0001]The present invention relates to a molded body and an optical material for the polymerizable composition containing a photochromic compound.
Background technique
[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.
　The lens obtained from the poly (thio) urethane Among them, a high refractive index, and from the viewpoint of excellent properties such as strength, has been attracting attention.
[0003]
　Patent Document 1, a predetermined photochromic compound, a composition containing a di (meth) acrylate compounds, lenses. In 0009 paragraph, when using the high refractive index urethane resin or a thiourethane resin, an isocyanate is a resin material in the monomer phase is reacted with photochromic compounds are described and eliminates exhibited at all photochromic performance.
[0004]
　Patent Document 2, a coating layer comprising a composition containing a photochromic compound and a phenol compound having a chromene skeleton, a lens provided on the surface of the thiourethane plastic lens is disclosed.
[0005]
　Patent Document 3, a lens base material made of a thiourethane resin, on to the substrate, a photochromic lens having a photochromic film solution formed by applying a containing a photochromic compound and a radically polymerizable monomer There has been disclosed. Patent Document 4, a compound having photochromic properties is disclosed.
[0006]
　Patent Document 5, and one or more isocyanate compounds selected from the aliphatic isocyanate compounds and alicyclic isocyanate compounds, di- and tri- or higher functional active hydrogen compound comprises a photochromic compound, a polymerizable composition for an optical material things have been disclosed.
　Patent Document 6, a polyisocyanate compound, and a predetermined polyol compound, an active hydrogen compound having two or more functional, and a photochromic compound, for optical materials polymerizable compositions are disclosed. The relevant literature, to the sum of the OH and SH groups contained in the active hydrogen compound and a polyol compound, the molar ratio of NCO groups contained in the polyisocyanate compound (NCO groups / (OH group + SH group)) is 0.8 in the range of ~ 1.2, it is described that the most preferred range is 0.9 to 1.1.
CITATION
Patent Document
[0007]
Patent Document 1: JP-A-8-272036 JP
Patent Document 2: JP 2005-23238 JP
Patent Document 3: JP 2008-30439 JP
Patent Document 4: JP 2011-144181 Patent Publication
Patent Document 5: International Publication No. 2014/002844 pamphlet
Patent Document 6: WO 2015/115648 pamphlet
Patent Document 7: US Patent 6,506,538 Patent
Patent Document 8: JP 2005-305306 JP
Patent Document 9: WO 2005/087829 pamphlet
Patent Document 10: International Publication No. 2006/109765 pamphlet
Patent Document 11: WO 2007/020817 pamphlet
Patent Document 12: WO 2007/020818 pamphlet
Patent Document 13: WO 2014/002844 pamphlet
Patent Document 14 : International Publication No. 201 5/115648 pamphlet
Summary of the Invention
Problems that the Invention is to Solve
[0008]
　The present inventors have investigated the photochromic performance of the resulting resin molded article in Examples of Patent Document 6. As a result, in the resin composition, to the sum of the OH and SH groups included in the "active hydrogen compound and a polyol compound, the molar ratio of NCO groups contained in the polyisocyanate compound (NCO groups / (OH group + SH group)) "than if the 1.0, is more enriched more NCO groups, we have found that deterioration of the photochromic performance is suppressed.
　Accordingly, the present inventors have made sure residue concentration of NCO groups and SH groups in the resin molded product by IR spectroscopy, and stability of the photochromic properties of the resin molded body, the remaining SH groups in the resin molded body It found that there is a correlation between the concentration. Incidentally, the correlation between the stability and residual NCO group concentration of the photochromic performance was not confirmed. Further, if the specific range above molar ratio in the resin composition is more than 1.0, it was found that the residual SH group concentration in the resin molded product is suppressed. That is, the molar ratio in the resin composition, a predetermined range including many NCO groups, deterioration over time of the photochromic performance by then reducing the residual SH group concentration in the resin molded body is less than predetermined value There was found to be suppressed.
Means for Solving the Problems
[0009]
　The present invention can be illustrated below.
[1] (A) a polyisocyanate
　compound, (B) the following general formula (1)
[Chemical formula 1]

(In the formula (1), m represents a number of 1 ~ 20, k represents the 0 ~ 2m, n represents a number of 1 ~ 20, l represents 0 ~ 2n, a is 0 or more numeric, b is 0 or more numeric, d represents 0 or more numeric, e is 1 or more numeric shown .Q 1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, Q is plurality of 1 good .Q be the same or different 2 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms , Q there exist a plurality of 2 in good .Z be different also identical, it represents a divalent organic group contain an ~ 1 carbon atoms which may 30 aromatic radical, the Z presence of a plurality are identical or different which may be.)
represented by a polyol compound a number average molecular weight of 100 or more,
(C) difunctional or more active Containing compound (provided that the compound (B) except for) and,
(D) and a photochromic compound,
a polymerizable composition polymerized hardened molded body comprising,
　SH group concentration by IR spectrometry 1.0 wt% less than a is molded body.
[2] Polyisocyanate compound (A), hexamethylene diisocyanate, pentamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane diisocyanate, 2,5-bis (isocyanatomethyl) bicyclo - [2.2.1] - heptane, 2,6-bis (isocyanatomethyl) bicyclo - [2.2.1] - 1 heptane is selected from tolylene diisocyanate, phenylene diisocyanate, and the group consisting of diphenylmethane diisocyanate is species than, the molded body according to [1].
[3] polyol compound (B) is one or more compounds selected from compounds represented by the following general formula (I) ~ the following general formula (IV), according to [1] or [2] moldings;
[formula 2]

(. wherein (I), p represents a number between 4 ~ 100, X represents a hydrogen atom or a methyl group, X that existing in plural numbers may be the same or different)
[of 3]

(in the formula (II), q, r may be the same or different, each represent one or more numbers, and the total of q and r is a number between 2 ~ 100 .R 1 and R 2 may be the same or different, represent a hydrogen atom or a methyl radical, R presence of a plurality of 1 or R 2 is optionally be the same or different each .Z represents a divalent aromatic substituted or unsubstituted group may contain a substituted or unsubstituted aromatic group having 1 to 20 carbon atoms divalent aliphatic group The show.)
[Formula 4]

(In the formula (III), q, r may be the same or different, each represent one or more numerical and .R sum of q and r is a number from 2 to 100 1 and R 2 are, it may be the same or different, represent a hydrogen atom or a methyl radical, R presence of a plurality of 1 or R 2 may each be the same or different.)
[Chemical formula 5]

(in the formula (IV), m is 1 shows the numerical value of ~ 20, k represents 0 ~ 2m, n represents a number of 1 ~ 20, l represents 0 ~ 2n, f represents 0 or more numeric, g represents 1 or more numeric , h represents 1 or more numeric, j is .Q exhibit one or more of the numerical value 1 represents a hydrogen atom or an alkyl group having a carbon number of 1 ~ 6, Q there exist a plurality 1 may be the same or different. Q 2 represents a hydrogen atom or an alkyl group having a carbon number of 1 ~ 6, Q there exist a plurality 2 is be the same or different .R 3 represents a linear or branched alkylene group or a linear or branched alkyl group which may have as a substituent a phenylene group having 1 to 10 carbon atoms, from 1 to 20 carbon atoms, R presence of a plurality of 3 is different may be.) in the same
compound [4]
[5] The compound represented by the general formula (I) is a polyethylene glycol or polypropylene glycol, molded product according to [3] or [4].
[6] The number average molecular weight of the compound represented by the general formula (I) is 200 to 4000, and [3] molded body according to any one of to [5].
[7] The number average molecular weight of the compound represented by the general formula (I) of 300 to 3000, [3] molded body according to any one of to [5].
[8] The number average molecular weight of the compound represented by the general formula (II) is 400-2000, molded product according to [3].
[9] The number average molecular weight of the compound represented by the general formula (III) is 400-2000, molded product according to [3] or [4].
[10] The number average molecular weight of the compound represented by the general formula (IV) is 600 to 3000, molded product according to [3] or [4].
[11] active hydrogen compound (C), a polyol compound, one or more selected from the group consisting of thiol compounds having a polythiol compound and a hydroxy group, molded according to any one of [1] to [10] body.
[12] active hydrogen compound (C) is an active hydrogen compound having three or more functional, compact according to any one of [1] to [11].
[13] active hydrogen compound (C), glycerol, pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), 4-mercaptomethyl-1,8-dimercapto-3,6 dithiaoctane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 1,1,3,3-tetrakis (mercaptomethylthio) propane and trimethylolpropane tris (3-mercaptopropionate, at least one selected from the group consisting of sulfonate), [1] - [1 Molded body according to any one of 2].
[14] The photochromic compound (D) is represented by the following general formula (5), molded article according to any one of [1] to [13];
[Chemical Formula 6]

(wherein, R 1 and R 2 may be the same or different, are independently hydrogen;
linear or branched alkyl group of 1 to 12 carbon atoms;
a cycloalkyl group having 3 to 12 carbon atoms;
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, hydroxy 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 number 1 linear or branched haloalkoxy group having 1-12, and at least one linear or branched alkyl group or a phenoxy group or a naphthoxy group substituted by an alkoxy group having 1 to 12 carbon atoms, 2 to 12 carbon atoms linear or branched alkenyl group, -NH 2 group, -NHR group, -N (R) 2 group (R is a straight-chain or branched alkyl group having 1 to 6 carbon atoms .R is One If present, 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 (1 to 4 carbon atoms . the linear or branched alkyl group is replaced with the aryl or heteroaryl group)
represents,
　R 3 may be the same or different, is independently a halogen atom;
having 1 to 12 carbon atoms ; 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 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 halogen atom linear or branched haloalkoxy group substituted having 1 to 12 carbon atoms;
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, hydroxy 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 linear carbon number of 1 to 12 substituted by a halogen atom or branched haloalkyl group, at least one straight-chain or branched haloalkoxy group having 1 to 12 carbon atoms which is substituted with a halogen atom, at least one A phenoxy group or a naphthoxy group substituted by straight-chain or branched alkyl or alkoxy group having 1 to 12 carbon atoms, straight-chain or branched alkenyl group having 2 to 12 carbon atoms, and amino groups, selected from that has at least 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 of (as a substituent, having at least one substituent selected from linear or branched alkyl or alkoxy group having 1 to 6 carbon
atoms.) phenoxy or naphthoxy group; -NH 2 , -NHR, -CONH 2 , or -CONHR
(R is a linear or branched alkyl group having 1 to 6 carbon atoms.);
-OCOR 8 or -COO R 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, the substituted aryl or substituted heteroaryl group a phenyl group or an unsubstituted phenyl group substituted by at least one substituent);.
represents,
m is an integer from 0 to 4;
a is a compound represented by the following formula (a 2 ) or formula ( a 4 )
[Chemical formula 7]

represents Asnelles of rings, in these Asnelles of rings,
the dotted line, carbon C naphthopyran ring in the general formula (5) 5 carbon C 6 represents a bond;
Aner of ring (a 4 ) of α bonds, the general formula (5) of the naphthopyran ring carbon C 5 or carbon C 6 can be coupled to;
R 4 is the same or different, independently, OH, having 1 to 6 carbon atoms It represents a linear or branched alkyl group or alkoxy group, or One of R 4 form a carbonyl
(CO); R 5 is halogen;
Linear or branched alkyl group having 1 to 12 carbon atoms;
substituted by at least one halogen atom, a haloalkyl group linear or branched having 1 to 6 carbon atoms;
a cycloalkyl group having 3 to 12 carbon atoms;
linear or branched alkoxy group having 1 to 6 carbon atoms;
substituted or as unsubstituted phenyl or benzyl group (substituent radical, R in the general formula (5) 1 , R 2 groups are independently aryl or heteroaryl group may correspond to, 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 straight-chain or branched having 1 to 6 carbon atoms an alkyl group of branches);.
as 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);.
-C R 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, as the phenyl or benzyl group (substituent radical, R in the general formula (5) 1 , R 2When a group independently correspond to an aryl or heteroaryl group, R 1 , R 2 has at least one of the substituents mentioned above in the definition of groups. ));
A is (A 4 may exhibit) is an integer of from n is 0 to 2, p is an integer from 0 to 4, A is (A 2 may exhibit), from n 0 2 it is an integer of up to. ).
[15] functional groups of the polyisocyanate compound a polyol compound to the (A) (B) the functional group equivalent ratio of (B / A) of 0.02 to 0.6, and the polyisocyanate compound active hydrogen compound for (A) (C) the equivalent ratio is (C / a) of 0.4 to 0.98 molded body according to any one of [1] to [14].
[16] [1] optical material comprising a molded body according to any one of - [15].
[17] [1] to a plastic lens comprising a molded body according to any one of [15].
[18] and a polarizing film, at least one of which is formed on the surface, [1] to plastic polarized lens comprising: a base material layer made of a molded product according to any one of [15] of the polarizing film.
[19] (A) a polyisocyanate
　compound, (B) the following general formula (1)
[formula 8]

(In the formula (1), m represents a number of 1 ~ 20, k represents the 0 ~ 2m, n represents a number of 1 ~ 20, l represents 0 ~ 2n, a is 0 or more numeric, b is 0 or more numeric, d represents 0 or more numeric, e is 1 or more numeric shown .Q 1 represents a hydrogen atom or an alkyl group having a carbon number of 1 ~ 6, Q presence of a plurality of1 may be the same or different. Q 2 represents a hydrogen atom or an alkyl group having a carbon number of 1 ~ 6, Q there exist a plurality 2 may be the same or different. Z represents a divalent organic group contain an ~ carbon atoms 1 be 30 aromatic group, Z that existing in plural numbers may be the same or different. )
Is represented by a polyol compound a number average molecular weight of 100 or more,
and (C) bifunctional or polyfunctional active hydrogen compound (provided that the compound (B) except for)
, and (D) a photochromic compound
containing, a polymerizable composition,
　to the sum of the OH and SH groups contained in the active hydrogen compound (C) and the polyol compound (B), the molar ratio of NCO groups contained in the polyisocyanate compound (a) (NCO group / ( OH group + SH group)) is in the range of 1.1-1.6, the optical material for the polymerizable composition.
[20] (A) a polyisocyanate
　compound, (B) the following general formula (1)
[Formula 9]

(In the formula (1), m represents a number of 1 ~ 20, k represents the 0 ~ 2m, n represents a number of 1 ~ 20, l represents 0 ~ 2n, a is 0 or more numeric, b is 0 or more numeric, d represents 0 or more numeric, e is 1 or more numeric shown .Q 1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, Q is plurality of 1 good .Q be the same or different 2 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms , Q presence of a plurality of 2It may be the same or different. Z represents a divalent organic group contain an ~ carbon atoms 1 be 30 aromatic group, Z that existing in plural numbers may be the same or different. )
Is represented by a polyol compound a number average molecular weight of 100 or more,
and (C) bifunctional or polyfunctional active hydrogen compound (provided that the compound (B) except for),
and a (D) a photochromic compound, the active hydrogen compound for (C) and the sum of OH and SH groups contained in the polyol compound (B), the polyisocyanate compound (a) the molar ratio of NCO groups contained in the (NCO groups / (OH group + SH group)) is, 1.1 were mixed so that the range of ~ 1.6, a step of preparing an optical material for the polymerizable composition,
　a lens by cast polymerization to the mold the optical material for the polymerizable composition forming a substrate,
comprising the method of manufacturing a plastic lens.
[21] (A) a polyisocyanate
　compound, (B) the following general formula (1)
[Formula 10]

(In the formula (1), m represents a number of 1 ~ 20, k represents the 0 ~ 2m, n represents a number of 1 ~ 20, l represents 0 ~ 2n, a is 0 or more numeric, b is 0 or more numeric, d represents 0 or more numeric, e is 1 or more numeric shown .Q 1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, Q is plurality of 1 good .Q be the same or different 2 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms , Q presence of a plurality of 2It may be the same or different. Z represents a divalent organic group contain an ~ carbon atoms 1 be 30 aromatic group, Z that existing in plural numbers may be the same or different. )
Is represented by a polyol compound a number average molecular weight of 100 or more,
and (C) bifunctional or polyfunctional active hydrogen compound (provided that the compound (B) except for),
and a (D) a photochromic compound, the active hydrogen compound for (C) and the sum of OH and SH groups contained in the polyol compound (B), the polyisocyanate compound (a) the molar ratio of NCO groups contained in the (NCO groups / (OH group + SH group)) is, 1.1 were mixed so that the range of ~ 1.6, a step of preparing an optical material for the polymerizable composition,
　to fix the polarizing film, the lens casting in a mold in a state of being spaced apart from the mold a step,
　wherein a polarizing film, wherein the step of injecting an optical material for the polymerizable composition to at least one of the gap formed between the mold
　hard polymerizing said optical material for the polymerizable composition To, a step of laminating the base material layer on at least one surface of the polarizing film
including the method for producing a plastic polarized lens.
Effect of the invention
[0010]
　According to the molding of the present invention, the deterioration over time is suppressed photochromic performance, the photochromic performance can be exerted stably, polyurethane optical materials or polythiourethane optical material containing a photochromic compound from the molded product it is possible to provide a.
　According to the optical material for the polymerizable composition of the present invention, it is possible to obtain the molded article suitably.
DESCRIPTION OF THE INVENTION
[0011]
　Molding of the present invention, the following (A) ~ obtained by polymerizing composition polymerized curing comprising a compound of (D), SH group concentration by IR spectrometry is less than 1.0 wt%.
　(A) the polyisocyanate compound
　(B) represented by the following general formula (1), a polyol compound a number average molecular weight of 100 or more
(but excluding the compound (B)) (C) bifunctional or polyfunctional active hydrogen compound
(D) a photochromic compound
[0012]
[Of 11]

[0013]
　Wherein (1), m represents a number of 1 ~ 20, k represents 0 ~ 2m, n represents a number of 1 ~ 20, l represents 0 ~ 2n, a represents 0 or numbers , b represents 0 or more numeric, d represents 0 or more numeric, e is shown one or more values. Q 1 represents a hydrogen atom or an alkyl group having a carbon number of 1 ~ 6, Q there exist a plurality 1 may be the same or different. Q 2 represents a hydrogen atom or an alkyl group having a carbon number of 1 ~ 6, Q there exist a plurality 2 may be the same or different. Z represents a divalent organic group contain an ~ carbon atoms 1 be 30 aromatic group, Z that existing in plural numbers may be the same or different.
　According to the molding of the present invention, the deterioration over time is suppressed photochromic performance can be stably exhibit photochromic properties.
[0014]
　Molding of the present invention can be obtained by using the optical material for the polymerizable composition of the present embodiment. First, the optical material for the polymerizable composition on the basis of the following embodiments.
　The optical material for the polymerizable composition of the present embodiment,
　(A) a polyisocyanate compound,
　represented by (B) the following general formula (1), a polyol compound a number average molecular weight of 100 or more,
　(C) two functional or more active hydrogen compound (provided that the compound (B) except for) and,
　including the (D) a photochromic compound.
　Active hydrogen compound for (C) and the sum of OH and SH groups contained in the polyol compound (B), the polyisocyanate compound (A) the molar ratio of NCO groups contained in the (NCO groups / (OH group + SH group)) is , it is within the range of from 1.1 to 1.6.
[0015]
[Chem. 12]

[0016]
　Wherein (1), m represents a number of 1 ~ 20, k represents 0 ~ 2m, n represents a number of 1 ~ 20, l represents 0 ~ 2n, a represents 0 or numbers , b is 0 or more, d represents 0 or more numeric, e is shown one or more values. Q 1 represents a hydrogen atom or an alkyl group having a carbon number of 1 ~ 6, Q there exist a plurality 1 may be the same or different. Q 2 represents a hydrogen atom or an alkyl group having a carbon number of 1 ~ 6, Q there exist a plurality 2 may be the same or different. Z represents a divalent organic group contain an ~ carbon atoms 1 be 30 aromatic group, Z that existing in plural numbers may be the same or different.
[0017]
　The optical material for the polymerizable composition of the present embodiment, the (A) by including the structure of the compound of ~ (C), the photochromic compound within the polymer matrix of the composition of the isomerization reaction of (D) It is presumed to be effectively suppressed disorder. That, (A) and the conventional resins which are used in ophthalmic lenses such as a compound of (C), by adding the compound of an essential component of the present invention (B), the photochromic in the matrix molecular chain moderate space as isomerization reaction easily occur compound is formed, as a result, are considered to achieve good photochromic performance. Further, this configuration can be provided with exhibits high photochromic performance, that have excellent mechanical properties which are characteristic of the poly (thio) urethane resin, an excellent optical material balance.
　Further, according to the optical material for the polymerizable composition of the present invention, the deterioration over time is suppressed photochromic compounds, the photochromic performance can provide a molded article can be stably exhibited.
　Each component is explained below.
[0018]
[(A) a polyisocyanate compound]
　polyisocyanate compound (A), hexamethylene diisocyanate, pentamethylene diisocyanate, 2,2,4-trimethyl hexane diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanato methyl ester, lysine triisocyanate, m- xylylene diisocyanate, o- xylylene diisocyanate, p- xylylene diisocyanate, xylylene diisocyanate, α, α, α ', α'- tetramethylxylylene diisocyanate, bis (isocyanatomethyl ) naphthalene, 1,3,5-tris (isocyanatomethyl) benzene, bis (isocyanatomethyl) sulfide, bis (isocyanatoethyl) sulfide, bis (Isoshianatome Le) disulfide, bis (isocyanatoethyl) disulfide, bis (isocyanatomethyl thio) methane, bis (isocyanatoethyl thio) methane, bis (isocyanatoethyl) ethane, bis (aliphatic poly such as isocyanatomethyl) ethane isocyanate compounds;
Isophorone diisocyanate, bis (isocyanatomethyl) cyclohexane, 1,2-bis (isocyanatomethyl) cyclohexane, 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane diisocyanate , dicyclohexylmethane-4,4'-diisocyanate, dicyclohexylmethane-2,4'-diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, dicyclohexyl dimethyl methane diisocyanate, 2,5-bis (isocyanatomethyl) bicyclo - [2.2. 1] - heptane, 2,6-bis (isocyanatomethyl) bicyclo - [2.2.1] - heptane, 3,8-bis (isocyanatomethyl) tricyclodecane, 3 9- bis (isocyanatomethyl) tricyclodecane, 4,8-bis (isocyanatomethyl) tricyclodecane, 4,9-bis (isocyanatomethyl) alicyclic polyisocyanate compounds such as tricyclodecane;
diphenyl sulfide 4,4-diisocyanate, tolylene diisocyanate, phenylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, aromatic such as diphenylmethane diisocyanate polyisocyanate compound;
2,5-diisocyanato-thiophene, 2,5-bis (isocyanatomethyl) thiophene, 2,5-diisocyanato-tetrahydrothiophene, 2,5-bis (isocyanatomethyl) tetrahydrothiophene, 3,4-bis ( isocyanatomethyl) tetrahydrothiophene, 2,5-diisocyanato-1,4-dithiane, 2,5-bis (isocyanatomethyl) -1,4-dithiane, 4,5-diisocyanato-1,3-dithiolane, 4, 5-bis can be mentioned (isocyanatomethyl) -1,3-heterocyclic polyisocyanate compounds such dithiolane like. As the polyisocyanate compound (A), it can be used at least one selected from these.
[0019]
　As the polyisocyanate compound (A), in addition to the monomers, including the case of a mixture of modified products and / or modified product, the modified product of an isocyanate, for example, multimers, biuret modified products, allophanate modified products, oxadiazinetrione-modified products, and the like polyol-. The multimers, for example, uretdione, uretonimine, dimers, such as carbodiimide, isocyanurate, trimers or multimers of such imino oxa Jian-dione can be cited.
[0020]
　As the polyisocyanate compound (A), hexamethylene diisocyanate, pentamethylene diisocyanate, m- xylylene diisocyanate, isophorone diisocyanate, bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane diisocyanate, 2,5-bis (isocyanatomethyl) bicyclo - [2.2.1] - heptane, 2,6-bis (isocyanatomethyl) bicyclo - [2.2.1] - heptane, tolylene diisocyanate, phenylene diisocyanate, diphenylmethane diisocyanate
　preferably, m-xylylene diisocyanate, isophorone diisocyanate, bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane diisocyanate, 2,5-bis (isocyanatomethyl) bicyclo - [ .2.1] - heptane, 2,6-bis (isocyanatomethyl) bicyclo - [2.2.1] - heptane is more preferred. These polyisocyanate compounds may be used alone or may be used as a mixture of two or more thereof.
[0021]
[(B) a polyol compound]
　In the present embodiment, the polyol compound (B), is represented by the following general formula (1), number average molecular weight is used one or more compounds selected from compounds of 100 or more be able to.
[0022]
[Formula 13]

[0023]
　The number average molecular weight of the polyol compound (B), the lower limit is 100 or more, preferably 200 or more, more preferably 300 or more, more preferably 400 or more, the upper limit is 4000 or less, more preferably 3000 or less, more preferably 2000 is less than or equal to. Upper and lower limits can be combined as appropriate.
[0024]
　Wherein (1), m is 1-20, preferably 1-10, more preferably it shows values of 2-5.
　n is 1 to 20, preferably 1 to 10, more preferably shows values of 2-5.
　a is 0 or more, preferably 0-100, more preferably shows a value of 0-25.
　b is 0 or more, preferably 0-200, more preferably indicates a number between 0 and 100.
　d is 0 or more, preferably 1 to 200, more preferably shows a value of 1 to 100.
　e is 1 or more, preferably 1 to 200, more preferably shows a value of 1 to 100.
　k represents an 0 ~ 2m, l indicates a 0 ~ 2n.
[0025]
　Q 1 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Q presence of a plurality of 1 may be the same or different.
　Q 2 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Q presence of a plurality of 2 may be the same or different.
[0026]
　Z is a divalent organic group contain an ~ 1 carbon atoms which may 30 aromatic group, preferably a divalent organic group of the aromatic group of carbon atoms which may contain 1 to 20. Z existing in plural numbers may be the same or different.
　As the "divalent organic group of the aromatic carbon atoms which may contain a group 1-30", methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, a cyclopentylene group, a hexamethylene group , cyclohexylene group, a heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, undecamethylene group, dodecamethylene group, tridecamethylene group, tetradecamethylene group, having 1 to 30 carbon atoms such as a pentadecamethylene group substituted or unsubstituted linear or cyclic aliphatic group;
a phenylene group, naphthylene group, anthracene group, diphenylmethane group, 1,1-diphenylethane group, 1,1,1-methyl diphenyl ethane group, diphenyl propane group, diphenyl ether group , diphenyl sulfide group, diphenyl sulfoxide group, diphenyl Sulfone group, diphenyl ketone group, a phenyl benzoate group, a biphenyl group, a stilbene group, di-azobenzene group, a substituted or unsubstituted aromatic group having 6 to 30 carbon atoms of such as aniline benzylidene group;
-C 6 H 4 -CH 2 - group, -CH 2 -C 6 H 4 -CH 2 - group, -CH 2 -C 6 H 3(Cl) -CH 2 - group, -C 10 H 6 -CH 2 - group, -CH 2 -C 10 H 6 -CH 2 - group, -CH 2 CH 2 -C 6 H 4 -CH 2 CH 2 - substituted or unsubstituted 6 to 30 aromatic carbons of such groups - aliphatic group; or
-C (O) -R 7 -C (O) - (R 7 is a substituted or unsubstituted C 1 -C linear or branched alkylene group of 1-20, an aromatic group or a substituted or unsubstituted carbon atoms to 20 6), -. C (O) -R 8 - (R 8 is a substituted or unsubstituted carbon atoms . a linear or branched alkylene group of 1 to 20) of 1 to 30 carbonyl group-containing compound carbon atoms such as,
and the like.
　These organic groups, C 1-10 straight or branched alkyl group having a carbon may be substituted with C 1-10 linear or branched alkoxy group such as carbon.
[0027]
　To impart good color performance polymer obtained from the polymerizable composition of the present embodiment (molded body), it is necessary to set the molecular weight of the polyol compound (B) in the appropriate range to be added.
[0028]
　In this embodiment, the polyol compound (B), the general formula (I) can be used one or more compounds selected from - a compound represented by the general formula (IV).
[0029]
(Compound represented by the general formula (I))
[Formula 14]

[0030]
　Wherein (I), p represents a number from 4-100, preferably a value of 15 to 50. X represents a hydrogen atom or a methyl group, X that existing in plural numbers may be the same or different. X is preferably a methyl group.
[0031]
　Examples of the compound represented by the general formula (I), polyethylene glycol, include polypropylene glycol, which may include a low-molecular oligomers such as ethylene glycol or diethylene glycol, triethylene glycol, also, be used alone it may also be used as a mixture of two or more thereof.
[0032]
　The number average molecular weight of the compound represented by the general formula (I), the lower limit is 100 or more, preferably 200 or more, more preferably 300 or more, more preferably 400 or more, the upper limit is 4000 or less, more preferably 3000 or less , and even more preferably 2000 or less. Upper and lower limits can be combined as appropriate.
[0033]
　Formula number average molecular weight of the compound represented by the general formula (I) is by the range of the effectively express photochromic performance without impairing the excellent properties such as mechanical strength of the poly (thio) urethane resin be able to.
　For example, when the compound represented by the general formula (I) is polyethylene glycol, coloring performance and the number average molecular weight of 400-2000 is more improved, cloudiness of the polymer is further suppressed.
　Further, when the compound represented by the general formula (I) are polypropylene glycol, coloring performance and the number average molecular weight of from 400 to 1000 are more improved, cloudiness of the polymer is further suppressed.
　In the case of polypropylene glycol high heat resistance polymer obtained than polyethylene glycol, provide rigidity. Therefore, for applications that are used in a variety of environments, conditions such as eyeglass lenses in some cases more preferably is more polypropylene glycol than polyethylene glycol.
[0034]
(Compound represented by the general formula (II))
[Formula 15]

[0035]
　Wherein (II), q, r may be the same or different, represents one or more respective numerical, preferably a value of 6-25. q and r, the sum of 2-100 figures q and r, preferably those that can take a number to satisfy a number of 12-50.
　R 1 and R 2 , which may be the same or different, represent a hydrogen atom or a methyl radical, R presence of a plurality of 1 or R 2 may each be the same or different.
[0036]
　Z 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, the. Incidentally, Z is, -Ph-C (CH 3 ) 2 -Ph-: contains no (Ph phenylene group).
[0037]
　The substituted or unsubstituted divalent aromatic group, a phenylene group, naphthylene group, anthracene group, diphenylmethane group, 1,1-diphenylethane group, 1,1,1-methyl diphenyl ethane group, 1,3-diphenyl propane group, 1,2-diphenyl propane group, diphenyl ether group, diphenyl sulfide group, diphenyl sulfoxide group, diphenyl sulfone group, diphenyl ketone group, a phenyl benzoate group, a biphenyl group, a stilbene group, di-azobenzene group, aniline benzylidene group, and their derivatives, and the like.
　Substituted or The unsubstituted aliphatic aromatic group to comprise not divalent or having 1 to 20 carbon atoms, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, bis 1 to 20 carbon atoms divalent group derived from an alkoxy aromatic compound may be mentioned.
　The alkylene group in the substituted or unsubstituted 1 to 20 carbon atoms, butylene, pentylene group, and a nonylene group.
　The Bisuarukokishi aromatic compound having 1 to 20 carbon atoms, 1,4-bis (hydroxyethoxy) benzene, (1,3-bis (m-hydroxyethoxy) benzene, 2,2 [(1,1-biphenyl ) -4,4-diylbis (oxy)] bis ethanol, and the like.
　divalent as the substituent of the aromatic group and the divalent aliphatic group having 1 to 10 alkyl group carbon, carbon atoms . can be cited 1 to 10 alkoxy group or the like
　in this embodiment, Z is a phenylene group, a naphthylene group is preferably a biphenylene group.
[0038]
　Examples of the compound represented by the general formula (II), 1,4-butanediol, 3-methyl-1,5-pentanediol, 1,9-nonanediol, 1,4-bis (hydroxyethoxy) benzene, 1 , 1,3-bis (m-hydroxyethoxy) benzene, 2,2 [(1,1-biphenyl) -4,4-diylbis (oxy)] polyethylene glycol adduct of bis-ethanol, or polypropylene glycol adduct is exemplified is, it may be used alone or may be used as a mixture of two or more thereof.
　In general formula (II) compound represented by the free of the compound represented by the general formula (III).
[0039]
　The number average molecular weight of the compound represented by formula (II), the lower limit is 200 or more, preferably 300 or more, more preferably 400 or more, more preferably 500 or more, and the upper limit is 4000 or less, preferably 3000 or less, more preferably 2,000 or less, more preferably 1,000 or less. Upper and lower limits can be combined as appropriate.
　Formula (II) compound has a number average molecular weight which is expressed by, by the range of the effectively express photochromic performance without impairing the excellent properties such as mechanical strength of the poly (thio) urethane resin be able to.
[0040]
(Compound represented by the general formula (III))
[Formula 16]

[0041]
　Wherein (III), q, r may be the same or different, represents one or more respective numerical, preferably a value of 6-25. q and r, the sum of 2-100 figures q and r, preferably those that can take a number to satisfy a number of 12-50.
　R 1 and R 2 , which may be the same or different, represent a hydrogen atom or a methyl radical, R presence of a plurality of 1 or R 2 may each be the same or different.
[0042]
　Examples of the compound represented by formula (III), polypropylene glycol adduct of a polyethylene glycol adduct or bisphenol A may be mentioned bisphenol A, these may be used alone, using as a mixture of two or more it may be.
[0043]
　The number average molecular weight of the compound represented by formula (III), the lower limit is 316 or more, preferably 400 or more, more preferably 500 or more, and the upper limit is 4000 or less, preferably 3000 or less, more preferably 2000 or less, more preferably 1500 or less. Upper and lower limits can be combined as appropriate.
　Formula (III) compound has a number average molecular weight which is expressed by, by the range of the effectively express photochromic performance without impairing the excellent properties such as mechanical strength of the poly (thio) urethane resin be able to.
　For example, when the compound represented by the general formula (III) is polypropylene glycol adduct of polyethylene glycol adduct and bisphenol A bisphenol A, coloring performance and the number average molecular weight of from 400 to 1000 are more improved, the polymer cloudiness is further suppressed.
[0044]
(Compound represented by the general formula (IV))
[Formula 17]

[0045]
　Wherein (IV), m is 1-20, preferably 1-10, more preferably it shows values of 2-5.
　n is 1 to 20, preferably 1 to 10, more preferably shows values of 2-5.
　f is 0 or more, preferably 0-100, more preferably shows a value of 0-25.
　g is 1 or more, preferably from 1 to 200, more preferably shows a value of 1 to 100.
　h is 1 or more, preferably 1 to 200, more preferably shows a value of 1 to 100.
　j is 1 or more, preferably 1 to 200, more preferably shows a value of 1 to 100.
　k represents an 0 ~ 2m, l indicates a 0 ~ 2n.
[0046]
　Q 1 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Q presence of a plurality of 1 may be the same or different.
　Q 2 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Q presence of a plurality of 2 may be the same or different.
　R 3 represents a linear or branched alkylene group or a linear or branched alkyl group which may have as a substituent a phenylene group having 1 to 10 carbon atoms, from 1 to 20 carbon atoms. R presence of a plurality of 3 may be the same or different.
[0047]
　Examples of the compound represented by formula (IV), and polyester compounds comprising a diol compound and a dicarboxylic acid.
　Is not particularly limited as diol compounds constituting the polyester compounds, aliphatic diols having 2 to 12 carbon atoms in the main chain is preferably used, ethylene glycol, propylene glycol as these examples, 1,4-butanediol, 3-methyl-1,5-pentanediol, 1,9-nonanediol and the like.
　Although there is no particular limitation as dicarboxylic acid constituting the polyester compounds, aliphatic dicarboxylic acids and aromatic dicarboxylic acids having 2 to 12 carbon atoms in the main chain is suitably used, succinic acid, adipic acid as the examples , sebacic acid, isophthalic acid, terephthalic acid, and the like.
　Polyester compounds may be used in combination with one or more of these diol compounds, and one or more dicarboxylic acids as appropriate.
　Also, the polyester compound obtained by ring-opening polymerization of lactones may be used in the present invention. Examples of the lactone compound, alpha-acetolactone, beta-propiolactone, .gamma.-butyrolactone, .delta.-valerolactone, and the like.
[0048]
　The number average molecular weight of the compound represented by formula (IV), the lower limit is 600 or more, preferably 800 or more, more preferably 1,000 or more, the upper limit is 4000 or less, more preferably 3000 or less, more preferably 2000 or less it is. Upper and lower limits can be combined as appropriate.
[0049]
　Formula number average molecular weight of the compound represented by the general formula (IV) is, by the range of the effectively express photochromic performance without impairing the excellent properties such as mechanical strength of the poly (thio) urethane resin be able to.
　For example, the compound represented by the general formula (IV) is, in the case of the polyester compound obtained by reacting an equimolar mixture equimolar 3-methyl-1,5-adipic acid and isophthalic acid pentanediol, number average molecular weight 1000 to the color performance of 2000 is further improved, cloudiness of the polymer is further suppressed.
[0050]
　By using polyol compound comprising a compound as described above and (B), it is possible to express photochromic performance effectively.
[0051]
　In this embodiment, as the polyol compound (B), can be used the formula (I) compound represented by - formula (IV) with one or more compounds selected from the compounds represented, the from the standpoint of effects, the general formula (I), the general formula (III) or the general formula represented by (IV) can be preferably used compounds.
[0052]
　In this embodiment, the polyol compound (B), relative to the weight of bifunctional or polyfunctional active hydrogen compound (C), it is possible to use a range of 0.3 times by weight to 6 times by weight. In the present embodiment, resin performance required by the application while maintaining high photochromic performance can be used within the range so as to obtain. Preferably from 0.7 times by weight to 5 times by weight.
[0053]
　Times by weight of the active hydrogen compound polyol compound for (C) (B) is, by the range of the high light modulating performance, i.e., it is possible to suitably exert the dark color density and fast concentration changes. Furthermore, since the crosslinking density becomes optimum range, it is possible to obtain rigid, surface hardness, excellent optical material by heat resistance and the like.
[0054]
[(C) bifunctional or polyfunctional active hydrogen compound]
　bifunctional or polyfunctional active hydrogen compound (C) (hereinafter, simply "active hydrogen compound (C)") include, but are not particularly limited, a polyol compound, polythiol compound include thiol compounds having a hydroxy group. These can be combined as appropriate. It can not be selected polyol compound only. Active hydrogen compound (C), the molar ratio of SH groups to the sum of the SH group and the OH group (SH / (SH + OH) ) is 0.01-1.0, preferably 0.1-1.0, further preferably from 0.3 to 1.0. The active hydrogen compound (C) does not include the polyol compound (B).
[0055]
　As the polyol compound, such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, butylene glycol, neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane, ditrimethylolpropane, butanetriol, 1,2 methyl glucoside, pentaerythritol, dipentaerythritol, tripentaerythritol, sorbitol, erythritol, threitol, ribitol, arabinitol, xylitol, allitol, mannitol, Dorushitoru, iditol, glycol, inositol, hexanetriol, Toriguriserosu, Jiguriperoru, triethylene glycol, polyethylene glycol, tris 2-hydroxyethyl) isocyanurate, cyclobutanediol, cyclopentane diol, cyclohexane diol, cycloheptane diol, cyclooctane diol, cyclohexane dimethanol, hydroxypropyl cyclohexanol, tricyclo [5.2.1.0 2, 6 ] decane - dimethanol, bicyclo [4.3.0] - nonane diol, di-cyclohexanediol, tricyclo [5.3.1.1] dodecanediol, bicyclo [4.3.0] nonane methanol, tricyclo [5.3. 1.1] dodecane - diethanol, hydroxypropyl tricyclo [5.3.1.1] dodecanol, spiro [3.4] octanediol, butyl cyclohexanediol, 1,1'-bi cyclohexylidene dimethylene-ol, cyclohexane tri Lumpur, maltitol, aliphatic polyols such as lactose;
Dihydroxynaphthalene, tri-hydroxynaphthalene, tetrahydroxynaphthalene, dihydroxybenzene, benzene triol, biphenyl tetraol, pyrogallol, (hydroxynaphthyl) pyrogallol, trihydroxy phenanthrene, bisphenol A, bisphenol F, xylylene glycol, di (2-hydroxyethoxy) ; benzene, bisphenol A- bis - - (2-hydroxyethyl ether), tetrabromobisphenol a, tetrabromobisphenol A- bis (2-hydroxyethyl ether) aromatic polyols such as
halogenated polyols such as dibromoneopentyl glycol;
polymeric polyols such as epoxy resin. In the present embodiment, it can be used in combination of at least one selected from these.
[0056]
　Also, the other as a polyol compound, oxalic acid, glutamic acid, adipic acid, acetic acid, propionic acid, cyclohexanecarboxylic acid, beta-oxo-cyclohexane-propionic acid, dimer acid, phthalic acid, isophthalic acid, salicylic acid, 3-bromopropionic acid, 2 - bromo glycol, dicarboxylate-cyclohexane, pyromellitic acid, butane tetracarboxylic acid, a condensation reaction product of an organic acid and the polyol, such as bromophthalic acid;
addition reaction products of an alkylene oxide such as the above polyol with ethylene oxide or propylene oxide ;
and alkylene polyamines and ethylene oxide, propylene oxide addition reaction products of an alkylene oxide; further,
bis - [4- (hydroxyethoxy) phenyl] sulfide, bis - [4- ( - hydroxypropoxy) phenyl] sulfide, bis - [4- (2,3-dihydroxy-propoxy) phenyl] sulfide, bis - [4- (4-hydroxy-cyclohexyloxy) phenyl] sulfide, bis - [2-methyl-4- (hydroxyethoxy) -6-butylphenyl] sulfide and compounds having an average 3 molecules or less of ethylene oxide and / or propylene oxide hydroxyl per added to these compounds;
Di - (2-hydroxyethyl) sulfide, 1,2-bis - (2-hydroxyethyl-mercapto) ethane, bis (2-hydroxyethyl) disulfide, 1,4-dithiane-2,5-diol, bis (2, 3-dihydroxypropyl) sulfide, tetrakis (4-hydroxy-2-Chiabuchiru) methane, bis (4-hydroxyphenyl) sulfone (trade name bisphenol S), tetrabromobisphenol S, tetramethyl bisphenol S, 4,4'-thiobis (6-tert-butyl-3-methylphenol), 1,3-bis (2-hydroxyethyl thio ethyl) - polyols containing a sulfur atom, such as cyclohexane. In the present embodiment, it can be used in combination of at least one selected from these.
[0057]
　The polythiol compound, for example, methane dithiol, 1,2-ethanedithiol, 1,2,3-propane trithiol, 1,2-cyclohexane dithiol, bis (2-mercaptoethyl) ether, tetrakis (mercaptomethyl) methane, diethylene glycol bis (2-mercaptoacetate), diethylene glycol bis (3-mercaptopropionate), ethylene glycol bis (2-mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), trimethylolpropane tris (2-mercapto acetate), trimethylolpropane tris (3-mercaptopropionate), trimethylolethane tris (2-mercaptoacetate), trimethylolethane tris (3-Merukaputopuro Onato), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), bis (mercaptomethyl) sulfide, bis (mercaptomethyl) disulfide, bis (mercaptoethyl) sulfide, bis (mercaptoethyl ) disulfide, bis (mercaptopropyl) sulfide, bis (mercaptomethyl thio) methane, bis (2-mercaptoethyl thio) methane, bis (3-mercaptopropyl thio) methane, 1,2-bis (mercaptomethyl) ethane, 1, 2- bis (2-mercaptoethyl thio) ethane, 1,2-bis (3-mercaptopropyl) ethane, 1,2,3-tris (mercaptomethylthio) propane, 1,2,3-tris (2-Melka Toechiruchio) propane, 1,2,3-tris (3-mercaptopropyl thio) propane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 5,7-dimercaptomethyl-1,11-dimercapto -3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto -3 , 6,9-Doo Richiaundekan, tetrakis (mercaptomethyl thio) methane, tetrakis (2-mercaptoethylthiomethyl) methane, tetrakis (3-mercapto propyl thio methyl) methane, bis (2,3-mercaptopropyl) sulfide, 2,5-di mercaptomethyl-1,4-dithiane, 2,5-dimercapto-1,4-dithiane, 2,5-dimercapto-2,5-dimethyl-1,4-dithiane, and these thioglycolic acid and mercaptopropionic esters of acids, hydroxymethyl sulfide bis (2-mercaptoacetate), hydroxymethyl sulfide bis (3-mercaptopropionate), hydroxyethyl sulfide bis (2-mercaptoacetate), hydroxyethyl sulfide bis (3-mercapto Propionate), hydroxymethyl disulfide bis (2-mercaptoacetate), hydroxymethyl disulfide bis (3-mercaptopropionate), hydroxyethyl disulfide bis (2-mercaptoacetate), hydroxyethyl disulfide bis (3-mercapto propionate), 2-mercaptoethyl ether bis (2-mercaptoacetate), 2-mercaptoethyl ether bis (3-mercaptopropionate), thiodiglycolic acid bis (2-mercaptoethyl ester), thiodipropionic acid bis (2-mercapto ethyl ester), dithiodiglycolic acid bis (2-mercaptoethyl ester), dithiodipropionic acid bis (2-mercaptoethyl ester), 1,1,3,3-tetrakis (mercapto Methylthio) propane, 1,1,2,2-tetrakis (mercaptomethyl) ethane, 4,6-bis (mercaptomethyl thio) -1,3-dithiane, tris (mercaptomethyl thio) methane, tris (mercaptoethylthio) methane aliphatic polythiol compound of; Ropiruchiomechiru) methane, bis (2,3-mercaptopropyl) sulfide, 2,5-mercaptomethyl-1,4-dithiane, 2,5-dimercapto-1,4-dithiane, 2,5-mercaptomethyl - 2,5-dimethyl-1,4-dithiane, and esters of these thioglycolic acid and mercaptopropionic acid, hydroxymethyl sulfide bis (2-mercaptoacetate), hydroxymethyl sulfide bis (3-mercaptopropionate), hydroxy ethyl sulfide bis (2-mercaptoacetate), hydroxyethyl sulfide bis (3-mercaptopropionate), hydroxymethyl disulfide bis (2-mercaptoacetate), hydroxymethyl disulfide bis (3-mercaptopropionate) Hydroxyethyl disulfide bis (2-mercaptoacetate), hydroxyethyl disulfide bis (3-mercapto propionate), 2-mercaptoethyl ether bis (2-mercaptoacetate), 2-mercaptoethyl ether bis (3-mercaptopropionate) , thio diglycolic acid bis (2-mercaptoethyl ester), thiodipropionic acid bis (2-mercaptoethyl ester), dithiodiglycolic acid bis (2-mercaptoethyl ester), dithiodipropionic acid bis (2-mercaptoethyl ester), 1,1,3,3-tetrakis (mercaptomethylthio) propane, 1,1,2,2-tetrakis (mercaptomethyl) ethane, 4,6-bis (mercaptomethyl thio) -1,3-dithiane, tris ( Mercaptoethyloleates methylthio) methane, tris (mercaptoethylthio) aliphatic polythiol compounds such as methane; Ropiruchiomechiru) methane, bis (2,3-mercaptopropyl) sulfide, 2,5-mercaptomethyl-1,4-dithiane, 2,5-dimercapto-1,4-dithiane, 2,5-mercaptomethyl - 2,5-dimethyl-1,4-dithiane, and esters of these thioglycolic acid and mercaptopropionic acid, hydroxymethyl sulfide bis (2-mercaptoacetate), hydroxymethyl sulfide bis (3-mercaptopropionate), hydroxy ethyl sulfide bis (2-mercaptoacetate), hydroxyethyl sulfide bis (3-mercaptopropionate), hydroxymethyl disulfide bis (2-mercaptoacetate), hydroxymethyl disulfide bis (3-mercaptopropionate) Hydroxyethyl disulfide bis (2-mercaptoacetate), hydroxyethyl disulfide bis (3-mercapto propionate), 2-mercaptoethyl ether bis (2-mercaptoacetate), 2-mercaptoethyl ether bis (3-mercaptopropionate) , thio diglycolic acid bis (2-mercaptoethyl ester), thiodipropionic acid bis (2-mercaptoethyl ester), dithiodiglycolic acid bis (2-mercaptoethyl ester), dithiodipropionic acid bis (2-mercaptoethyl ester), 1,1,3,3-tetrakis (mercaptomethylthio) propane, 1,1,2,2-tetrakis (mercaptomethyl) ethane, 4,6-bis (mercaptomethyl thio) -1,3-dithiane, tris ( Mercaptoethyloleates methylthio) methane, tris (mercaptoethylthio) aliphatic polythiol compounds such as methane; Hydroxymethyl sulfide bis (2-mercaptoacetate), hydroxymethyl sulfide bis (3-mercaptopropionate), hydroxyethyl sulfide bis (2-mercaptoacetate), hydroxyethyl sulfide bis (3-mercaptopropionate), hydroxymethyl disulfide bis (2-mercaptoacetate), hydroxymethyl disulfide bis (3-mercaptopropionate), hydroxyethyl disulfide bis (2-mercaptoacetate), hydroxyethyl disulfide bis (3-mercapto propionate), 2-mercaptoethyl ether bis (2-mercaptoacetate), 2-mercaptoethyl ether bis (3-mercaptopropionate), thiodiglycolic acid bis (2-mercapto Ethyl ester), thiodipropionic acid bis (2-mercaptoethyl ester), dithiodiglycolic acid bis (2-mercaptoethyl ester), dithiodipropionic acid bis (2-mercaptoethyl ester), 1,1,3,3 - tetrakis (mercaptomethylthio) propane, 1,1,2,2-tetrakis (mercaptomethyl) ethane, 4,6-bis (mercaptomethyl thio) -1,3-dithiane, tris (mercaptomethyl thio) methane, tris (mercaptoethyl thio) aliphatic such as methane polythiol compound; Hydroxymethyl sulfide bis (2-mercaptoacetate), hydroxymethyl sulfide bis (3-mercaptopropionate), hydroxyethyl sulfide bis (2-mercaptoacetate), hydroxyethyl sulfide bis (3-mercaptopropionate), hydroxymethyl disulfide bis (2-mercaptoacetate), hydroxymethyl disulfide bis (3-mercaptopropionate), hydroxyethyl disulfide bis (2-mercaptoacetate), hydroxyethyl disulfide bis (3-mercapto propionate), 2-mercaptoethyl ether bis (2-mercaptoacetate), 2-mercaptoethyl ether bis (3-mercaptopropionate), thiodiglycolic acid bis (2-mercapto Ethyl ester), thiodipropionic acid bis (2-mercaptoethyl ester), dithiodiglycolic acid bis (2-mercaptoethyl ester), dithiodipropionic acid bis (2-mercaptoethyl ester), 1,1,3,3 - tetrakis (mercaptomethylthio) propane, 1,1,2,2-tetrakis (mercaptomethyl) ethane, 4,6-bis (mercaptomethyl thio) -1,3-dithiane, tris (mercaptomethyl thio) methane, tris (mercaptoethyl thio) aliphatic such as methane polythiol compound;
1,2-dimercapto benzene, 1,3-dimercapto benzene, 1,4-dimercapto benzene, 1,2-bis (mercaptomethyl) benzene, 1,3-bis (mercaptomethyl) benzene, 1,4 bis (mercaptomethyl) benzene, 1,2-bis (mercaptoethyl) benzene, 1,3-bis (mercaptoethyl) benzene, 1,4-bis (mercaptoethyl) benzene, 1,3,5-mercapto benzene, 1,3,5-tris (mercaptomethyl) benzene, 1,3,5-tris (mercaptomethyl methyleneoxy) benzene, 1,3,5-tris (mercaptomethyl ethyleneoxy) benzene, 2,5-toluene dithiol, 3, 4-toluene dithiol, 1,5-naphthalene dithiol, aromatic such as 2,6-naphthalene dithiol poly All
compounds; 2-methylamino-4,6-dithiol -sym- triazine, 3,4-thiophene dithiol, Bismuthiol, 4,6-bis (mercaptomethyl thio) -1,3-dithiane, 2- (2,2 bis (mercaptomethyl thio) ethyl) -1,3-heterocyclic polythiol compounds such dithietane;
compound represented by the following general formula (2); it can be given, to be limited only to these exemplified compounds Absent. In the present embodiment, it can be used in combination of at least one selected from these.
[0058]
[Chem. 18]

[0059]
　Wherein (2), a, b are independently an integer of from 1 to 4, c is an integer of 1-3. Z is hydrogen or methyl, if Z there is a plurality, may each be the same or different.
[0060]
　The thiol compound having a hydroxy group, e.g., 2-mercaptoethanol, 3-mercapto-1,2-propanediol, Guruserinbisu (mercaptoacetate), 4-mercaptophenol, 2,3-dimercapto-1-propanol, pentaerythritol tris (3-mercaptopropionate), pentaerythritol tris (thioglycolate) and the like
can be cited, but is not limited only to these exemplified compounds.
[0061]
　Further oligomeric or chlorine-substituted products of these active hydrogen compounds, may be used halogen-substituted derivatives, such as bromine substituents. These active hydrogen compound alone, can also be used as a mixture of two or more.
[0062]
　In the present embodiment, from the viewpoint of physical properties such as mechanical strength of the molded article obtained, as the active hydrogen compound (C), it is preferable to use a trifunctional or more active hydrogen compounds.
　Specifically, glycerin, pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 5,7 dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercapto At least selected from-1,11-dimercapto-3,6,9-trithiaundecane, 1,1,3,3-tetrakis (mercaptomethylthio) propane, trimethylolpropane tris (3-mercaptopropionate) one is preferably used.
　Active hydrogen compound (C) is preferably at least SH group of the active hydrogen compound having two or more functional with one or more.
[0063]
　As the preferred combination of polyol compound (B) an active hydrogen compound (C),
and polyethylene glycol, glycerin, pentaerythritol tetrakis (2-mercaptoacetate), and 4-mercaptomethyl-1,8-dimercapto -3, combination of at least one selected from 6-dithiaoctane,
and polypropylene glycol, at least it is selected from pentaerythritol tetrakis (2-mercaptoacetate) and 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane 1 the combination of the seed,
the combination of a polypropylene glycol adduct of bisphenol a, and
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 3-methyl-1,5-pentanediol, a Adipic acid, and at least one selected from polyester compound comprising isophthalic acid, a combination of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, but and the like, a combination thereof the present invention is not limited.
[0064]
[(D) a photochromic compound]
　In the present embodiment, as the photochromic compound (D), 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.
[0065]
　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.
[0066]
　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.
[0067]
　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.
[0068]
　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).
[0069]
[Of 19]

[0070]
[Of 20]

[0071]
　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.
[0072]
　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, hydroxy group, a linear or branched alkyl group having 1 to 12 carbon atoms, linear 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, the number of carbon atoms which is substituted with at least one halogen atom linear or branched haloalkoxy group having 1 to 12, at least one of carbon atoms 1 to 12 linear or branched alkyl group or a phenoxy group or a naphthoxy group substituted by an alkoxy group, having 2 to 12 carbon atoms straight or branched alkenyl group, -NH 2 group, -NHR group, -N (R) 2 exists group (R one 2 .R is a linear or branched alkyl group having 1 to 6 carbon atoms to If it, the two R may be the same or different.), And is at least one selected from a methacryloyl group or an acryloyl group.
[0073]
　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 , halogen atom, hydroxy 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 1 One of the straight-chain or branched haloalkyl group having 1 to 12 carbon atoms which is substituted with a halogen atom, at least one straight-chain or branched haloalkoxy group having 1 to 12 carbon atoms which is substituted with a halogen atom, at least one of linear or branched alkyl group or a phenoxy group or a naphthoxy group substituted by an alkoxy group, a straight-chain or branched alkenyl group having 2 to 12 carbon atoms having 1 to 12 carbon atoms and an amino group, selected from having at least one substituent);.
aralkyl or a linear or branched alkyl group of heteroaralkyl groups (having 1 to 4 carbon atoms are substituted with the aryl group or heteroaryl group);.
a substituted or unsubstituted as phenoxy or naphthoxy group (substituent of selected from linear or branched alkyl or alkoxy group having 1 to 6 carbon atoms That has at least 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 carbon linear or branched alkyl group having 1 to 6 or a cycloalkyl group having 3 to 6 carbon atoms, or R,, 1 , R 2 in, it is substituted by at least one substituent of the substituted aryl or substituted heteroaryl group and is a phenyl group or an unsubstituted phenyl group);.
it represents a.
[0074]
　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.
[0075]
　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.
[0076]
　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.
[0077]
[Of 21]

[0078]
　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).
[0079]
[Formula 22]

[0080]
　These Asnelles of rings (A 1 from) (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.
[0081]
　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).
[0082]
　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 9Group (wherein, R 9 is as linear or branched alkyl group or a cycloalkyl group, or a substituted or unsubstituted phenyl or benzyl group (the substituent, having 3 to 6 carbon atoms, 1 to 6 carbon atoms, formula (5) R of 1 , R 2 if groups independently correspond to an aryl or heteroaryl group, R 1 , R 2 represents a having) at least one of the substituents mentioned above in the definition of groups.) a representative.
[0083]
　n is an integer from 0 to 6, o is an integer from 0 to 2, p is an integer from 0 to 4, an integer from q is 0 to 3.
　Incidentally, A is (A 4 may exhibit), n is an integer from 0 to 2, p is an integer from 0 to 4, A is (A 2 may exhibit), from n is 0 to 2 of an integer.
[0084]
　The photochromic compounds of the general formula (5) (D) are combined with color change reaction rate to be applied to applications sought, high color suitability even at 40 ° C.. Colors that can be easily achieved, ranging from orange to blue.
[0085]
　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).
[0086]
　In the present embodiment, as the compound (5) can be preferably used a compound represented by the following general formula (6).
[0087]
[Of 23]

[0088]
　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.
[0089]
　As the compound (5), can be used more preferably a compound represented by the following general formula (7).
[0090]
[Of 24]

[0091]
　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.
[0092]
　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.
[0093]
[Of 25]

[0094]
[Of 26]

[0095]
　Compounds represented by the photochromic compound (D) 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.
[0096]
　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).
[0097]
[Of 27]

[0098]
　The naphthopyran compounds, may be used one or more compounds selected from the compounds described above.
[0099]
　It is also possible to use at least one as a photochromic compound (D) in this embodiment is selected from formula (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.
[0100]
[Formula 28]

[0101]
　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.
[0102]
　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.
[0103]
　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.
[0104]
　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.
[0105]
　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.
[0106]
　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.
[0107]
　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. Dotted line is R 3 carbon atoms and R which are bonded 4 represents a bond between the carbon atom to which they are attached.
[0108]
[Of 29]

[0109]
　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. The plurality of to R5 ~ R7 may be the same or different.
[0110]
　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.
[0111]
　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.
[0112]
　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.
[0113]
　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.
[0114]
[Formula 30]

[0115]
　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.
[0116]
　"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.
[0117]
　Specifically,
　"Chain", if the photochromic compound of general formula (a), a monovalent organic group of the general formula (p) or (q).
[0118]
[Of 31]

[0119]
　"Chain" when the photochromic compound is formula (b), represents a divalent organic group of the general formula (r) or (s).
[0120]
[Formula 32]

[0121]
　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 '.
[0122]
　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.
[0123]
　The photochromic compound (D) 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))) and the like.
[0124]
[Other Components]
　In the present embodiment, in addition to the (A) ~ (D) component, a polymerization catalyst, an internal mold release agent may further contain a resin modifier, and the like.
　As the polymerization catalyst, tertiary amine compounds and their inorganic or organic acid salts, metal compounds, it may be mentioned quaternary ammonium salt or an organic acid.
[0125]
　As the internal mold release agent, it is possible to use an acidic phosphoric acid ester. The acidic phosphoric acid esters, phosphoric acid monoesters, there may be mentioned phosphoric acid diester, can be used as a mixture either alone or two or more kinds.
[0126]
　The resin modifier, for example, an episulfide compound, an alcohol compound, amine compound, epoxy compound, organic acid and its anhydride include olefin compounds containing (meth) acrylate compounds.
[0127]

　for an optical material polymerizable composition of the present embodiment, the isocyanate compound (A), polyol compound (B), the active hydrogen compound (C), and photochromic compound (D) it can be mixed and prepared.
[0128]
　In this embodiment, the polyisocyanate compound a polyol compound to the (A) (B) the functional group equivalent ratio of (B / A) is the lower limit 0.02 or more, preferably 0.10 or more, more preferably 0.15 or more , more preferably 0.20 or more, particularly preferably 0.25 or more, and the upper limit is 0.60 or less, preferably 0.50 or less, more preferably 0.40 or less, more preferably 0.30 or less. Upper and lower limits can be combined as appropriate.
　Polyisocyanate compounds active hydrogen compound for (A) (C) the functional group equivalent ratio (C / A), the lower limit is 0.30 or more, preferably 0.40 or more, more preferably 0.50 or more, more preferably 0.60 or more, and the upper limit is 0.99 or less, preferably 0.98 or less, more preferably 0.90 or less, more preferably 0.80 or less. Upper and lower limits can be combined as appropriate.
　By the range of those corresponding amount ratio, with exhibits high photochromic performance, that have excellent mechanical properties which are characteristic of the poly (thio) urethane resin, it is possible to provide an excellent optical material balance .
[0129]
　For example, when the compound represented by the general formula (I) is polyethylene glycol, the functional group equivalent ratio (B / A) is improved more coloring performance and is 0.1-0.6, clouding of the polymer more is suppressed.
　Further, when the compound represented by the general formula (I) is polypropylene glycol, the functional group equivalent ratio (B / A) is improved more coloring performance and 0.06 to 0.6 clouding of the polymer more is suppressed.
[0130]
　As for the compound represented by formula (II), the functional group equivalent ratio (B / A) is improved and more is the coloring performance is 0.06 to 0.6 clouding of the polymer are further suppressed that.
[0131]
　The compound represented by formula (III), in the case of polypropylene glycol adduct of polyethylene glycol adduct and bisphenol A bisphenol A, the functional group equivalent ratio (B / A) in the 0.06 to 0.6 there the color performance is further improved, cloudiness of the polymer is further suppressed.
[0132]
　Further, the compound represented by the general formula (IV) is 3-methyl-1,5-case of a polyester compound obtained by reacting an equimolar mixture equimolar pentanediol adipic acid and isophthalic acid, the functional group equivalent ratio (B / a) is improved more coloring performance and from 0.02 to 0.2 clouding of the polymer is further suppressed.
[0133]
　In the composition, to the sum of the OH and SH groups contained in the active hydrogen compound (C) and the polyol compound (B), the molar ratio of NCO groups contained in the polyisocyanate compound (A) (NCO group / (OH group SH group)) + is in the range of 1.1-1.6, preferably in the range from 1.25 to 1.6, and more preferably in the range 1.25 to 1.5, particularly preferably in the range from 1.25 to 1.4.
　If the molar ratio of NCO groups / (OH group + SH group) is in the above range, molded articles obtained from the polymerizable composition of the present invention, can be suppressed from decreasing over time of the photochromic performance, thus the photochromic performance it is possible to stably exhibit a.
[0134]
　Photochromic compound (D), the total amount of the isocyanate compound (A), polyol compound (B) and the active hydrogen compound (C), it is possible to use at 10 ppm ~ 5000 ppm.
[0135]
　Polyisocyanate compound (A), polyol compound (B), the active hydrogen compound (C), and a photochromic compound and (D), the temperature in the case of preparing a polymerizable composition by mixing the other additive usually 25 ℃ 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, catalysts, internal release agents, if solubility in monomer additive is not satisfactory, it is also possible to dissolve beforehand warmed, monomers, a resin modifier.
　Mixing order and mixing method of the respective components in the composition is not particularly limited as long as mixing the components uniformly, can be carried out by known methods. Known methods, for example, to prepare a master batch containing an additive predetermined amount, the master batch and a method of dispersing and dissolving in a solvent.
[0136]
　In the present embodiment, it is possible to obtain a molded product by polymerizing and curing a polymerizable composition. SH group concentration of the formed body can be determined by IR spectrometry. For example, cutting the thickness of 0.35mm using a PERKIN-ELMER Inc. IR spectrometer Spectrum One, and IR spectrum of the polished resin samples, NCO is 2257Cm -1 , SH is 2550 cm -1 using the absorption of Te calculated absorbance at baseline method, can be determined by the following equation calculation from the calibration curve prepared in advance.
[0137]

[0138]
　SH group concentration of a molded article was measured by this is less than 1.0 wt%, preferably 0.5 wt% or less, more preferably less 0.3 wt%, particularly preferably not more than 0.1 wt%. Incidentally, it is most preferred that SH group of the shaped body is not substantially detected. Molded body in the range, can be suppressed from decreasing over time of the photochromic performance can be stably exhibited and thus the photochromic performance. Molded article of the present embodiment can be used as an optical material.
[0139]
　In the present embodiment, a manufacturing method of the optical material 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.
[0140]
　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 25 hours.
[0141]
　Optical material, 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..
[0142]
　In the present embodiment, in molding the resin, in addition to the above "other components" in the same manner as in a known molding method depending on the purpose, chain extenders, crosslinking agents, light stabilizers, UV absorbers, antioxidants, bluing agent, solvent dye, filler, various additives may be added, such as an adhesion improver.
[0143]

　The polymerizable composition of the present embodiment can be obtained as a molded article having various shapes by changing the type of mold during casting polymerization. Compacts are both provided with a photochromic performance, with high refractive index and high transparency, it can be used for various optical materials such as plastic lenses. In particular, it can be suitably used as a plastic spectacle lens or a plastic polarized lens.
[0144]
[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.
[0145]
　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.
[0146]
　Each of these coating layers, a UV absorber for the purpose of protecting the lens or the eyes from ultraviolet, infrared absorber 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 lens dyes and pigments for the purpose of enhancing fashion, 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.
[0147]
　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.
[0148]
　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.
[0149]
　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.
[0150]
　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.
[0151]
　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.
[0152]
　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.
[0153]
　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 .
[0154]
　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.
[0155]
[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.
[0156]
　Polarizing film in the present embodiment can be composed of a thermoplastic resin. As the thermoplastic resin include thermoplastic polyester, thermoplastic polycarbonate, thermoplastic polyolefin, thermoplastic polyimide. Water resistance, from the viewpoint of heat resistance and moldability, a thermoplastic polyester, thermoplastic polycarbonates are preferred, the thermoplastic polyester is more preferable.
[0157]
　As the thermoplastic polyester, polyethylene terephthalate, polyethylene naphthalate, and can be exemplified polybutylene terephthalate, water resistance, polyethylene terephthalate from the viewpoint of heat resistance and moldability preferred.
[0158]
　As the polarizing film, particularly, a dichroic dye-containing thermoplastic polyester polarizing film, iodine-containing polyvinyl alcohol polarizing film, dichroic dye-containing polyvinyl alcohol polarizing film and the like.
　Polarizing film drying, it may be used after having undergone a heat treatment for stabilization.
　Further, polarizing film, in order to improve the adhesion between the acrylic resin, a primer coating treatment, chemical treatment (gas or chemical solution treatment in an alkali and the like), a corona discharge treatment, plasma treatment, ultraviolet irradiation treatment, electron beam irradiation treatment roughening treatment, one or more preprocessing selected from such flame treatment may be used after conducting. Among such pretreatment, a primer coating treatment, chemical treatment, corona discharge treatment, one or two or more selected from plasma treatment is particularly preferred.
[0159]
　Plastic polarized lens of the present embodiment can be obtained by such on at least one surface of the polarizing film, the optical material for the polymerizable composition of the present embodiment is cured provided a substrate layer obtained by .
　Method for producing a plastic polarized lens is not particularly limited, preferably be mentioned casting polymerization method.
[0160]
　Method for producing a plastic polarized lens of the present embodiment, for example,
　a polarizing film, a step of fixing the lens casting in a mold in a state of being separated from the mold,
　is formed with the polarizing film, between the mold a step of injecting the optical material for the polymerizable composition to at least one of the air gap,
　the polymerized curing the optical material for the polymerizable composition, laminating a base layer on at least one surface of the polarizing film , it can contain.
[0161]
　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.
[0162]
　The polymerization conditions of the optical material for the polymerizable composition, the composition of the polymerizable composition, type and amount of catalyst used, although conditions vary depending on the shape or the like of the mold, over a period of 1-50 hours at a temperature of 5 ~ 140 ° C. row divide. Optionally, held or gradually heated in a temperature range of 5 ~ 130 ° C., is thereby is preferably cured for 1 to 25 hours.
　The laminate was cured by polymerization by releasing from the mold, it is possible to obtain a plastic polarized lens of the present embodiment.
[0163]
　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
[0164]
　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.
[0165]
(Stability Evaluation of the photochromic performance (acceleration
　test)) irradiation using a Q-Lab Corporation QUV accelerated weathering tester QUV / SE equipped with UVA-340 type lamp intensity 0.50 W / m 2 , the irradiation time of 150 hours, perform accelerated test at a temperature of 50 ° C., evaluation dimming performance before and after the accelerated (the color when light transmittance) was measured by the following method. Scarcely deteriorated as the photochromic performance is small difference in transmittance before and after the acceleration test, it can be determined to be stable.
[0166]
(Dimming performance evaluation)
　using a metal halide lamp (180 W) light source, a temperature 19 ° C., UV intensity 1.2 mW / cm was measured by integrating actinometer 2 under the condition of the molded article sample processed into 2.0mm thick spectroscopic when allowed to develop for 5 minutes to measure a transmission measurement system.
· Color when light transmittance: light transmittance at 550nm when developed with the conditions
　shielding property during color development and this value is smaller is high, so that the photochromic performance is high.
Light source: Hayashi Watch Industry Co., Ltd. metal halide light source apparatus "LA-180ME"
- integrating actinometer: Ushio Co. integrating actinometer "UIT-102 (photodetector UVD365PD)"
and transmission measurement system: JASCO ( Co., Ltd.) "MV-3150"
[0167]
(Residual by IR measurement functional group
　analysis) cutting the thickness of 0.35mm using a PERKIN-ELMER Inc. IR spectrometer Spectrum One, and IR spectra of polished resin samples. The NCO 2257Cm -1 , SH is 2550 cm -1 determined absorbance at baseline method using absorption was determined by the following equation calculation from the calibration curve prepared in advance.
[0168]

[0169]
[Comparative Example
　1] 2,5 (2,6) - bis (isocyanatomethyl) bicyclo [2.2.1] Formula as photochromic compound in heptane 41.0 parts by mass (9) Compound 0.05 part by weight , dimethyl rarity chloride 0.10 parts by weight was added and dissolved stirred together. Polypropylene glycol 22.5 parts by weight of the number average molecular weight of 700 to this mixture, and mixed by adding pentaerythritol tetrakis (2-mercaptoacetate) 36.5 parts by weight, and stirred. Degassed under 20 minutes 5mmHg where each solution became homogeneous, it was injected these solutions to each sheet type made of polyethylene. These were kept for 8 hours was put into a furnace of 20 ° C., the temperature was raised over a period of further 12 hours 120 ° C.. After heating as 120 ° C. for 3 hours, taken out the mold from the furnace, remove the mold, polymerization-obtained molded body was taken out (diameter 45 mm, disc-shaped thick 2.0 mm).
　Molded body was colorless and transparent, as soon as placed under sunlight colored purple, had a good light modulating performance that decolored when shielding light. Next, we residual -NCO groups of the molded article, the quantification of -SH groups by IR analysis. Further, to evaluate the light modulating performance before and after the accelerated testing of these shaped bodies. The results are shown in Table 1.
[0170]
[Comparative Example 2, Examples
　1-3] 2,5 (2,6) - bis (isocyanatomethyl) bicyclo [2.2.1] heptane, polypropylene glycol having a number average molecular weight of 700, pentaerythritol tetrakis (2- except that the amount of mercaptoacetate) was varied as shown in Table 1 was prepared in the same manner as the molded body of Comparative example 1.
　Each molded body was colorless and transparent, as soon as placed under sunlight colored purple, had a good light modulating performance that decolored when shielding light. Then it went residual -NCO groups of these shaped bodies, the quantification of -SH groups by IR analysis. Further, to evaluate the light modulating performance before and after the accelerated testing of these shaped bodies. The results are shown in Table 1.
[0171]
[Table 1]

[0172]
　Table The results of Comparative Examples 1 and 2 according to 1, transmittance after accelerated test and the residual amount of SH groups in the compact is increased to more than 1.0 wt% is lost most elevated dimming function significantly cage, the deterioration of the photochromic performance was observed. In contrast, as in Examples 1-3, the residual amount of SH groups in the compact is less than 1.0 wt%, the amount of change in transmittance is small, confirmed that the photochromic performance is stable It has been.
　Also in the plastic polarized lens it was estimated that similar results are obtained.
[0173]
　This application, the basic priority based on Japanese Patent Application No. 2015-183494, filed on September 16, 2015, and the Japanese Patent Application No. 2015-240357, filed on December 9, 2015 claims priority, the entire contents of which are incorporated herein.

claims

[Claim 1](A) a polyisocyanatecompound, (B) the following general formula (1)
[Chemical formula 1]

(In the formula (1), m represents a number from 1 to 20, k represents the 0 ~ 2m, n is 1 to shows the numerical value of 20, l represents 0 ~ 2n, a is 0 or more numeric, b is 0 or more numeric, d represents 0 or more numeric, e is shown one or more values. Q 1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, Q is plurality of 1 good .Q be the same or different 2 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, plurality of Q is 2 good .Z be the same or different represents a divalent organic group contain an ~ carbon atoms 1 be 30 aromatic group, Z that existing in plural numbers may be the same or different .)
is represented by, a polyol compound a number average molecular weight of 100 or more and,
(C) difunctional or more active hydrogenation Things (provided that the compound (B) except for) and,
(D) and a photochromic compound,
a polymerizable composition polymerized hardened molded body comprising,
　SH group concentration by IR spectrometry is less than 1.0 wt% the molded body is.
[Claim 2]
　Polyisocyanate compound (A), hexamethylene diisocyanate, pentamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane diisocyanate, 2,5-bis (isocyanatomethyl) bicyclo - [2. 2.1] - heptane, 2,6-bis (isocyanatomethyl) bicyclo - [2.2.1] - heptane, tolylene diisocyanate, with phenylene diisocyanate, and one or more selected from the group consisting of diphenylmethane diisocyanate there, the molded body according to claim 1.
[Claim 3]
　Polyol compound (B) is a compound of one or more selected from compounds represented by the following general formula (I) ~ the following general formula (IV), the molded body according to claim 1 or 2,
[Formula 2]

(in the formula (I), p represents a number between 4 ~ 100, X represents a hydrogen atom or a methyl group, the X presence of a plurality may be the same or different.)
[formula 3]

(formula ( during II), q, r may be the same or different, each represent one or more numerical and .R sum of q and r is a number from 2 to 100 1 and R 2 are different and the same even well, a hydrogen atom or a methyl radical, R presence of a plurality of 1 or R 2 is optionally be the same or different each .Z is a substituted or unsubstituted divalent aromatic group, a substituted or unsubstituted include an aromatic group having 1 to 20 carbon atoms substituted showing a good divalent aliphatic group.
[Formula 4]

(In the formula (III), q, r may be the same or different, each represent one or more numbers, and the total of q and r .R numerical 2-100 1 and R 2 may be the same or different, represent a hydrogen atom or a methyl radical, R presence of a plurality of 1 or R 2 may each be the same or different.)
[Formula 5]

(In the formula (IV), m represents a number of 1 ~ 20, k represents the 0 ~ 2m, n represents a number of 1 ~ 20, l represents an 0 ~ 2n, f is 0 or more numeric shows, g represents 1 or more numeric, h represents 1 or more numeric, j is .Q exhibit one or more of the numerical value 1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, there exist a plurality of Q 1 the same may .Q be different or 2 represents a hydrogen atom or an alkyl group having a carbon number of 1 ~ 6, Q there exist a plurality 2 good .R be the same or different 3 of 1 to 20 carbon atoms linear or branched alkylene group or a linear or branched alkyl group which may have as a substituent a phenylene group having 1 to 10 carbon atoms, R presence of a plurality of 3 may be the same or different. )
[Claim 4]
　Polyol compound (B) is the formula (I), a compound represented by the general formula (III) or the general formula (IV), the molded body according to claim 3.
[Claim 5]
　The compound represented by the general formula (I) is a polyethylene glycol or polypropylene glycol, molded product according to claim 3 or 4.
[Claim 6]
　The number average molecular weight of the compound represented by the general formula (I) is 200 to 4000, and the molded body according to any one of claims 3-5.
[Claim 7]
　The number average molecular weight of the compound represented by the general formula (I) is from 300 to 3,000, the molded body according to any one of claims 3-5.
[8.]
　The number average molecular weight of the compound represented by the general formula (II) is 400-2000, molded product according to claim 3.
[Claim 9]
　The number average molecular weight of the compound represented by the general formula (III) is 400-2000, molded product according to claim 3 or 4.
[Claim 10]
　The number average molecular weight of the compound represented by the general formula (IV) is 600 to 3000, molded product according to claim 3 or 4.
[Claim 11]
　Active hydrogen compound (C) is a polyol compound, one or more selected from the group consisting of thiol compounds having a polythiol compound and a hydroxy group, the molded body according to any one of claims 1 to 10.
[Claim 12]
　Active hydrogen compound (C) is an active hydrogen compound having three or more functional, compact according to any one of claims 1 to 11.
[Claim 13]
　Active hydrogen compound (C) is glycerol, pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 5 , 7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8 - dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, from 1,1,3,3-tetrakis (mercaptomethylthio) propane and trimethylolpropane tris (3-mercaptopropionate), is at least one selected from the group consisting of, claims 1 to 12 noise Molded body of the crab described.
[Claim 14]
　Photochromic compound (D) is represented by the following general formula (5), molded article according to any one of claims 1 to 13;
[Chemical Formula 6]

(wherein, R 1 and R 2 are either the same or different and may be, independently, hydrogen;
linear or branched alkyl group of 1 to 12 carbon atoms;
a cycloalkyl group having 3 to 12 carbon atoms;
a substituted or unsubstituted, having 6 to 24 carbon atoms an aryl group or a carbon as heteroaryl group (substituent having 4 to 24, a halogen atom, hydroxy 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 1 to 12 carbon atoms which is substituted with a halogen atom, at least one straight-chain or branched haloalkoxy group having 1 to 12 carbon atoms which is substituted with a halogen atom, at least one Horn Linear or branched alkyl or alkoxy group a phenoxy group or a naphthoxy group substituted by a straight-chain or branched alkenyl group having 2 to 12 carbon atoms having a carbon number of 1 ~ 12, -NH 2 group, -NHR group , -N (R) 2 group (when R is present .R two is a linear or branched alkyl group having 1 to 6 carbon atoms, two of R may be the same or different.), and having at least one substituent selected from a methacryloyl group or an acryloyl group);.
a linear or branched alkyl group aralkyl or heteroaralkyl group (having 1 to 4 carbon atoms is substituted with an aryl or heteroaryl group and are.)
represents,
　R 3It may be the same or different are independently a halogen atom;
a C 1-12 linear or branched alkyl group;
a cycloalkyl group having 3 to 12 carbon atoms;
a C 1-12 straight-chain 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 halogen linear or branched haloalkoxy group having carbon number of 1 to 12 substituted by atom;
a substituted or unsubstituted, aryl group or heteroaryl group (substituent group having a carbon number of 4 to 24 6 to 24 carbon atoms, halogen atom, hydroxy 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 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 (substituents are selected from linear or branched alkyl or alkoxy group having 1 to 6 carbon atoms Even without having one
substituent);. -NH 2 , -NHR, -CONH 2Or -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 straight-chain having 1 to 6 carbon atoms or branched alkyl group or a cycloalkyl group having 3 to 6 carbon atoms, or R, 1 , R 2 in at least one by a phenyl group or an unsubstituted substituted substituents of the substituted aryl or substituted heteroaryl group of a phenyl group);.
represents,
m is an integer from 0 to 4;
a is a compound represented by the following formula (a 2 ) or formula (a 4 )
[Chemical formula 7]

represents Asnelles of rings, these in 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 bond α) of the carbon C naphthopyran ring in the general formula (5) 5 or carbon C 6 can be coupled to;
R 4But 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);
R 5 is halogen;
linear or branched alkyl group having 1 to 12 carbon atoms;
substituted by at least one halogen atom, a haloalkyl group linear or branched having 1 to 6 carbon atoms;
cycloalkyl of 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 Al . A Le 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, R9 is a linear or branched alkyl group or a cycloalkyl group having 3 to 6 carbon atoms or a substituted or unsubstituted phenyl or benzyl group (the substituent, 1 to 6 carbon atoms, the general formula (5) R 1 , R 2 if groups independently correspond to an aryl or heteroaryl group, R 1 , R 2 has at least one of the substituents mentioned above in the definition of group));. a
is (a 4 a) If indicated, n is an integer from 0 to 2, p is an integer from 0 to 4, a is (a 2 may exhibit), ).
[Claim 15]
　Polyisocyanate compounds polyol compounds for (A) the functional group equivalent ratio of (B) (B / A) of 0.02 to 0.6, and the polyisocyanate compound active hydrogen compound for (A) (C) the functional group equivalent ratio of ( C / a) is 0.4 to 0.98 molded body according to any one of claims 1 to 14.
[Claim 16]
　Optical material comprising a molded body according to any one of claims 1 to 15.
[Claim 17]
　Plastic lenses made of molded product according to any one of claims 1 to 15.
[Claim 18]
　A polarizing film,
　at least one of which is formed on the surface, the plastic polarized lens comprising: a base material layer made of a molded product according to any one of claims 1 to 15 of the polarizing film.
[Claim 19]
　(A) a polyisocyanate
　compound, (B) the following general formula (1)
[formula 8]

(In the formula (1), m represents a number from 1 to 20, k represents the 0 ~ 2m, n is 1 to shows the numerical value of 20, l represents 0 ~ 2n, a is 0 or more numeric, b is 0 or more numeric, d represents 0 or more numeric, e is shown one or more values. Q 1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, Q is plurality of 1 good .Q be the same or different 2 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, plurality of Q is 2 good .Z be the same or different represents a divalent organic group contain an ~ carbon atoms 1 be 30 aromatic group, Z that existing in plural numbers may be the same or different .)
is represented by, a polyol compound a number average molecular weight of 100 or more and,
(C) difunctional or more active hydrogenation Things (provided that the compound (B) except for) and,
(D) and a photochromic compound,
containing a polymerizable composition,
　OH groups contained in the active hydrogen compound (C) and the polyol compound (B) and SH to the sum of the groups, the molar ratio of NCO groups contained in the polyisocyanate compound (a) (NCO group / (OH group + SH group)), is in the range of 1.1-1.6, the polymerizable optical material Composition.
[Claim 20]
　(A) a polyisocyanate
　compound, (B) the following general formula (1)
[Formula 9]

(In the formula (1), m represents a number from 1 to 20, k represents the 0 ~ 2m, n is 1 to shows the numerical value of 20, l represents 0 ~ 2n, a is 0 or more numeric, b is 0 or more numeric, d represents 0 or more numeric, e is shown one or more values. Q 1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, Q is plurality of 1 good .Q be the same or different 2 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, plurality of Q is 2 good .Z be the same or different represents a divalent organic group contain an ~ carbon atoms 1 be 30 aromatic group, Z that existing in plural numbers may be the same or different .)
is represented by, a polyol compound a number average molecular weight of 100 or more and,
(C) difunctional or more active hydrogenation Things (provided that the compound (B) except for) and,
and (D) a photochromic compound, a, to the sum of the OH and SH groups contained in the active hydrogen compound (C) and the polyol compound (B), the polyisocyanate compound the molar ratio of NCO groups contained in (a) (NCO group / (OH group + SH group)) is mixed to be within a range of 1.1-1.6, the optical material for the polymerizable composition a step of preparing,
　and forming a lens substrate by cast polymerization of the optical material for the polymerizable composition into a mold
comprising a method of manufacturing a plastic lens.
[Claim 21]
　(A) a polyisocyanate
　compound, (B) the following general formula (1)
[Formula 10]

(In the formula (1), m represents a number from 1 to 20, k represents the 0 ~ 2m, n is 1 to shows the numerical value of 20, l represents 0 ~ 2n, a is 0 or more numeric, b is 0 or more numeric, d represents 0 or more numeric, e is shown one or more values. Q 1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, Q is plurality of 1 good .Q be the same or different 2 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, plurality of Q is 2 good .Z be the same or different represents a divalent organic group contain an ~ carbon atoms 1 be 30 aromatic group, Z that existing in plural numbers may be the same or different .)
is represented by, a polyol compound a number average molecular weight of 100 or more and,
(C) difunctional or more active hydrogenation Things (provided that the compound (B) except for) and,
and (D) a photochromic compound, a, to the sum of the OH and SH groups contained in the active hydrogen compound (C) and the polyol compound (B), the polyisocyanate compound the molar ratio of NCO groups contained in (a) (NCO group / (OH group + SH group)) is mixed to be within a range of 1.1-1.6, the optical material for the polymerizable composition a step of preparing,
　the polarizing film, and a step of fixing in the lens casting mold in a state of being separated from the mold,
　the polarizing film, for the optical material at least one of the gap formed between the mold implanting a polymerizable composition,
　Said polymerizing and curing the optical material for the polymerizable composition, a step of laminating the base material layer on at least one surface of the polarizing film
including the method for producing a plastic polarized lens.