ (f), any one of the groups, and .L that bind to L or L 'is a divalent organic group L 'is an oxyethylene chain, oxypropylene chain, (thio) ester group, (thio) .Chain showing a divalent organic group containing one or more selected from bromide group, a monovalent or divalent organic group containing at least one selected polysiloxane chain, polyoxyalkylene chain. )
[Requested item 11]
　Molded body obtained by curing the optical material for the polymerizable composition according to any one of claims 1 to 10.
[Requested item 12]
　Optical material comprising a molded body according to claim 11.
[Requested item 13]
　Plastic lenses made of molded product according to claim 11.
[Requested item 14]
　A polarizing film,
　at least formed on the object plane side of the surface, the plastic polarized lens comprising: a base material layer made of a molded product according to claim 11 of the polarizing film.