[0001]The present invention relates to a polymerizable composition can be suitably used for the production of excellent photochromic cured product of the photochromic action.
Background technique
[0002]
　The photochromism, there rapidly changes color when irradiated with light containing ultraviolet light such as light of sun or mercury lamp compounds is that reversible effects when placed in a dark place to stop irradiation of light returns to the original color It has been applied to various uses.
[0003]
　For example, are photochromism applications in the field of spectacle lenses, plastic lenses having photochromic properties are obtained by curing a polymerizable monomer obtained by adding various photochromic compounds having such properties as described above. The photochromic compound, fulgimide compound that can be suitably used in such applications, spirooxazine compounds, have been found chromene compounds.
[0004]
　Also a photochromic eyeglass lens in the outdoor light containing the ultraviolet, such as sunlight is irradiated colored rapidly function as sunglasses, transparent usually fade in indoor no irradiation of such light a spectacle that functions as a spectacle, and the demand is increasing in recent years.
[0005]
　For the photochromic eyeglass lenses, particularly plastic from the standpoint of light weight and safety have been favored, made by compounding the photochromic compound in organic such photochromic imparting to the plastic lens is generally It has been. The method as composite method, the method of impregnating the photochromic compound on the surface of the lens having no photochromic properties (hereinafter, referred to as impregnation), or monomer dissolving a photochromic compound, to obtain a directly photochromic lens by polymerizing it (hereinafter, referred to as kneading method) is known. These impregnation techniques (Patent Documents 1 to 3 refer) and kneading method techniques (see Patent Documents 4-5), the various techniques have been proposed.
[0006]
Patent Document 1: U.S. Pat. No. 5,739,243
Patent Document 2: U.S. Patent No. 5,973,093 Pat
Patent Document 3: WO 95/10790 pamphlet
Patent Document 4: JP-A 5-306392 Patent Publication
Patent Document 5: JP No. 8-320534 JP
Patent Document 6: JP-a 7-2938 discloses
Patent Document 7: JP 2009-19157 JP
Patent Document 8: JP 2004-78052 JP
Patent Document 9: WO 2009/146509 pamphlet
Patent Document 10: International Publication No. 2010/20770 pamphlet
Patent Document 11: WO 2012/149599 pamphlet
Patent Document 12: WO 2012/162725 pamphlet
Summary of the Invention
Problems that the Invention is to Solve
[0007]
　Plastics having photochromic properties comprising these photochromic compounds and they generally exhibit excellent photochromic properties. However, these photochromic complex variety of applications, particularly for use in photochromic spectacle lenses, not only exhibit good photochromic action, as a convenient, inexpensive to manufacture, and a photochromic spectacle lens, mechanical or optical it is required to have excellent physical properties.
[0008]
　Exemplified above impregnation method, the case of using a photochromic plastic spectacles applications, creates a substrate separately, to impregnate the photochromic compound to the resulting substrate, not only manufacturing process is complicated, improved impregnation properties to, it is necessary to lower the glass transition temperature of the substrate (Tg), the flexibility of the base material becomes too high, resulting occur reduction in the hardness of the base material, lowering of heat resistance, optical strain It has arisen a new problem such as there are many.
[0009]
　In Patent Documents 4 and 5 illustrated above kneading inclusive method, because it uses a radical polymerizable monomer of the high reactivity of the di (meth) acrylate, control is difficult in the polymerization, the following 35 ° C. It can not be created photochromic spectacle lenses without distortion only by using a polymerization oven can strict temperature control in temperature, and that it requires special equipment for molding property, using a special acrylate-based material , there is room for improvement in such can not be manufactured at a low cost.
[0010]
　Moreover, diethylene glycol bis allyl carbonate cured product having a refractive index of 1.50 which is used as a general-purpose material for eyeglass lenses is obtained (hereinafter, it is called 'CR-39' may be abbreviated as also.) A radically polymerizable monomer used as dimer, a method for producing a photochromic eyeglass lenses are various attempts at kneading method. However, if the monomer is, because of the low reactivity, high oxidation activity, diisopropyl peroxydicarbonate was (hereinafter, also. Be abbreviated as known as 'IPP') was polymerized coexist photochromic compound , IPP is to oxidize the photochromic compound has a problem that the photochromic spectacle lenses exhibit sufficient photochromic properties are not obtained.
Means for Solving the Problems
[0011]
　The present inventors have conducted the polymerization by mixing a specific photochromic compound and a polymerizable monomer, a photochromic cured product which is represented by a photochromic spectacle lens, the polymerizable composition can be inexpensively and simply produced by kneading method things carried out an extensive research on. As a result, in the spectacle lens applications, diallyl phthalate, which is used as an inexpensive material diethylene glycol bis allyl carbonate and / or its oligomers and the medium refractive index market generic used as an inexpensive material of lower refractive index market generic and / or photochromic photochromic polymerizable composition comprising an oligomer thereof specific photochromic dye further radical polymerization initiator, does not require strict temperature control can produce a good yield photochromic cured product in equipment, obtained and It found that photochromic properties of the cured product are superior to those of conventional, and completed the present invention.
[0012]
　The present invention can be shown below.
[1] (A) represented by the following general formula (1) is represented by a compound containing two or more allyloxycarbonyl group,
　(B) peroxy ketal radical polymerization initiator, peroxy monocarbonate based radical polymerization initiator and at least one polymerization initiator selected from the group consisting of peroxyester polymerization initiator,
　and at least one photochromic compound selected from (C) naphthopyran compounds
containing polymerizable composition ;
formula 1]

(wherein, n is an integer of 2 ~ 6 .R 1 represents a hydrogen atom or a methyl radical, R presence of a plurality of 1 . may be the same or different
　X is an oxygen atom It has carbon atoms which may have 3 to 12 linear or branched divalent to hexavalent derived from aliphatic polyols organic group a of carbon atoms which may contain an oxygen atom 5 16 divalent to hexavalent organic group b derived from a cyclic aliphatic polyol or a divalent to hexavalent organic group c derived from an aromatic compound having 6 to 12 carbon atoms, an organic group a or organic, group b are joined to the allyloxycarbonyl group via an ether group derived from the hydroxyl group to which they are provided to form the allyl carbonate groups.).
[2] a compound containing two or more allyloxycarbonyl group (A) is represented by allyl carbonate polymerizable compound represented by the following general formula (2) and oligomers thereof or the following general formula (3) or (4) that allyl ester polymerizable compound and its oligomer or polymer compound containing at least one of the allyl ester group and an allyl carbonate group represented by the following general formula (5), and including their oligomers, polymerization according to [1] sex composition;
[formula 2]

in (formula (2), X derived from a linear or branched C3 ~ 2 ~ 6-valent group or C5 of ~ C16 cycloaliphatic polyols derived from aliphatic polyols C12 represents a divalent to hexavalent groups, n represents an integer of 2-6.)
[Chemical formula 3]

[formula 4]

in (equation (4), X is linear or branched C2 ~ C8 fat It represents a divalent group or 3-6-valent group derived from an aliphatic polyol linear or branched C3 ~ C10 having 3-6 hydroxyl groups, which are derived from the group diol, n represents 2-6 It represents an integer.).
[Chemical Formula 5]

In (Equation (5), X is linear or branched C2 2 divalent group derived from an aliphatic diol ~ C8 or linear or branched C3 ~ C10 having 3-6 hydroxyl groups, represents a 3-6 valent group derived from an aliphatic polyol, m and n are summation of and m and n represent an integer of 0 to 6 represents an integer of 2-6.).
10 [3] polymerization initiator (B) is 10-hour half-life temperature of 80 ° C. or more peroxy ketal polymerization initiator represented by the following general formula (6), represented by the following general formula (7) time half-life temperature of 80 ° C. or more peroxy monocarbonate based polymerization initiator, and the group 10-hour half-life temperature represented by the following general formula (8) is made of 65 ° C. or more peroxyester polymerization initiator is at least one selected, [1] or polymerizable composition according to [2];
[formula 6]

in (equation (6), R 3 is a tertiary alkyl group, R 1 and R 2 -methyl each independently ethyl, propyl and alkyl group selected from butyl, alkyl groups of said can having an alkyl ester group at the terminal, or R 1 and R 2 are bonded they together with the carbon atom Is able to form a cycloalkylene group, the cycloalkylene group may have 1 to 3 alkyl substituents.)
[Formula 7]

In (Equation (7), R 1 is C3 ~ C6 is a tertiary alkyl group, R 2 is a linear or branched of C3 ~ C8 alkyl group)
formula 8]

in (equation (8), R 1 tertiary alkyl groups of C3 ~ C6 at is, R 2Is an alkyl group or a phenyl group linear or branched C3 ~ C9).
[4] photochromic compound (C) is at least one selected from the following general formula (9) or the following general formula (10), polymerizable composition according to any one of [1] to [3];
　PC-L-Chain
　(9) '(10) PC-L-Chain-L'-PC
(in the formula (9) or formula (10), PC and PC' of the general formula (11) compound to (14) .PC a PC to a monovalent group derived from a 'may be the same or different.
[Chem 9]

(in the formula (11) ~ (14), R 1 ~ R 18 is hydrogen, halogen atom , carboxyl group, an acetyl group, a formyl group, an aliphatic group which may be C1 ~ C20 substituted, aromatic organic alicyclic group or may be substituted C6 ~ C20, the optionally substituted C3 ~ C20 represents a group, it may be the same or different. these aliphatic groups, also alicyclic group L is an aromatic organic group, an oxygen atom, contained in the compound represented by the nitrogen atom may contain. Formula (11) to (14), one of the groups is a divalent organic group or L 'binds.)
　equation (9) or formula (10), L and L' are oxyethylene chain, oxypropylene chain, (thio) ester group, one selected from (thio) amido group represents a divalent organic group containing a least.
　in formula (9) or formula (10), chain polysiloxane chain, monovalent or divalent organic group containing at least one selected from polyoxyalkylene chain are shown.)
[5] The allyl carbonate polymerizable compound, diethylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6 hexanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-methyl-2-ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2,2, 4-trimethyl-1,3-pentanediol, 1,4-dimethylolcyclohexane and 4,8-bis (hydroxymethyl) - [5.2.1.0 2, 6 ] at least one selected from tricyclodecane bis (allyl carbonate) compound species of diol,
glycerol, trimethylol Propane and tris least one triol tris (allyl carbonate) is selected from (hydroxyethyl) isocyanurate compounds,
pentaerythritol, at least one tetraol tetra (allyl carbonate selected from diglycerol and ditrimethylolpropane ) compounds,
hexa dipentaerythritol (allyl carbonate) compounds, and
the diols, the triol, mixed poly (allyl carbonate) compounds of at least two compounds selected from tetraols and said dipentaerythritol is selected from that comprises at least one composition according to [2].
[6] The allyl carbonate polymerizable compound,
(i) diethylene glycol bis (allyl carbonate) compounds and mixtures and oligomers thereof,
(ii) diethylene glycol and mixtures of neopentyl glycol bis (allyl carbonate) compounds and mixtures and oligomers thereof,
(iii) diethylene glycol and tris mixture of (hydroxyethyl) isocyanurate poly (allyl carbonate) compound and the oligomer thereof mixture,
(iv) diethylene glycol and poly (allyl carbonate) of a mixture of trimethylol propane compounds and mixtures and oligomers thereof,
(v) poly (allyl carbonate) of a mixture of diethylene glycol and pentaerythritol compounds and mixtures and oligomers thereof,
( vi) poly (allyl carbonate of diethylene glycol and neopentyl glycol and mixtures pentaerythritol) compounds and mixtures and oligomers thereof, and
(vii) diethyl And poly glycol and neopentyl glycol and mixtures of pentaerythritol (allyl carbonate) compounds and mixtures thereof with oligomers,
diethylene glycol bis (allyl carbonate) compounds and mixtures and poly (allyl carbonate) mixture comprising the oligomer thereof ,
comprises at least one member selected from a composition according to [2].
[7] The allyl ester polymerizable compound,
diallyl isophthalate or diallyl terephthalate or diallyl phthalate monomer selected from diallylorthophthalate,
Wherein the diallyl phthalate monomer, ethylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol , 1,6-hexanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-methyl-2-ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol , 2,2,4-trimethyl-1,3-pentanediol, 1,4 least one diol diallyl ester monomers and oligomers thereof obtained by transesterification of a mixture of selected from dimethylol cyclohexane,
the Jiarirufutare A monomer, glycerol, poly obtained trimethylol propane, tris (hydroxyethyl) isocyanurate, pentaerythritol, diglycerol, ditrimethylolpropane, by transesterification of a mixture of at least one polyol selected from dipentaerythritol allyl ester monomers and oligomers, and
dialkyl isophthalate having an alkyl group of C1 ~ C3, dialkyl terephthalate, and at least one dialkyl phthalate selected from dialkyl ortho phthalate, allyl alcohol, diallyl carbonate, the diol or the allyl ester monomers and oligomers containing allyl carbonate group obtained by transesterification of a mixture of polyols , Comprises at least one member selected from A composition according to [2].
[8] The allyl ester polymerizable compound,
(i) and diallyl terephthalate, the diallyl terephthalate 30 wt% of diethylene glycol bis respect phthalate (allyl carbonate) compounds and oligomer, mixtures,
obtained by transesterification of (ii) a mixture of diallyl terephthalate and propylene glycol allyl ester compound,
allyl ester compound (iii) (ii), 20 wt% of diethylene glycol bis relative to the allyl ester compound (allyl carbonate) compounds and oligomer, mixtures,
and (iv) dimethyl terephthalate obtained by transesterification of allyl alcohol and diallyl carbonate and a mixture of diethylene glycol, allyl ester compound, allyl carbonate compound and an allyl ester group and an allyl carbonate group Yes Mixtures of compounds, and
(v) and the mixture obtained in (iv), the mixture to 10 wt% of diethylene glycol bis (allyl carbonate) compounds and oligomer, mixtures,
at least one selected from including species, polymerizable composition according to [2].
[9] The compound containing two or more allyloxycarbonyl group (A),
　its oligomer wherein allyl ester polymerizable compound and according to [7], the allyl carbonate polymer compound according to [5] and its the composition according to the oligomer, a mixture of [2].
[10] in an amount of component (A) 0.3 - 5.0 parts by weight said component (B) relative to 100 parts by weight, the composition according to any one of [1] to [9].
[11] in an amount of component (A) 0.01 - 0.5 parts by weight said component (C) relative to 100 parts by weight, the composition according to any one of [1] to [9].
[12] [1] - comprising the step of radical polymerization of a polymerizable composition according to any one of [11], a method of manufacturing an organic glass having photochromic properties.
[13] The process [1] to the polymerizable composition according to any one of [11] is injected into a mold, which is polymerized 1 to 100 hours at a temperature in the range of 50 - 120 ° C. , including casting polymerization process, the method described in [12].
[14] [1] to [11] the polymerizable composition polymerized hardened organic glasses according to any one of.
[15] lenses made of organic glass according to [14].
[16] and a polarizing film,
　formed in said at least one surface of the polarizing film, polarizing lens and a base layer made of an organic glass according to [14].
[0013]
　In the present invention, for example, a "bis diol (allyl carbonate) compound", two hydroxyl groups of the diol is meant a compound having the replaced structure with an allyl carbonate group.
　Further, in the present invention, for example, a "diethylene glycol bis (allyl carbonate) compounds in the mixture of neopentyl glycol",
compounds having a (1) two hydroxyl groups of diethylene glycol was replaced with an allyl carbonate group structure,
(2 ) neopentyl two hydroxyl groups in glycol is meant a compound having a structure which is replaced by an allyl carbonate group.
　Further, in the present invention, for example, a "diethylene glycol and oligomer bis (allyl carbonate) compounds in the mixture of neopentyl glycol", oligomers of said compound (1), oligomer of the compound (2), and the compound (1 ) and oligomers of said compound (2), means.
Effect of the invention
[0014]
　Polymerizable composition polymerized to the resulting cured product of the present invention is not only excellent photochromic properties, excellent moldability, good yield can be produced by not require strict temperature control equipment, and mechanical, color is superior optical properties and the like. Therefore, the photochromic polymerizable composition polymerized to the obtained cured product of the present invention are useful as organic glasses having photochromic properties, for example, can be suitably used for applications such as photochromic spectacle lenses.
DESCRIPTION OF THE INVENTION
[0015]
　Of the present invention, the polymerizable composition comprises a compound comprising (A) 2 or more allyloxycarbonyl group, (B) peroxy ketal radical polymerization initiator, peroxy monocarbonate based radical polymerization initiator and peroxy ester system comprising at least one polymerization initiator selected from a radical polymerization initiator group consisting, and at least one photochromic compound selected from (C) naphthopyran compounds.
[0016]
[Compound (A) containing two or more allyloxycarbonyl group]
　in the present invention, compounds containing 2 or more allyloxycarbonyl group (A) can be expressed by the following equation.
[0017]
[Formula 10]

[0018]
　Wherein, n is an integer of 2-6. R 1 represents a hydrogen atom or a methyl radical, R presence of a plurality of 1 may be the same or different.
[0019]
　X is divalent to hexavalent organic group optionally having an oxygen atom derived from a linear or branched aliphatic polyol a1 of which may carbon atoms 3 ~ 12 a, have an oxygen atom divalent to hexavalent organic group b or divalent to hexavalent organic radical derived from an aromatic compound c1 of 6 to 12 carbon atoms, which is also derived from cycloaliphatic polyols b1 good carbon atoms 5-16 a c, organic group a or an organic group b are linked to form allyl carbonate group and an allyloxycarbonyl group via an ether group derived from a hydroxyl group.
　These polyols, 2-6 in the normal molecule, preferably containing 2 to 4 hydroxyl groups.
[0020]
　The aliphatic polyol a1, diethylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neo neopentyl glycol, 3-methyl-1,5-pentanediol, 2-methyl-2-ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2,2,4-trimethyl - 1,3-pentanediol, glycerol, trimethylolpropane, tris (hydroxyethyl) isocyanurate, pentaerythritol, and di pentaerythritol.
　The cyclic aliphatic polyols b1, 1,4-dimethylolcyclohexane, 4,8-bis (hydroxymethyl) - [5.2.1.0 2, 6 ] can be given tricyclodecane and the like.
　The aromatic compounds c1, benzene, toluene, xylene, naphthalene and the like.
　As the compound containing two or more allyloxycarbonyl group (A), specifically, include allyl carbonate polymer compound, allyl ester polymerizable compound, a polymerizable compound containing at least one allyl carbonate group and allyl ester group be able to.
[0021]
　Compounds containing 2 or more allyloxycarbonyl group can contain oligomers thereof. Compounds containing 2 or more allyloxycarbonyl group, at room temperature a liquid product, the viscosity measured at 25 ° C. is 10 ~ 1000 cSt, the oligomer content can vary within wide limits, for example, 0 to about 80 in weight percent.
[0022]
(Allyl carbonate polymer compound)
　allyl carbonate polymer compound can be represented by the following general formula (2), and may include oligomers thereof. Oligomer is a poly via carbonate groups produced by transesterification of allyl carbonate and a polyol produced by the production process 2 molecules or more polyols linked (allyl carbonate).
　The allyl carbonate polymer compound is a linear or poly (allyl carbonate) compounds of branched aliphatic polyols having 3 to 12 carbon atoms. Poly (allyl carbonate) compounds of cycloaliphatic polyols having 5 to 16 carbon atoms in the molecule are also suitable for this purpose. These polyols, 2-6 in the normal molecule, preferably having 2 to 4 hydroxyl groups. Mixed poly (allyl carbonate) compounds, i.e. derived from two or more polyols, one can be obtained by mechanical mixing of poly (allyl carbonate) compounds each polyol, or starting from a mixture with diallyl carbonate polyol it is also possible to use those which can be obtained directly by a chemical reaction. Finally, all of the poly (allyl carbonate) compounds these may be in the form of a mixture of monomer or monomers and oligomers. In general, allyl carbonate polymer compound is a liquid product at room temperature, the viscosity measured at 25 ° C. is 10 ~ 1000 cSt, the oligomer content can vary within wide limits, for example, 0 to about 80 in weight percent.
[0023]
[Of 11]

[0024]
　In formula (2), X a linear or branched C3 ~ 2 ~ hexavalent group derived from a cyclic aliphatic polyol aliphatic 2 to be derived from polyols hexavalent group or C5-C16 of C12 It represents, n represents an integer of 2-6.
[0025]
　Polyols constituting the X in the general formula (2), as a specific example, diethylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5 pentanediol, 1,6-hexanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-methyl-2-ethyl-1,3-propanediol, 2,2-diethyl-1,3 propanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,4-dimethylolcyclohexane, 4,8-bis (hydroxymethyl) - [5.2.1.0 2, 6 ] tricyclo decane, glycerol, trimethylolpropane, tris (hydroxyethyl) isocyanurate, Pentaeri Lithol, diglycerol, ditrimethylolpropane, and di pentaerythritol.
[0026]
　Accordingly, examples of the allyl carbonate compound, for example, diethylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6 - hexanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-methyl-2-ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2,2 , 4-trimethyl-1,3-pentanediol, 1,4-dimethylolcyclohexane and 4,8-bis (hydroxymethyl) - [5.2.1.0 2, 6 ] at least selected from tricyclodecane one diol bis (allyl carbonate) compounds, glycerol, DOO Trimethylolpropane and tris (hydroxyethyl) at least one triol tris (allyl carbonate) is selected from the isocyanurate compound, pentaerythritol, at least one tetraol tetra (allyl selected from diglycerol and ditrimethylolpropane carbonate) compounds, selected hexa dipentaerythritol (allyl carbonate) compounds, and the diols, the triol, mixed poly (allyl carbonate) compounds of at least two compounds selected from tetraols and the dipentaerythritol, from It is the at least one.
[0027]
　Note that "at least two bis mixture of diol (allyl carbonate)", for example, if the diol is diethylene glycol and neopentyl glycol is obtained as a mixture of monomer component and oligomer component follows.
Monomer component
(1) diethylene glycol bis (allyl carbonate)
(2) neopentyl glycol bis (allyl carbonate)
oligomer component
(3) an oligomer that contains only diethylene glycol-derived hydrocarbons (and ether)
(4) neopentyl glycol-derived hydrocarbons oligomers containing only
composite oligomer containing a (5) a hydrocarbon (or ethers) derived from diethylene both hydrocarbons from neopentyl glycol in the same molecule
[0028]
　The following are preferred examples of suitable allyl carbonate polymer compound for the purposes of the present invention.
(i) diethylene glycol bis (allyl carbonate) and mixtures thereof with oligomers
　of diethylene glycol bis (allyl carbonate) can be defined by the formula (I).
[0029]
[Chem. 12]

[0030]
　Also, oligomers of diethylene glycol bis (allyl carbonate) can be defined by the formula (II).
[0031]
[Formula 13]

[0032]
　In the formula, n is 2 or more.
　Compound (I), for example, "Encyclopedia of Chemical Technology", Kirk-Othmer, III Edition, Volume 2, as described in 111-112 pages, reacting diethylene glycol bis (chloroformate) with allyl alcohol it can be produced by. Mixtures of diethylene glyceryl Corbis (allyl carbonate) (Formula (I)) and oligomers thereof (formula (II)), for example, European as described in patent 35.304, the presence of a basic catalyst by operating at lower, it may be conveniently prepared by transesterification of diallyl carbonate and diethylene glycol. These mixtures usually contain up to about 80 wt% oligomers.
[0033]
(ii) diethylene glycol bis (allyl carbonate) of a mixture of neopentyl glycol compounds and mixtures and oligomers thereof
　The bis (allyl carbonate) compounds, except for replacing diethylene glycol with a mixture of diethylene glycol and neopentyl glycol, wherein is the same as the bis (allyl carbonate) of a point (i).
[0034]
(iii) diethylene glycol and tris poly (allyl carbonate) of a mixture of (hydroxyethyl) isocyanurate compounds and mixtures and oligomers thereof
　The poly (allyl carbonate) compounds, for example, is described in U.S. Patent No. 4,812,545 and as can be obtained by transesterification of diethylene glycol and tris diallyl carbonate of a mixture of (hydroxyethyl) isocyanurate.
[0035]
(iv) diethylene glycol and poly (allyl carbonate) of a mixture of trimethylol propane compounds and mixtures and oligomers thereof
　The poly (allyl carbonate) compounds, except for replacing tris (hydroxyethyl) isocyanurate with trimethylolpropane, is similar to the poly (allyl carbonate) of said point (iii).
[0036]
(v) diethylene glycol and poly (allyl carbonate) of a mixture of pentaerythritol compound and a mixture of oligomers thereof
　The poly (allyl carbonate) compounds, except for replacing tris (hydroxyethyl) isocyanurate with pentaerythritol, of the similar to the poly (allyl carbonate) compounds point (iii).
[0037]
(vi) diethylene glycol and poly (allyl carbonate) of neopentyl glycol and mixtures of pentaerythritol compound and a mixture of oligomers thereof
　The poly (allyl carbonate) compounds, the diethylene glycol being substituted by two diols diethylene glycol neopentyl glycol except that is the same as the poly (allyl carbonate) of said point (v).
[0038]
(vii) diethylene glycol and neopentyl glycol and poly (allyl carbonate) of a mixture of pentaerythritol compound and a mixture of oligomers thereof,
poly comprising a mixture of diethylene glycol bis (allyl carbonate) compound and its oligomer, a (allyl carbonate) blend
[0039]
(Allyl ester polymerizable compound)
　The allyl ester polymerizable compound, diallyl phthalate represented by the following general formula (3); represented by the following general formula (4), by transesterification of a mixture of diallyl phthalate with a polyol allyl ester compound obtained; or a polymerizable compound containing at least one of allyl ester group and an allyl carbonate group represented by the following general formula (5) and can be exemplified oligomers thereof.
　Polymerizable compound represented by the general formula (5) is obtained by transesterification of a mixture of a dialkyl phthalate and allyl alcohol and diallyl carbonate with a polyol, an allyl ester compound, allyl carbonate compound, and allyl esters and allyl carbonate group comprising a mixture of compounds having.
　In the present embodiment, the compounds of the following general formula (3) to (5) is intended to include positional isomers.
[0040]
[Formula 14]

[0041]
　Diallyl phthalate represented by the general formula (3) is at least one selected diallyl isophthalate, diallyl terephthalate, and diallyl ortho phthalate.
[Of 15]

[0042]
　In the formula (4), X is a divalent group or aliphatic polyols of linear or branched C3 ~ C10 having 3-6 hydroxyl groups, which are derived from aliphatic diols linear or branched C2 ~ C8 It represents the induced 3-6-valent radical, n is an integer of 2-6.
[0043]
[Chemical Formula 16]

[0044]
　In the formula (5), X is a divalent group or aliphatic polyols of linear or branched C3 ~ C10 having 3-6 hydroxyl groups, which are derived from aliphatic diols linear or branched C2 ~ C8 represents the induced 3-6 monovalent group, m and n are summation of and m and n represent an integer of 0 to 6 represents an integer of 2-6.
[0045]
　Diallyl phthalate used, as a specific example is diallyl isophthalate, diallyl terephthalate, diallyl ortho phthalate,
dialkyl phthalate with phthalic diester having an alkyl group of C1 ~ 3, dimethyl isophthalate Specific examples, dimethyl terephthalate , dimethyl ortho phthalate, diethyl isophthalate, diethyl terephthalate, diethyl ortho phthalate, dipropyl isophthalate, dipropyl terephthalate, dipropyl ortho phthalate.
　The polyol constituting the X of formula (4) and (5), specific examples include ethylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, 1,3 - propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-methyl-2-ethyl-1, 3-propanediol, 2,2-diethyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,4-dimethylolcyclohexane and is diol and glycerol, trimethylol propane there triols and tris (hydroxyethyl) isocyanurate Rate, pentaerythritol, diglycerol, ditrimethylolpropane, a polyol is dipentaerythritol.
[0046]
　Formula (4) and the compound of formula (5) may comprise the oligomer. Oligomers are those produced by transesterification of the allyl ester compound and a polyol produced by the production process in the equation (4). Oligomers in the formula (5) is an allyl ester compound or allyl carbonate compound produced by the production process is produced by transesterification of a polyol.
[0047]
　Thus, the allyl ester polymerizable compound, for example, diallyl isophthalate, diallyl phthalate monomer selected diallyl terephthalate, and diallyl ortho phthalate,
and the diallyl phthalate monomer, ethylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol , tetraethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 3-methyl-1, 5-pentanediol, 2-methyl-2-ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, 1, 4 At least one diol diallyl ester monomers and oligomers thereof obtained by transesterification of a mixture of selected from such dimethylolcyclohexane,
said diallyl phthalate, glycerol, a triol is trimethylol propane, tris (hydroxyethyl) isocyanurate, pentaerythritol, diglycerol, ditrimethylolpropane, polyallyl ester monomer and oligomers thereof obtained by transesterification of a mixture of at least one polyol selected from dipentaerythritol,
Dimethyl isophthalate, dimethyl terephthalate, dimethyl ortho phthalate, diethyl isophthalate, and diethyl terephthalate, diethyl ortho phthalate, dipropyl isophthalate, dipropyl terephthalate, at least one C1 ~ C3 dialkyl phthalate selected from dipropyl ortho phthalate, and allyl alcohol, at least a diallyl carbonate, is selected allyl ester compounds obtained by transesterification of mixtures of the aforementioned diols or polyols, allyl carbonate compound and the compound having an allyl carbonate group and allyl ester group and their oligomers, from including the one.
[0048]
　The allyl ester polymerizable compound, more specifically,
(i) and diallyl terephthalate, the diallyl terephthalate 30 wt% of diethylene glycol bis respect phthalate (allyl carbonate) compounds and oligomer, mixtures,
(ii) allyl ester compound obtained by transesterification of a mixture of diallyl terephthalate and propylene glycol,
(iii) allyl ester compound of (ii) and, 20 wt% of diethylene glycol bis relative to the allyl ester compound (allyl carbonate) compound and its oligomer, a mixture of,
(iv) obtained by transesterification of dimethyl terephthalate and allyl alcohol and diallyl carbonate and a mixture of diethylene glycol, allyl ester compound, allyl carbonate compound Allyl mixture of compounds having an ester group and an allyl carbonate group, and and
and (v) the mixture obtained in (iv), 10 wt% of diethylene glycol bis to the mixture (allyl carbonate) and compounds and oligomers thereof, mixture preferably contains at least one selected from.
[0049]
　The following are preferred examples of suitable allyl ester polymerizable compound for the purposes of the present invention.
(i) dimethyl terephthalate, allyl alcohol, diallyl carbonate, allyl ester compound obtained by the transesterification of a mixture of diethylene glycol, a mixture of allyl carbonate compound and the compound having an allyl ester group and an allyl carbonate group
　above allyl ester compound of the formula (III) can be defined by ~ (V), a main component diallyl terephthalate of the formula (III), each containing oligomer is obtained by reacting polyol and transesterification.
[0050]
[Chemical Formula 17]

[0051]
　In this embodiment, said compound containing two or more allyloxycarbonyl group (A), from the viewpoint of the effect of the present invention, and the allyl ester polymerizable compound and its oligomer, the allyl carbonate polymer compound and its oligomer it can be a mixture of.
[0052]
[Radical polymerization initiator (B)]
　then the radical polymerization initiator in the present invention for (B) will be described.
　As the radical polymerization initiator (B) of the present invention, represented by (a) 10-hour half-life temperature of 80 ° C. or more peroxy ketal radical polymerization initiator and / or the following general formula by the following general formula (6) (7) represented by (b) 10-hour half-life temperature is represented by more than 80 ° C. the peroxy monocarbonate based radical polymerization initiator and / or the following general formula (8) (c) 10-hour half-life temperature There using a 65 ° C. or more peroxyester polymerization initiator. By using the initiator of the specific decomposition temperature, without degrading the photochromic compound, it is possible to provide excellent photochromic cured product in photochromic properties.
[0053]
[Formula 18]

in the (equation (6), R 3 is a tertiary alkyl group, R 1 and R 2 are alkyl groups selected independently from methyl, ethyl, propyl and butyl, said alkyl group may have a non-interfering functional groups such as alkyl ester group at the end of example the chain, or R 1 and R 2 form a cycloalkylene group together with the carbon atoms to which they are attached it is possible to, the cycloalkylene group may have 1 to 3 alkyl substituents.)
[0054]
[Of 19]

[0055]
(In the formula (7), R 1 is a tertiary alkyl group of C3 ~ C6, R 2 is an alkyl group of C3 ~ C8 linearized or branched)
[0056]
[Of 20]

[0057]
(In the formula (8), R 1 is a tertiary alkyl group of C3 ~ C6, R 2 is an alkyl group or a phenyl group linear or branched C3 ~ C9).
[0058]
　Peroxy ketal radical initiator (a) in {() shows the 10 hour half-life temperature. Specific examples of the}, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane (83 ° C.), 1,1-bis (t-hexyl peroxy) -3,3 , 5-trimethyl cyclohexane (90 °
C.), 2,2-bis (t-butylperoxy) butane (107 °
C.) n-butyl-4,4-bis (t-butylperoxy) Vallee rate (109 ° C.)
ethyl 3,3-bis (t-butylperoxy) Vallee rate (114 °
C.) 1,1-bis (t-butylperoxy) cyclohexane (91 °
C.) 1,1-bis (t-butylperoxy) -2 - methylcyclohexane (83 °
C.) 1,1-bis (t-amyl peroxy) cyclohexane (93 °
C.) 1,1-bis (t-hexyl peroxy) cyclohexane (87 °
C.) 1,1-bis (t - hexyl peroxy) -3,3,5-trimethylcyclohexane (87 °
C.) 2,2-Bis [4,4- (di -t- butyl peroxy) cyclohexyl] propane (95 ° C.)
and the like can be mentioned .
[0059]
　Peroxy monocarbonate based radical initiator (b) in {() shows the 10 hour half-life temperature. Specific examples of
the}, OO- (t-butyl) -O- isopropyl monoperoxycarbonate (99 °
C.) OO- (t-amyl) -O- isopropyl monoperoxycarbonate (96 °
C.) OO- (t - butyl) -O- (2-ethylhexyl) monoperoxycarbonate (99 °
C.) OO- (t-amyl) -O- (2-ethylhexyl) monoperoxycarbonate (99 ° C.)
and the like.
[0060]
　Peroxyester radical initiator (c) in {() shows the 10 hour half-life temperature. Specific examples of
the}, t-butyl peroxy-2-ethylhexanoate (72 °
C.) t-butylperoxy isobutyrate (82 °
C.) t-butylperoxy-3,3,5-trimethylhexamethylene Noeto (97 °
C.) t-butyl peroxy acetate (102 °
C.) t-butylperoxy isononanoate Na benzoate (102 °
C.) t-butyl peroxybenzoate (104 °
C.) t-amyl peroxy-2-ethylhexanoate (75 °
C.) t-amyl peroxy-n-octoate (96 °
C.) t-amyl peroxy acetate (100 ° C.)
t-amyl peroxy isononanoate Na benzoate (96 °
C.) t-amyl peroxybenzoate (100 °
C.) t- hexyl peroxy-2-ethylhexanoate (70 °
C.) t-hexyl peroxybenzoate (99 °
C.) 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate (65 ° C.)
and the like.
[0061]
　In the present invention, the amount of the radical polymerization initiator, kind of the polymerization conditions and initiator differs depending on the composition of the monomer and is variable. Compounds comprising the allyloxycarbonyl group (A) 100 0.3-5.0 parts by weight per part by weight, preferably 0.5 to 3.0 parts by weight, can also be used in combination of two or more radical polymerization initiator.
[0062]
　Further, when polymerizing the polymerizable composition of the present invention, among the polymerization conditions, especially temperature affects the properties of the photochromic cured product obtained. The temperature condition is, can not unconditionally limit is affected by the type of the type and amount and the monomer of the radical polymerization initiator, typically initiates at a relatively low temperature polymerization, it will slowly raising the temperature it is preferred that the curing at a high temperature at the end of polymerization. Time also differs depending on factors temperature as well as various polymerization, the advance but it is preferable to determine the optimum time according to these conditions, typically choose conditions such that polymerization at 12-24 hours to complete It is preferred. The polymerizable composition of the present invention, 35 ° C. without strict control of the following, even in a pattern starting from 60 ° C. or higher are possible curing, because molding is easy, and high yield.
[0063]
[Photochromic compound (C)]
　will be described photochromic compound (C) in the present invention. The photochromic compound (C) may be any employed without limitation compounds exhibiting photochromic effect may be at least one selected from naphthopyran compounds.
[0064]
　The photochromic compounds of the present invention is one or more selected from the following general formula (9) or the following general formula (10).
　PC-L-Chain
　(9) PC-L-Chain-L'-PC
　'(10) PC and PC' represents a monovalent group derived from a compound of general formula (11) to (14). PC and PC 'may be the same or different.
[0065]
[Of 21]

[0066]
　Equation (11) in ~ (14), 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 (11) contained in the compound represented by - (14), one of the group is attached to L or L 'is a divalent organic group.
[0067]
　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 ~ C1 ~ C10 alkyl group substituted with C10 alkoxy group, C1 ~ C10 C1 ~ substituted with an alkoxy group C10 alkoxy, 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 mention may be made of the group, and the like.
[0068]
　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.
[0069]
　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.
[0070]
　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.
[0071]
　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 group, C1 ~ C10 aminoalkyl group, linear or branched chain C1 ~ C20 alkoxycarbonyl group, etc., aliphatic group which may be substituted C1 ~ by
C20; cycloalkyl group C3 ~ C20, such as bicycloalkyl group C6 ~ C20, may be substituted C3 alicyclic group ~ C20;
arylcarbonyl group, an aroyl group, a phenyl group, C7 ~ C16 alkoxyphenyl group, C1 ~ C10 Gia And the like can be given; Kokishifeniru group, C1 ~ C10 alkyl phenyl group, such as C1 ~ C10 dialkyl phenyl group, an aromatic organic group which may be substituted C6 ~ to C20.
[0072]
　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 (15) or (16) can be mentioned. 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.
[0073]
[Formula 22]

[0074]
　R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 14 , R 15 , R 16 is, R 1 , R 2 shows a similar functional group. R presence of a plurality of 5 ~ R 7 and may be the same or different.
[0075]
　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.
[0076]
　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.
[0077]
　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.
[0078]
　L and L 'are of the general formula (9) or (10), 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 (17) to (23). L and L 'may be the same or different.
[0079]
[Of 23]

[0080]
　Wherein (17) ~ (23),
　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.
[0081]
　"Chain" in the general formula (9) or (10) 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.
[0082]
　Specifically,
　"Chain", if the photochromic compound of general formula (9) represents a monovalent organic group of the general formula (24) or (25).
[0083]
[Of 24]

[0084]
　"Chain" when the photochromic compound is of the general formula (10) represents a divalent organic group of the general formula (26) or (27).
[0085]
[Of 25]

[0086]
　Wherein (24) ~
(27), 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 '.
[0087]
　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.
[0088]
　The photochromic compound of the present invention, Vivimed's Reversacol Humber Blue (polydimethylsiloxane chain, naphthopyran chromophore (Formula 11)), Reversacol Calder Blue (polydimethylsiloxane chain, naphthopyran chromophore (Formula 11)) , Reversacol Trent Blue (polydimethylsiloxane chain, naphthopyran chromophore (formula 11)), Reversacol Pennine Green (polydimethylsiloxane chain, naphthopyran chromophore (formula 11)), Reversacol Heath Green (polyoxyalkylene chain, naphthopyran chromophore (formula 11)), Reversacol Chilli Red (polydimethylsiloxane chain, naphthopyran chromogenic (Formula 11)), Reversacol Wembley Gray (polyoxyalkylene chain, naphthopyran chromophore (Formula 11)), Reversacol Cayenne Red (polyoxyalkylene chain, naphthopyran chromophore (Formula 11)), exemplified etc It is.
[0089]
　In the polymerizable composition of the present invention, according to the predetermined combination of the polymerization initiator and (B) given photochromic compound and (C), degradation of the photochromic compound (C) is suppressed by the polymerization initiator (B) . Therefore, the polymerization initiator (B) and photochromic compound (C) and can coexist in the polymerizable composition at low cost and simple way kneading method, excellent photochromic properties, excellent more hues it is possible to obtain a cured body.
　In the present invention, the mixing ratio of the photochromic compound of component (C), when too much is happening aggregation of the photochromic compound, the durability is rapidly lowered. Thus, relative to compound (A) 100 parts by weight of containing two or more allyloxycarbonyl group, the photochromic compound (C) is generally used in the range of 0.001 to 5 parts by weight, preferably 0.01 to 1 part by weight, more preferably used in the range of 0.01 to 0.5 part by weight, best photochromic performance is obtained in this range.
[0090]
　The polymerizable composition of the present invention may further release agents, ultraviolet absorbers, infrared absorbers, ultraviolet stabilizers, antioxidants, coloring agents, antistatic agents, fluorescent dyes, dyes, pigments, various perfumes stabilizers, and mixed as necessary additives may be used.
[0091]
　It is suitable to be able to further improve the durability of the photochromic compound when used in a mixture of UV absorbers as described above. As the ultraviolet absorber, benzophenone ultraviolet absorbers, benzotriazole ultraviolet absorbers, triazine ultraviolet absorbers, malonate type ultraviolet absorber, can be suitably used oxanilide-based ultraviolet absorbers.
[0092]
　The ultraviolet absorber while improving the durability of the photochromic compound, to inhibit color development by ultraviolet radiation of the photochromic compound. Although the ultraviolet region is absorbed by the type of ultraviolet absorber can not differ unconditionally limited, usually, 0.001 to 5 parts by weight amount of the ultraviolet absorber of the radical polymerizable compound 100 parts by weight, more it is preferred that from 0.01 to 1 part by weight.
[0093]
　The polymerization method for obtaining a cured product from the polymerizable composition of the present invention is not particularly limited, it can employ a known radical polymerization method. To illustrate a typical polymerization process, between molds held by an adhesive tape or an elastomeric gasket or a spacer, and injecting the polymerizable composition of the present invention mixed with a radical polymerization initiator, it was oxidized in an air furnace after, casting polymerization to be removed is adopted.
[0094]
　Further, the photochromic cured product obtained by the above method may also be subjected to the following processing depending on the application. In other words, staining with a dye such as disperse dye, silane coupling agent and silicon, zirconium, antimony, aluminum, tin, tungsten, etc. sol hard coating agent and mainly composed of, SiO 2 , TiO 2 , ZrO 2 , etc. anti-reflection treatment by coating a thin film deposition or an organic polymer thin film of a metal oxide, can be subjected to processing and secondary processing of anti-static treatment.
[0095]
　Polymerizable composition polymerized cured photochromic cured product of the present invention (organic glass), the of (A) a radical polymerizable compound, (B) to become a radical polymerization initiator, and (C) a photochromic compound, is prepared with easier, while excellent photochromic properties, 20 ° C., the refractive index at the wavelength of 589.3nm can be in the range of 1.49 to 1.57, can be used in various optical materials it is. In particular, it can be suitably used as a lens or a polarized lens.
[0096]
[Lens
　lens made of organic glass of this embodiment may optionally be used after the coating layer on one or both sides. It can be preferably used as a spectacle lens.
　Lens of this embodiment is composed of a lens substrate and the coating layer comprising a polymerizable composition described above.
[0097]
　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.
[0098]
　Each of these coating layers, the infrared absorbing agent for the purpose of protecting the eyes from infrared rays, a light stabilizer or antioxidant for the purpose of improving the weather resistance of the lens, the photochromic compound, purpose dyes or pigments to enhance the fashion of the lens , antistatic agents, other may be used in combination known additive for increasing the performance of the lens.
　It may be used various leveling agents for the purpose of improving the coating properties with respect to the layer to perform coating by the coating.
[0099]
　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.
[0100]
　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.
[0101]
　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.
[0102]
　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.
[0103]
　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.
[0104]
　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.
[0105]
　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 .
[0106]
　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.
[0107]
[Polarizing lens]
　polarizing lens of the present embodiment includes a polarizing film, formed in said at least one surface of the polarizing film, a base material layer made of an organic glass, a.
[0108]
　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.
[0109]
　As the thermoplastic polyester, polyethylene terephthalate, polyethylene naphthalate, and can be exemplified polybutylene terephthalate, water resistance, and more preferably polyethylene terephthalate from the viewpoint of heat resistance and moldability.
[0110]
　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.
[0111]
　Polarizing lens of the present embodiment can be such on at least one surface of the polarizing film, obtained by the polymerizable composition of the present embodiment is cured provided a substrate layer made of an organic glass obtained by .
　Method for producing a plastic polarized lens is not particularly limited, preferably be mentioned casting polymerization method.
[0112]
　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 implanting at least one in the polymerizable composition of the air gap,
　the polymerizable composition is polymerized and cured, and laminating a base layer on at least one surface of the polarizing film may include .
[0113]
　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.
[0114]
　The polymerization conditions of the polymerizable composition, the composition of the polymerizable composition, type and amount of catalyst used, although conditions vary depending on the shape or the like of the mold, is carried out over 1 to 50 hours at a temperature of 5 ~ 140 ° C.. Optionally, held or gradually heated in a temperature range of 5 ~ 130 ° C., is thereby is preferably cured for 1 to 25 hours.
　The laminate was cured by polymerization by releasing from the mold, it is possible to obtain a polarizing lens of the present embodiment.
[0115]
　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 lens.
Example
[0116]
　The present invention will be described below with reference to Examples and Comparative Examples, the present invention is not limited to these examples.
[0117]
　Examples 1-9, Comparative Examples 1-6
　in Table 1 of Example 1-9, as shown in Comparative Examples 1-6, (A) a radical polymerizable compound, (C) a photochromic compound, and other additive components 70 It was sufficiently mixed in a ℃. The mixture was cooled to room temperature and mixed at room temperature until the added, homogenized (B) a radical polymerization initiator. These mixing ratio shown in Table 1.
[0118]
　The mixture containing the photochromic compound, two of the outer periphery of disk-shaped glass plate was poured into a mold wrapped with adhesive tape and subjected to cast polymerization. The polymerization using an air furnace, was polymerized and gradually raise the temperature. After the polymerization, remove the template from the air furnace, removed after cooling, the cured body from the glass type template.
[0119]
　Resin yellowness of the obtained photochromic cured product was tested in the following manner photochromic properties. The results are shown in Table 2.
[0120]
　(2) resin yellowness (YI)
　was measured YI obtained photochromic cured product colorimeter CM-5 measuring spectral (thickness 2 mm) made by Konica Minolta.
[0121]
　(3) photochromic properties
　light transmittance at 550nm after color: Otsuka using Denshi MC-2563 xenon lamp (180 W) light source device (illumination 50000Lx), at a temperature 23 ° C., the resulting photochromic cured product (thickness 2mm spectroscopic when) was allowed to develop for 5 minutes was measured with MCPD-7700 transmission measurement system.
　Color before transmission, after color transmittance was evaluated photochromic performance by transmittance change amount before and after the color development.
　Since the maximum absorption wavelength at color development by the photochromic compound (.lambda.max) are different, to evaluate the photochromic performance by transmission at .lambda.max.
The lower the transmittance after color development is high shielding properties during color development and color high density difference before and after coloring the larger the transmittance variation before and after, show that the photochromic performance is high.
[0122]
　(4) at Atago Co. Abbe refractometer to measure the refractive index of the cured product at 20 ° C. with a wavelength of 589.3 nm. In Examples 1-7, all of the cured product of Comparative Example 1-6, the refractive index 1.500 ± 0.002, the cured materials of Examples 8 and 9, the refractive index 1.550 ± 0. It was 002.
[0123]
(Materials used)
polymerizable compound
· RAV 7MC (diethylene glycol, neopentyl glycol and pentaerythritol poly (allyl carbonate) compounds and oligomers thereof, manufactured ACOMON
Ltd.) · RAV 7AT (diethylene glycol and pentaerythritol poly (allyl carbonate) compounds, and oligomers thereof, ACOMON
Ltd.) · RAV 7 ng (diethylene glycol and pentaerythritol poly (allyl carbonate) compounds and oligomers thereof, manufactured ACOMON
Ltd.) · RAV 755T (dimethyl terephthalate, allyl alcohol, diallyl carbonate, obtained by diethylene glycol transesterification allyl ester compound, allyl carbonate compound and an allyl ester group and A Mixtures of compounds having Lil carbonate groups, manufactured by ACOMON Co.)
[0124]
Radical polymerization initiator
· LUPEROX TAEC (OO- (t- amyl) -O- (2-ethylhexyl) monoperoxycarbonate, manufactured by
Arkema) · PERHEXA HC (1,1-bis (t-hexyl peroxy) cyclohexane, manufactured by NOF
CORPORATION) · LUPEROX 570 (t-amyl peroxy isononanoate Na benzoate, Arkema Yoshitomi
Ltd.) · TRIGONOX ADC-NS30 (isopropyl isobutyl peroxydicarbonate, diisopropyl peroxydicarbonate and diisobutyl peroxydicarbonate, a total of diethylene glycol bis containing 30 parts by weight (allyl carbonate) solution, Akzo Nobel)
[0125]
Photochromic compound
· Reversacol Heath Green (polyoxyalkylene chain, naphthopyran chromophore (Formula
11)) · Reversacol Wembley Gray (polyoxyalkylene chain, naphthopyran chromophore (Formula
11)) · Reversacol Pennine Green (polydimethylsiloxane chain, naphthopyran chromophore (formula
11)) · Reversacol Humber Blue (polydimethylsiloxane chain, naphthopyran chromophore (formula 11))
[0126]
(Example 1)
　with respect to RAV 7NG (ACOMON Ltd.) 99.1 parts by weight of a commercially available poly (allyl carbonate), a photochromic compound Reversacol Heath Green (product name, manufactured by Vivimed Ltd.) 0.035 parts by weight, Reversacol Wembley Gray (trade name, manufactured by Vivimed Ltd.) 0.065 parts by weight of 2-hydroxy-4-methoxybenzophenone (product name, SEESORB 101, manufactured by Shipro Kasei Co., Ltd.) and 0.15 parts by weight was dissolved at 70 ° C., cooled to room temperature LUPEROX TAEC as the curing agent after the addition of (product name, made by Arkema) 0.9 parts by weight, by injecting two outer periphery of the disk-shaped glass plate mold wrapped with adhesive tape, to 110 ° C. from room It was polymerized for 24 hours while gradually raising the temperature. Thereafter, the molded body was demolded and post polymerization by heating 1 hour 120 ° C., to obtain a flat plate of 2mm thickness. YI of the obtained resin was a pale yellow 4.1. color after transmission at λmax 29.6% transmittance change amount before and after the color development was 58.4%.
[0127]
(Example 2)
　with respect to RAV 7NG (ACOMON Ltd.) 99.1 parts by weight of a commercially available poly (allyl carbonate), a photochromic compound Reversacol Heath Green (product name, manufactured by Vivimed Ltd.) 0.035 parts by weight, Reversacol Wembley Gray (trade name, manufactured by Vivimed Ltd.) 0.065 parts by weight of 2-hydroxy-4-methoxybenzophenone (product name: SEESORB 101, manufactured by Shipro Kasei Co., Ltd.) 0.15 parts by weight, 1,4-bis [(2, 6- diethyl-4-methylphenyl) amino] -9,10-anthraquinone (trade name: Macrolex Blue RR, manufactured by LANXESS) 2.5 ppm, 1,4-diamino-2,3-phenoxy-9,10-anthraquinone ( product name: Solvaperm Red Iolet R, manufactured by Clariant) 2.5 ppm dissolved at 70 ° C. The, LUPEROX TAEC (product name as the curing agent after cooling to room temperature, manufactured by Arkema) was added 0.9 part by weight, the two disk-shaped glass by injecting the outer periphery of the plate to the mold wrapped with adhesive tape, and polymerized for 24 hours while raising gradually the temperature to 110 ° C. from room temperature. Thereafter, the molded body was demolded and post polymerization by heating 1 hour 120 ° C., to obtain a flat plate of 2mm thickness. YI of the obtained resin was neutral color in 1.7. color after transmission at λmax 29.3% transmittance change amount before and after the color development was 57.4%.
[0128]
(Example 3)
　with respect to RAV 7NG (ACOMON Ltd.) 98.8 parts by weight of a commercially available poly (allyl carbonate), a photochromic compound Reversacol Heath Green (product name, manufactured by Vivimed Ltd.) 0.035 parts by weight, Reversacol Wembley Gray (trade name, Vivimed Ltd.) 0.065 parts by weight of 2-hydroxy-4-methoxybenzophenone (product name: SEESORB 101, manufactured by Shipro Kasei Co., Ltd.) and 0.15 parts by weight was dissolved at 70 ° C., cooled to room temperature PERHEXA HC as a curing agent after the addition of (product name, manufactured by NOF CORPORATION) 1.2 parts by weight, by injecting two outer periphery of the disk-shaped glass plate mold wrapped with adhesive tape, 100 ° C. from room temperature It was polymerized for 24 hours while gradually raising the temperature to. Thereafter, the molded body was demolded and post polymerization by heating 1 hour 110 ° C., to obtain a flat plate of 2mm thickness. YI of the obtained resin was a pale yellow 4.8. color after transmission at λmax is 30.1%, the transmittance variation before and after the color development was 56.7%.
[0129]
(Example 4)
　with respect to RAV 7NG (ACOMON Ltd.) 98.8 parts by weight of a commercially available poly (allyl carbonate), a photochromic compound Reversacol Heath Green (product name, manufactured by Vivimed Ltd.) 0.03 parts by weight, Reversacol Wembley Gray (trade name, Vivimed Ltd.) was dissolved 0.06 parts by weight 70 ° C., was added LUPEROX 570 (product name, manufactured by Arkema Yoshitomi, Ltd.) 1.2 parts by weight of curing agent after cooling to room temperature, two the outer periphery of the glass plate was poured into molds wrapped with adhesive tape disk-shaped, and polymerized for 24 hours while raising gradually the temperature to 110 ° C. from room temperature. Thereafter, the molded body was demolded and post polymerization by heating 1 hour 120 ° C., to obtain a flat plate of 2mm thickness. YI of the obtained resin was a pale yellow 3.8. color after transmission at λmax 27.8% transmittance change amount before and after the color development was 59.6%.
[0130]
(Example 5)
　to RAV 7MC (ACOMON Co.) mixture of 29.7 parts by weight of the RAV 7AT (ACOMON Ltd.) 69.4 parts by weight of a commercially available poly (allyl carbonate) of a commercially available poly (allyl carbonate) Te, photochromic compound Reversacol Heath Green (product name, Vivimed Corp.) 0.03 part by weight, Reversacol Wembley Gray (trade name, manufactured by Vivimed Ltd.) 0.06 parts by weight of 2-hydroxy-4-methoxybenzophenone (product name: SEESORB 101, dissolved in Cipro Kasei Co., Ltd.) 0.2 parts by weight of 70 ° C. the, LUPEROX TAEC (product name as the curing agent after cooling to room temperature, was added Arkema) 0.9 parts by weight, the two discs injecting a periphery shaped for glass plates mold wrapped with adhesive tape Te, and polymerized for 24 hours while raising gradually the temperature to 120 ° C. from room temperature. Thereafter, the molded body was demolded and post polymerization by heating 1 hour 120 ° C., to obtain a flat plate of 2mm thickness. YI of the obtained resin was a pale yellow with 4.0. color after transmission at λmax 33.7% transmittance change amount before and after the color development was 53.2%.
[0131]
(Example 6)
　(manufactured by ACOMON Co.) RAV 7MC commercial poly (allyl carbonate) relative to 99.2 parts by weight, the photochromic compound Reversacol Pennine Green (product name, manufactured by Vivimed Ltd.) 0.046 parts by weight of 70 ° C. The in dissolved, LUPEROX TAEC as the curing agent after cooling to room temperature was added (product name, made by Arkema) 0.8 parts by weight, was injected two outer periphery of the disk-shaped glass plate mold wrapped with adhesive tape Te, and polymerized for 24 hours while raising gradually the temperature to 120 ° C. from room temperature. Thereafter, the molded body was demolded and post polymerization by heating 1 hour 120 ° C., to obtain a flat plate of 2mm thickness. YI of the obtained resin was a pale yellow 3.7. color after transmission at λmax is 45.4%, the transmittance variation before and after the color development was 44.1%.
[0132]
(Example 7)
　photochromic compound Reversacol Pennine Green (product name, manufactured by Vivimed Co.) Reversacol Humber Blue (product name, manufactured by Vivimed Co.) instead Except for using, 2 mm thickness in the same manner as in Example 6 to obtain a flat plate. YI of the obtained resin was a pale yellow 2.6. color after transmission at λmax 66.3% transmittance change amount before and after the color development was 24.5%.
[0133]
(Example 8)
　against a commercially available poly (allyl ester) and poly (manufactured ACOMON Co.) RAV 755T of the mixture of (allyl carbonate) (ACOMON Co.) 99.2 parts by weight, the photochromic compound Reversacol Pennine Green (product name , Vivimed Ltd.) 0.046 is dissolved in parts by weight 70 ° C. the, LUPEROX TAEC (product name as the curing agent after cooling to room temperature, manufactured by Arkema) was added 0.8 part by weight, the two disk-shaped glass by injecting the outer periphery of the plate to the mold wrapped with adhesive tape, and polymerized for 24 hours while raising gradually the temperature to 120 ° C. from room temperature. Thereafter, the molded body was demolded and post polymerization by heating 1 hour 120 ° C., to obtain a flat plate of 2mm thickness. YI of the obtained resin was a pale yellow 2.8. color after transmission at λmax 35.5% transmittance change amount before and after the color development was 52.4%.
[0134]
(Example 9)
　Photochromic compound Reversacol Pennine Green (product name, manufactured by Vivimed Co.) Reversacol Humber Blue (product name, manufactured by Vivimed Co.) instead Except for using, 2 mm thickness in the same manner as in Example 8 to obtain a flat plate. YI of the obtained resin was a pale yellow 3.2. color after transmission at λmax 63.0% transmittance change amount before and after the color development was 26.4%.
[0135]
(Comparative Example 1)
　against RAV 7MC (manufactured ACOMON Ltd.) (ACOMON Co.) 90 parts by weight of a commercially available poly (allyl carbonate), a photochromic compound Reversacol Pennine Green (product name, manufactured by Vivimed Ltd.) 0.046 parts by weight was dissolved at 70 ℃, TRIGONOX ADC-NS30 as a curing agent after cooling to room temperature (product name, manufactured by Akzo Nobel) was added 10 parts by weight, wound two outer periphery of the disk-shaped glass plate with an adhesive tape It was poured into molds and polymerization for 20 hours while raising gradually the temperature to 80 ° C. from room temperature. Thereafter, the molded body was demolded and post polymerization by heating for 2 hours to 110 ° C., to obtain a flat plate of 2mm thickness. YI of the obtained resin was dark yellow 13.7. color after transmission at λmax 77.4% transmittance change amount before and after the color development was 1.0%.

claims

[Claim 1](A) represented by the following general formula (1), a compound containing two or more allyloxycarbonyl group,
　(B) peroxy ketal radical polymerization initiator, peroxy monocarbonate based radical polymerization initiator and peroxy at least one polymerization initiator selected from the group consisting of ester-based radical polymerization initiator,
　and at least one photochromic compound selected from (C) naphthopyran compounds
containing polymerizable composition;
Formula 1]

(wherein, n .R is an integer of 2-6 1 represents a hydrogen atom or a methyl radical, R presence of a plurality of 1 may. be the same or different
　X is not an oxygen atom carbon atoms may be 3 to 12 linear or bivalent to hexavalent derived from branched aliphatic polyols organic group a, an oxygen atom and an optionally carbon atoms 5-16 also have A divalent to hexavalent organic group c derived from an aromatic compound of the divalent to hexavalent organic group b or 6 to 12 carbon atoms, derived from cycloaliphatic polyol, an organic group a or an organic group b is bonded to the allyloxycarbonyl group via an ether group derived from the hydroxyl group to which they are provided to form the allyl carbonate groups.).
[Claim 2]
　Compounds containing 2 or more allyloxycarbonyl group (A) include allyl ester represented by the allyl carbonate polymerizable compound represented by the following general formula (2) and oligomers thereof or the following general formula (3) or (4) polymerizable compound and its oligomer, or a polymerizable compound containing at least one of allyl ester group and an allyl carbonate group represented by the following general formula (5) and including oligomers thereof, the polymerizable composition according to claim 1 ;
[formula 2]

(2 in formula (2), X is derived from a cyclic aliphatic polyols linear or divalent to hexavalent group derived from an aliphatic polyol branched C3 ~ C12 or C5 ~ C16 represents a 1-6 valent radical, n is an integer of 2 to 6.)
[Chemical formula 3]

[formula 4]

in (equation (4), X is linear or aliphatic branched C2-C8 It represents a divalent group or 3-6-valent group derived from an aliphatic polyol linear or branched C3 ~ C10 having 3-6 hydroxyl groups, which are derived from all, n represents an integer of 2 to 6 a representative.).
[Chemical Formula 5]

In (Equation (5), X is linear or branched C2 2 divalent group derived from an aliphatic diol ~ C8 or linear or branched C3 ~ C10 having 3-6 hydroxyl groups, represents a 3-6 valent group derived from an aliphatic polyol, m and n are summation of and m and n represent an integer of 0 to 6 represents an integer of 2-6.).
[Claim 3]
　The polymerization initiator (B) is 10-hour half-life temperature of 80 ° C. or more peroxy ketal polymerization initiator represented by the following general formula (6), 10-hour half-life represented by the following general formula (7) temperature 80 ° C. or more peroxy monocarbonate based polymerization initiator, and 10-hour half-life temperature represented by the following general formula (8) is selected from the group consisting of 65 ° C. or more peroxyester polymerization initiator is at least one polymerizable composition according to claim 1 or 2,
[formula 6]

in (equation (6), R 3 is a tertiary alkyl group, R 1 and R 2 are each independently methyl, ethyl, alkyl group selected from propyl and butyl, said alkyl group may have an alkyl ester group at the terminal, or R 1 and R 2 together with the carbon atoms to which they are attached it was Can form Kuroarukiren group, the cycloalkylene group may have 1 to 3 alkyl substituents.)
[Formula 7]

In (Equation (7), R 1 is a C3 ~ C6 a tertiary alkyl group, R 2 is an alkyl group of C3 ~ C8 linearized or branched)
[Chem 8]

in (equation (8), R 1 is tertiary alkyl groups of C3 ~ C6 , R 2 is an alkyl group or a phenyl group linear or branched C3 ~ C9).
[Claim 4]
　Photochromic compound (C) is at least one selected from the following general formula (9) or the following general formula (10), the polymerizable composition according to any one of claims 1 ~ 3;
　PC-L-Chain
　(9) '(10) PC-L-Chain-L'-PC
1 which is derived from compound (formula (9) or formula (10), PC and PC' of the general formula (11) to (14) valent .PC of the proximal and PC 'may be the same or different.
[Chem 9]

(in the formula (11) ~ (14), R 1 ~ R 18 is hydrogen, halogen atom, carboxyl group, acetyl show group, a formyl group, an aliphatic group which may be C1 ~ C20 substituted, an alicyclic group or which may be substituted C6 ~ by C20 aromatic organic group, the which may be C3 ~ C20 substituted, respectively it may be the same or different. these aliphatic group, alicyclic group or aromatic Kimoto represents an oxygen atom, contained in the compound represented by the nitrogen atom may contain. Formula (11) to (14), one of the groups is a divalent organic group L or L ' binds to.)
　(9) or formula (10), L and L 'comprises oxyethylene chains, oxypropylene chains, (thio) ester group, one or more selected from (thio) amido group It represents a divalent organic group.
　in the formula (9) or formula (10), chain represents a monovalent or divalent organic group containing at least one selected polysiloxane chain, polyoxyalkylene chain. )
[Claim 5]
　The allyl carbonate polymer compound is diethylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-methyl-2-ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2,2,4-trimethyl 1,3-pentanediol, 1,4-dimethylolcyclohexane and 4,8-bis (hydroxymethyl) - [5.2.1.0 2, 6 ] at least one diol selected from tricyclodecane bis (allyl carbonate) compounds,
glycerol, trimethylolpropane And tris tris at least one triol selected from (hydroxyethyl) isocyanurate (allyl carbonate) compounds,
pentaerythritol, at least one tetraol tetra (allyl carbonate) selected from diglycerol and ditrimethylolpropane compounds,
hexa dipentaerythritol (allyl carbonate) compounds, and
it is selected the diols, mixed poly (allyl carbonate) compounds of the triol, the at least two compounds selected from tetraols and the dipentaerythritol, from comprising at least one composition according to claim 2.
[Claim 6]
　The allyl carbonate polymerizable compound,
(i) diethylene glycol bis (allyl carbonate) compounds and mixtures and oligomers thereof,
(ii) bis mixture of diethylene glycol and neopentyl glycol (allyl carbonate) compounds and mixtures and oligomers thereof,
(iii) diethylene glycol and tris poly (allyl carbonate) of a mixture of (hydroxyethyl) isocyanurate compounds and mixtures and oligomers thereof,
(iv) diethylene glycol and a mixture of trimethylolpropane poly (allyl carbonate) compound and the oligomer thereof mixture,
(v) poly (allyl carbonate) of a mixture of diethylene glycol and pentaerythritol compounds and mixtures and oligomers thereof,
(vi) diethylene glycol and neopentyl Poly mixture chill glycol and pentaerythritol (allyl carbonate) compounds and mixtures and oligomers thereof, and
(vii) poly (allyl carbonate) of diethylene glycol and neopentyl glycol and mixtures of pentaerythritol compound and a mixture of oligomers thereof and,
diethylene glycol bis (allyl carbonate) compounds, and poly (allyl carbonate) mixture comprising a mixture of oligomers thereof, and
comprises at least one member selected from a composition according to claim 2.
[Claim 7]
　The allyl ester polymerizable compound,
diallyl isophthalate or diallyl terephthalate or diallyl phthalate monomer selected from diallylorthophthalate,
said diallyl phthalate monomer, ethylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol, 1 , 2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2 - methyl-2-ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,4-dimethylol cyclo At least one diol diallyl ester monomers and oligomers thereof obtained by transesterification of a mixture of selected from hexane,
and the diallyl phthalate monomer, glycerol, trimethylolpropane, tris (hydroxyethyl) isocyanurate, pentaerythritol, diglycerol, ditrimethylolpropane, at least one polyol transesterification polyallyl ester monomer and oligomers thereof obtained by reaction of a mixture, and is selected from dipentaerythritol
dialkyl isophthalate having C1 ~ C3 alkyl group, dialkyl terephthalate, and at least one dialkyl phthalate selected from dialkyl ortho phthalate, allyl alcohol, diallyl And Boneto, comprises at least one selected from allyl ester monomer and oligomers thereof containing allyl carbonate group obtained by transesterification of a mixture of the diol or the polyol composition of claim 2.
[8.]
　The allyl ester polymerizable compound,
(i) and diallyl terephthalate, the diallyl terephthalate against 30% by weight of diethylene glycol bis (allyl carbonate) compounds and oligomer, mixtures,
(ii) of diallyl terephthalate and propylene glycol allyl ester compound obtained by transesterification of the mixture,
and the allyl ester compound, 20 wt% of diethylene glycol bis relative to the allyl ester compound (allyl carbonate) compound and its oligomer, of (iii) (ii) mixture,
(iv) obtained by transesterification of dimethyl terephthalate and allyl alcohol and diallyl carbonate and a mixture of diethylene glycol, allyl ester compound, allyl carbonate compound and Ariruesu Mixtures of compounds having Le and allyl carbonate groups, and
(v) the mixture obtained in (iv) and diethylene glycol bis (allyl carbonate) of 10 wt% relative to the mixture compound and its oligomer, a mixture of ,
comprises at least one selected from the polymerizable composition according to claim 2.
[Claim 9]
　The compound containing two or more allyloxycarbonyl group (A) is,
　with the allyl ester polymerizable compound and its oligomer as claimed in claim 7, and oligomers thereof wherein the allyl carbonate polymer compound and according to claim 5, the composition of claim 2 wherein the mixture of.
[Claim 10]
　An amount of the components (A) 0.3 ~ 5.0 parts by weight said component (B) relative to 100 parts by weight, the composition according to any one of claims 1-9.
[Claim 11]
　An amount of the components (A) 0.01 ~ 0.5 part by weight said component (C) relative to 100 parts by weight, the composition according to any one of claims 1-9.
[Claim 12]
　Including the claims 1 to 11 step of radically polymerizing a polymerizable composition according to any one of the method of manufacturing the organic glass comprising a photochromic performance.
[Claim 13]
　The process, the polymerizable composition according to any one of claims 1 to 11 is injected into a mold, which is polymerized 1 to 100 hours at a temperature in the range of 50 ~ 120 ° C., cast polymerization step including method of claim 12.
[Claim 14]
　Polymerizable composition polymerized hardened organic glasses according to any one of claims 1 to 11.
[Claim 15]
　Lenses made of organic glass according to claim 14.
[Claim 16]
　A polarizing film,
　at least one of which is formed on the surface, polarizing lens and a base layer made of an organic glass according to claim 14 of the polarizing film.