Composition for optical material, cured product, optical article, lens, and glasses

Abstract

The purpose of the present invention is to provide a composition for an optical material, a cured product, an optical article, a lens, and glasses, which are capable of achieving excellent performance of a functional dye. According to one embodiment, a composition for an optical material is provided. The composition for optical materials comprises: a compound for optical materials represented by formula (I); and at least one compound selected from the group consisting of a compound having a radically polymerizable group, a compound having an addition polymerization group, and a compound having a reactive group that reacts with the addition polymerization group.

Description

Technical Field

[0001] The present invention relates to a composition for optical materials, a cured product, an optical article, a lens and glasses. Background Art

[0002] Photochromic compounds are compounds that can reversibly obtain two or more isomers with different absorption spectra when irradiated with light containing ultraviolet rays such as sunlight. For example, if a colorless photochromic compound in a decolorized state is irradiated with ultraviolet rays, the color rapidly changes and isomerizes to a colored state. Photochromic compounds having such properties are used as lens materials for dimmer sunglasses that appear dark outdoors and transparent indoors.

[0003] Light-adjusting sunglasses use, for example, plastic lenses obtained by curing a polymerizable composition containing a photochromic compound. In order to improve the reactivity, durability, and other properties of the photochromic compound in the light-adjusting lens, the addition of various polymer compounds to the polymerizable composition has been studied.

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: International Publication No. 2021 / 241596

[0007] Patent Document 2: International Publication No. 2018 / 070383 Summary of the invention

[0008] Problem that the invention aims to solve

[0009] An object of the present invention is to provide an optical material composition, a cured product, an optical article, a lens, and glasses that can realize the excellent performance of a functional dye.

[0010] Solutions for solving problems

[0011] According to an embodiment, a composition for an optical material is provided, comprising: a compound for an optical material represented by formula (I); and at least one compound selected from the group consisting of a compound having a free radical polymerizable group, a compound having an addition-polymerizable group, and a compound having a reactive group that reacts with the addition-polymerizable group.

[0012]

[0013] In formula (I), p and q are each independently 1 to 43. p+q is 2 to 44. 1 and X 2R is independently hydrogen, mercaptoethyl, 3-mercaptopropionyl, allyl, acryloyl or methacryloyl. 1 is a divalent group represented by the following formula (Ia) or (Ib). 2 and R 3 It is methylene or ethylene.

[0014]

[0015] In formula (Ia), R 11 It is a linear or branched alkylene group having 2 to 10 carbon atoms. 12 and R 13 For the 11 Different structural groups. 12 and R 13 is a linear or branched alkylene group having 3 to 10 carbon atoms. a is 1 to 27. m and n are each independently 1 to 32. m+n is 2 to 32.

[0016]

[0017] In formula (Ib), R 14 It is a linear or branched alkylene group having 3 to 10 carbon atoms. 15 For the 14 Different structural groups. 15 is a linear or branched alkylene group having a carbon number of 3 or more and 10 or less. b is 1 or more and 25 or less. c is 1 or more and 31 or less.

[0018] According to an embodiment, a cured product is provided. The cured product is a cured product of the composition for an optical material according to an embodiment.

[0019] According to an embodiment, an optical article is provided, wherein the optical article includes the cured product according to the embodiment.

[0020] According to an embodiment, a lens is provided, which includes the optical article according to the embodiment.

[0021] According to an embodiment, a pair of glasses is provided, wherein the pair of glasses comprises the lens according to the embodiment.

[0022] Effects of the Invention

[0023] According to the present invention, there are provided a composition for an optical material, a cured product, an optical article, a lens, and glasses capable of realizing the excellent performance of a functional dye. DETAILED DESCRIPTION

[0024] [Optical material composition]

[0025] The optical material composition according to the embodiment comprises an optical material compound represented by formula (I) and other matrix-forming compounds. The matrix-forming compound comprises at least one compound selected from the group consisting of a compound having a free radical polymerizable group, a compound having an addition-polymerizable group, and a compound having a reactive group that reacts with an addition-polymerizable group.

[0026] In the cured product of the optical material composition according to the embodiment, a microphase separation structure is formed by the optical material compound represented by formula (I), and thus the performance of the functional pigment can be improved. The reason for this is described below.

[0027] First, functional pigments include compounds that have the ability to selectively absorb visible light, and compounds that develop, decolorize, or change color using energy such as light, heat, electric field, or pressure. Such functional pigments can exert specific functions by undergoing structural changes under specific conditions. Generally speaking, the matrix of plastic solids has a rigid structure. Therefore, functional pigments in solids are less likely to undergo structural changes than in solutions, and their functions may be limited.

[0028] In the compound for optical material represented by formula (I), R 1 The part is configured in R 1 The repeating structure with subscripts p and q at both ends of the part, that is, 2 O and R 3 The number of O atoms is greater than that of carbon atoms. 1 The part shows a ratio of R 2 O and R 3 O part has higher hydrophobicity. It can be considered that in a highly hydrophilic matrix, the more hydrophobic R 1 The parts gather together to form a hydrophobic domain. The hydrophobic domain is a soft area compared to the surrounding hydrophilic matrix. Moreover, the relatively hydrophobic functional pigment is easily arranged in the hydrophobic domain. Therefore, compared with the case where it is located in a rigid hydrophilic matrix, it is not easy to hinder the structural change and can exert excellent functionality. Here, if excessive R 1 If the solidified product is not aggregated, it may become cloudy and lose its optical properties. The compound for optical material represented by formula (I) has R 1 Contains R 11 O part, R 12 O and R 13 O or including R 14 O and R 15 O part, i.e., has at least two repeating structures, therefore, R 1 The excessive aggregation of the part is suppressed.1 The two ends of the part are equipped with highly hydrophilic R 2 O and R 3 O part, thereby improving the compatibility with a highly hydrophilic matrix and being able to inhibit R 1 It can be considered that, in a highly hydrophobic matrix, contrary to the above, R 1 The part can improve the compatibility with hydrophobic matrix, R 2 O and R 3 The O portion can form a hydrophilic domain.

[0029] As an example, polyurethane is used as a highly hydrophilic matrix, and X 1 and X 2 The case where the compound for an optical material represented by the formula (I) is hydrogen, that is, the case where the compound for an optical material represented by the formula (I) is a diol, will be described more specifically.

[0030] First, polyurethane is a resin containing a plurality of carbamate bonds (-OC(=O)N(H)-), wherein the carbamate bonds are generated by the addition polymerization of an isocyanate group (-N=C=O) as an addition polymerization reactive group and a hydroxyl group (-OH) as a reactive group that reacts with the addition polymerization reactive group. If a diisocyanate having isocyanate groups at both ends and a diol having hydroxyl groups at both ends undergo an addition polymerization reaction, a straight polymer chain containing a plurality of carbamate bonds is formed. It can be considered that in the polyurethane, hydrogen bonds are generated between polymer chains at the amine sites (-N(H)-) of the plurality of carbamate bonds of the polymer chain, thereby generating strong intermolecular interactions, thereby forming a rigid matrix. Here, as one of the diols, if a compound for optical materials represented by formula (I) is included, a matrix containing R 1 Department, R 2 O and R 3 A straight-chain polymer chain consisting of O parts and a part that does not form hydrogen bonds. 1 The hydrophobicity of the part is high, so it is easy to aggregate with each other in the polyurethane. Therefore, a structure in which multiple polymer chains are bonded to each other by hydrogen bonds is formed, and the R 1 Department, R 2 O and R 3 O-part and does not generate a hydrophobic domain at a site. This hydrophobic domain does not have a hydrogen bond inside, so it is softer than a urethane matrix in which polymer chains are bonded to each other by hydrogen bonds. And, as mentioned above, relatively hydrophobic functional pigments are easily arranged in this hydrophobic domain, so it is not easy to hinder structural changes and can exert excellent functionality.

[0031] (Compound for optical material represented by formula (I))

[0032] The optical material compound represented by formula (I) can be used as a compound for forming optical articles such as lenses, filters, films, window materials, etc. The optical material compound is, for example, a colorless, transparent or translucent liquid at room temperature. The optical material compound can be a diol, a dithiol, a diacrylate or a dimethacrylate. The structure of the optical material compound can be identified by, for example, nuclear magnetic resonance spectroscopy.

[0033]

[0034] In formula (I), X 1 and X 2 Each is independently hydrogen, mercaptoethyl, 3-mercaptopropionyl, allyl, acryloyl or methacryloyl.

[0035] X 1 and X 2 It is preferably a group that can react with or has high compatibility with the compound that becomes the main component of the matrix. 1 and X 2 It can be determined according to the type of the matrix. For example, in the case of a compound for an optical material used as a (thio)urethane resin, X 1 and X 2 Preferably, X is hydrogen, mercaptoethyl or 3-mercaptopropionyl. When used as a compound for an optical material for a (meth) acrylic resin, 1 and X 2 Preferred is an allyl group, an acryloyl group or a methacryloyl group.

[0036] R 2 and R 3 is methylene or ethylene. That is, the repeating unit R 2 O and R 3 O is (poly)methylene oxide or (poly)ethylene oxide. 2 O chain and R 3 O chain is respectively 1 The base is more hydrophilic.

[0037] In formula (I), p is a repeating unit R 2 O is the number of repetitions. q is the repeating unit R 3 O is repeated. p and q are each independently 1 or more and 43 or less. p and q may be 2 or more, 3 or more, 5 or more, or 7 or more. p and q may be 10 or less, 15 or less, or 20 or less.

[0038] p+q is 2 or more and 44 or less. p may be the same number as q or different numbers. If the values ​​of p and q are large, there is a tendency that the hydrophilicity of the optical material compound is improved, and there is a tendency that the compatibility of the optical material compound in the (thio)urethane matrix is ​​improved. p+q may be 4 or more, 6 or more, 7 or more, or 10 or more. p+q may be 15 or less, 16 or less, 20 or less, or 28 or less.

[0039] R 1 The compound for optical material represented by formula (I) having the following formula (Ia) may be a divalent group represented by formula (Ia) or (Ib). 12 O-based and R 13 O-based block adducts have R 2 O-based and R 3 The compound for optical material represented by formula (I) having the following formula (Ib) may be a compound having R 14 O-based and R 15 O-based random adducts have block additions R 2 O-based and R 3 O-based compounds.

[0040]

[0041] In formula (Ia), R 11 It is a linear or branched alkylene group having 2 to 10 carbon atoms. 11 It is preferably a linear or branched alkylene group having 3 to 10 carbon atoms, and more preferably an n-butylene group or an isobutylene group (-CH2CH(CH2CH3)-). 11 A linear alkylene group is preferred.

[0042] R 12 and R 13 is a linear or branched alkylene group having 3 or more and 10 or less carbon atoms. 11 O.R 12 O and R 13 O is (poly) alkylene oxide. 12 and R 13 are the same groups as each other.

[0043] R 12 and R 13 For the 11 Different structural groups. 12 and R 13 With R 11Due to the different structure, the aggregation of the compound for optical material is suppressed and white turbidity is less likely to occur. 12 and R 13 Preferably with R 2 and R 3 It is preferred that: the presence of R 12 O chain and R 13 The O chain has a higher hydrophobicity than the R 2 O chain and R 3 O chain. In this form, it is easy to obtain both the effect of forming a hydrophobic domain of the compound for optical material and the effect of inhibiting aggregation. 12 and R 13 It is preferably a branched alkylene group, more preferably a branched alkylene group having 3 to 5 carbon atoms, and still more preferably an isopropylidene group (—CH 2 CH(CH 3 )—).

[0044] a is 1 or more and 27 or less. If a is large, the hydrophobicity of the compound for optical material tends to be improved. a may be 2 or more, or 3 or more. a may be 5 or less, or 9 or less, or 15 or less.

[0045] m and n are each independently 1 or more and 32 or less. If the numbers of m and n are large, there is a tendency that the hydrophobicity of the compound for optical materials is improved. m and n are each independently 2 or more, 3 or more, 5 or more, or 7 or more. m and n can be 10 or less, 13 or less, or 15 or less. m can be the same number as n or a different number.

[0046] m+n is 2 or more and 32 or less. m+n may be 4 or more, 6 or more, 7 or more, or 10 or more. m+n may be 13 or less, 15 or less, or 20 or less.

[0047]

[0048] In formula (Ib), R 14 It is a linear or branched alkylene group having 3 to 10 carbon atoms. 14 can be the same as the above R 11 Same group.

[0049] R 15 For the 14 Different structural groups. 15 It is a linear or branched alkylene group having 3 to 10 carbon atoms. 15 can be the same as the above R 12 and R 13 Same group.

[0050] b is 1 or more and 25 or less. If the number of b is large, there is a tendency that the hydrophobicity of the compound for optical material is improved. b can be 2 or more, 3 or more, 5 or more, or 7 or more. b can be 9 or less, 10 or less, 13 or less, or 15 or less.

[0051] c is 1 or more and 31 or less. If the number of c is large, there is a tendency that the hydrophobicity of the compound for optical material is improved. c can be 2 or more, 3 or more, 5 or more, or 7 or more. c can be 10 or less, 13 or less, 15 or less, or 20 or less.

[0052] Specific examples of the compound for optical material are shown below.

[0053]

[0054]

[0055] The number average molecular weight of the optical material compound is, for example, greater than 500 and less than 2000. If a compound for optical materials having a large number average molecular weight is used, the photochromic properties of the cured product tend to be improved. If a compound for optical materials having a small number average molecular weight is used, the optical properties of the cured product tend to be improved (white turbidity is suppressed). The number average molecular weight of the optical material compound is preferably greater than 800 and less than 1600. The number average molecular weight of the optical material compound having a hydroxyl group can be calculated based on the hydroxyl value based on Japanese Industrial Standard (JIS) K 1557-1:2007. The number average molecular weight of the optical material compound not having a hydroxyl group can be calculated by nuclear magnetic resonance (NMR) spectroscopy.

[0056] Relative to the number average molecular weight of the compound for optical materials, R 2 The number average molecular weight of O chain and R 3 The ratio of the sum of the number average molecular weights of the O chains is, for example, 4% or more and 97% or less. A compound for optical materials having a high ratio tends to have high hydrophilicity. The ratio is preferably 10% or more and 70% or less, more preferably 20% or more and 60% or less, and further preferably 30% or more and 50% or less. 2 O chain and R 3 The number average molecular weight of the O chain can be calculated by combining the NMR method with the number average molecular weight of the above-mentioned compound for optical material. 2 O chain and R 3 O chain refers to R 2 O-based and R 3 A domain formed by repeating the O group according to the repetition number.

[0057] R 1 The number average molecular weight of the group is, for example, 300 or more and 1500 or less. 1 Optical material compounds having a high number average molecular weight of the group tend to have high hydrophobicity. 1 The number average molecular weight of the group is preferably 450 or more and 1300 or less, and more preferably 600 or more and 1000 or less. 1 The number average molecular weight of the group can be calculated by combining the NMR method with the number average molecular weight of the above-mentioned compound for optical material.

[0058] Relative to the number average molecular weight of the compound for optical materials, R 1 The ratio of the number average molecular weight of the base is, for example, 3% or more and 96% or less. The optical material compound with a high ratio tends to be highly hydrophobic. The ratio is preferably 30% or more and 90% or less, more preferably 35% or more and 70% or less, and further preferably 40% or more and 65% or less.

[0059] Relative to R 1 The number average molecular weight of the base, R 11 O chain or R 14 The ratio of the number average molecular weight of the O chain is, for example, 3% or more and 100% or less. A compound for optical materials having a high ratio tends to have high hydrophilicity. The ratio is preferably 5% or more and 60% or less, and more preferably 10% or more and 30% or less. 11 O chain and R 14 The number average molecular weight of the O chain can be calculated by combining the NMR method with the number average molecular weight of the above-mentioned compound for optical material. 11 O chain and R 14 O chain refers to R 11 O-based and R 14 A domain formed by repeating the O group according to the repetition number.

[0060] In the optical material composition, the proportion of the optical material compound is, for example, 5% by mass or more and 60% by mass or less. If the proportion is high, there is a tendency that the photochromic performance of the cured product is improved. If the proportion is too high, there is a tendency that the optical properties of the cured product are reduced. The proportion is preferably 10% by mass or more and 50% by mass or less, more preferably 15% by mass or more and 40% by mass or less. The proportion can be calculated by, for example, the NMR method.

[0061] The compound for optical material can be produced by, for example, the following method.

[0062] First, as a starting material, a first compound is prepared. As the first compound, HO-R 11 O-OH etc. have R in formula (Ia) 11 O structure compounds.

[0063] The first compound is reacted with the second compound to obtain a third compound. Regarding the reaction conditions, for example, in an autoclave replaced with nitrogen, the reaction temperature is set to 100° C. or more and 150° C. or less, the reaction pressure is set to 0.1 MPa or more and 1 MPa or less, and the reaction time is set to 1 hour or more and 10 hours or less. The reaction is preferably carried out in the presence of a catalyst. As a catalyst, an alkali metal hydroxide such as potassium hydroxide is used. The amount of the catalyst is, for example, 0.01 g or more and 1 g or less relative to 1 g of the first compound.

[0064] As the second compound, a compound having R represented by the following formula (A) is used. 12 O-structured cyclic ether compound. 12 The same as in formula (Ia). The amount of the second compound is, for example, 0.1 g or more and 10 g or less relative to 1 g of the first compound. By adjusting this amount, the value of a and the value of m+n in formula (I) can be adjusted.

[0065]

[0066] The third compound can be, for example, HO-(R 12 O)m-(R 11 O)a-(R 12 O)n-OH. 11 , R 12 , a, m and n have the same meanings as in formula (Ia).

[0067] Next, the third compound and the fourth compound are reacted to obtain a diol-type optical material compound represented by formula (I). Regarding the reaction conditions, for example, in an autoclave substituted with nitrogen, the reaction temperature is set to 100° C. to 150° C., the reaction pressure is set to 0.1 MPa to 1 MPa, and the reaction time is set to 1 hour to 10 hours.

[0068] As the fourth compound, for example, ethylene oxide is used. The amount of the fourth compound is, for example, 0.1 g or more and 10 g or less relative to 1 g of the first compound. By adjusting this amount, the value of p+q in formula (I) can be adjusted.

[0069] A functional group such as an acryloyl group can be introduced into the terminal of the diol type compound for an optical material obtained by the above method by a known method.

[0070] (Matrix-forming compound)

[0071] The matrix-forming compound includes at least one compound selected from the group consisting of a compound having a radical polymerizable group, a compound having an addition-polymerizable group, and a compound having a reactive group that reacts with the addition-polymerizable group.

[0072] As the radical polymerizable group, at least one functional group selected from the group consisting of acryloyl, (meth)acryloyl, allyl and vinyl can be cited. As the addition polymerization reactive group, at least one functional group selected from the group consisting of isocyanate, isothiocyanate and epoxy can be cited. As the reactive group that reacts with the addition polymerization reactive group, at least one functional group selected from the group consisting of hydroxyl, amino, mercapto and carboxyl can be cited.

[0073] In the optical material composition, the ratio of the matrix forming compound is, for example, 40% by mass or more and 95% by mass or less. If the ratio is low, there is a tendency that the photochromic performance of the cured product is improved. If the ratio is too low, there is a tendency that the optical properties of the cured product are reduced. The ratio is preferably 50% by mass or more and 90% by mass or less, more preferably 60% by mass or more and 85% by mass or less. The ratio can be calculated by, for example, NMR method.

[0074] When the optical material composition contains a compound having a radical polymerizable group, the optical material compound preferably has at least one acryloyl group or methacryloyl group. Such an optical material composition can be used as a photocurable composition that can be cured by photopolymerization.

[0075] When the optical material composition includes at least one of a compound having an addition-polymerization reactive group and a compound having a reactive group that reacts with the addition-polymerization reactive group, the optical material compound preferably has at least one hydroxyl group or thiol group. The optical material composition including both the compound having an addition-polymerization reactive group and the compound having a reactive group that reacts with the addition-polymerization reactive group can be used as a one-component curable composition. In addition, an optical material composition that does not contain a compound having an addition-polymerization reactive group and only contains a compound having a reactive group that reacts with the addition-polymerization reactive group and an optical material compound can be used as a curing agent for a two-component curable composition.

[0076] Below, as an example of a compound having an addition-polymerizing reactive group, a polyiso(thio)cyanate compound is described, as an example of a compound having a reactive group that reacts with an addition-polymerizing reactive group, a compound containing active hydrogen is described, and as an example of a compound having a free radical polymerizing group, a (meth)acrylate compound is described.

[0077] (Polyiso(thio)cyanate compounds)

[0078] The "polyiso(thio)cyanate compound" is a compound having two or more isocyanate groups, a compound having two or more isothiocyanate groups, or a compound having one or more each of an isocyanate group and an isothiocyanate group.

[0079] The polyisocyanate compound includes aliphatic isocyanate compounds, alicyclic isocyanate compounds, aromatic isocyanate compounds, sulfur-containing heterocyclic isocyanate compounds, sulfur-containing aliphatic isocyanate compounds, aliphatic sulfide isocyanate compounds, aromatic sulfide isocyanate compounds, aliphatic sulfone isocyanate compounds, aromatic sulfone isocyanate compounds, sulfonate isocyanate compounds, aromatic sulfonic acid amide isocyanate compounds, and the like.

[0080] In addition, the polyisocyanate compound includes a blocked isocyanate compound obtained by blocking the isocyanate group of the above-mentioned isocyanate compound using at least one blocking agent selected from the group consisting of alcohols, lactams, phenols, oximes, pyrazoles, thiols, active methylene compounds, malonic acid diester compounds and acetoacetate compounds.

[0081] The amount of the polyiso(thio)cyanate compound in the curable composition is preferably 10 parts by mass or more and 200 parts by mass or less, and more preferably 50 parts by mass or more and 150 parts by mass or less, based on 100 parts by mass of the active hydrogen-containing compound.

[0082] Among the polyisocyanate compounds, compounds suitable for forming optical articles having excellent transparency and mechanical strength, and particularly suitable for producing optical articles containing a photochromic compound, include compounds represented by the following formulae (I′) to (VIII).

[0083] Preferred aliphatic isocyanate compounds include compounds represented by the following formula.

[0084] OCN—R 100 —NCO (I')

[0085] In the formula, R 100 The alkylene group is an alkylene group having 1 to 10 carbon atoms, and may be a group in which a part of the methylene groups in the alkylene chain is substituted by a sulfur atom. Among them, a straight-chain group of pentamethylene, hexamethylene, heptamethylene, or octamethylene is preferred; or a branched-chain group in which a part of the hydrogen atoms of pentamethylene, hexamethylene, heptamethylene, or octamethylene is substituted by a methyl group. In addition, an alkylene group in which a part of the methylene groups is substituted by a sulfur atom is preferably a -CH2CH2SCH2CH2SCH2CH2- group.

[0086] Specific examples of the compound represented by formula (I') include pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,2-bis(2-isocyanatoethylthio)ethane, etc. These compounds may be used alone or in combination of two or more.

[0087] Preferred examples of the alicyclic isocyanate compound and the aromatic isocyanate compound include compounds represented by the following formula (II) and the following formula (III).

[0088]

[0089]

[0090] In the formula, R 101 R is an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, and may be the same group or different groups. 102 The alkyl group having 1 to 4 carbon atoms, when there are plural groups, may be the same group or different groups.

[0091] a 100 The integer is 2 or 3, b 100 Integer from 0 to 4, c 100 The integer is 0 to 4.

[0092] In R 101 In the formula (a), the alkyl group having 1 to 4 carbon atoms may be a straight chain group or a branched chain group. 101 Particularly preferred are a hydrogen atom, a methyl group, and an ethyl group. 102 In the formula (a), the alkyl group having 1 to 4 carbon atoms may be a straight chain group or a branched chain group. 102 A methyl group and an ethyl group are particularly preferred.

[0093] If the compound represented by formula (II) or formula (III) is specifically exemplified, it includes isophorone diisocyanate, xylene diisocyanate (o-, m-, p-), 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, etc. These compounds may be used alone or in combination of two or more.

[0094] Preferred examples of the alicyclic isocyanate compound and the aromatic isocyanate compound include compounds represented by the following formula (IV) and the following formula (V).

[0095]

[0096]

[0097] In the formula, R 103 are alkyl groups having 1 to 4 carbon atoms or hydrogen atoms, which may be the same group or different groups. 100 The integer is 0 to 4.

[0098] In R 103 In the formula (a), the alkyl group having 1 to 4 carbon atoms may be a straight chain group or a branched chain group. 103 A hydrogen atom, a methyl group, and an ethyl group are particularly preferred.

[0099] Specific examples of the compound represented by formula (IV) or the above formula (V) include 4,4'-diphenylmethane diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, etc. These compounds may be used alone or in combination of two or more.

[0100] Moreover, as a preferable alicyclic isocyanate compound, the compound represented by the following formula (VI) is mentioned.

[0101]

[0102] In the formula, R 104 are alkyl groups having 1 to 4 carbon atoms or hydrogen atoms, which may be the same group or different groups. 100 The integer is 0 to 4.

[0103] In R 104 In the formula (a), the alkyl group having 1 to 4 carbon atoms may be a straight chain group or a branched chain group. 104 A hydrogen atom, a methyl group, and an ethyl group are particularly preferred.

[0104] Specific examples of the compound represented by formula (VI) include norbornane diisocyanate, 2,5-bis(isocyanatomethyl)bicyclo〔2,2,1〕heptane, and 2,6-bis(isocyanatomethyl)-bicyclo〔2,2,1〕heptane. These compounds may be used alone or in combination of two or more.

[0105] (Sulfur-containing heterocyclic isocyanate compounds)

[0106] Preferred examples of the sulfur-containing heterocyclic isocyanate compound include compounds represented by the following formula (VII) and the following formula (VIII).

[0107]

[0108] In the formula, R 105R is an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, and may be the same group or different groups. 106 is a methylene or sulfur atom, R 107 is an alkylene group having 1 to 6 carbon atoms, or a group in which a part of the methylene groups in the alkylene group having 1 to 6 carbon atoms is substituted with a sulfur atom, 100 The integer is 0 to 2.

[0109] If the compound represented by formula (VII) or formula (VIII) is specifically exemplified, 2,5-bis(isocyanatomethyl)thiophene, 2,5-bis(isocyanatomethyl)-1,4-dithiane, 3,4-bis(isocyanatomethyl)tetrahydrothiophene, 4,5-bis(isocyanatomethyl)-1,3-dithiolane, etc. can be listed. These compounds can be used alone or in combination of two or more.

[0110] Furthermore, halogen-substituted products, alkyl-substituted products, alkoxy-substituted products, nitro-substituted products, prepolymer-type modified products formed with polyols, carbodiimide-modified products, urea-modified products, biuret-modified products, dimerization or trimerization reaction products of the above-mentioned polyisocyanates can also be used.

[0111] As the polyisothiocyanate compound, a compound in which the isocyanate group in the polyisocyanate compound represented by formula (I') to (VIII) is substituted with an isothiocyanate group can be used. More specifically, examples thereof include aliphatic isothiocyanate compounds, alicyclic isothiocyanate compounds, aromatic isothiocyanate compounds, sulfur-containing heterocyclic isothiocyanate compounds, heterocyclic isothiocyanate compounds, sulfur-containing aliphatic isothiocyanate compounds, and sulfur-containing aromatic isothiocyanate compounds.

[0112] If suitable isothiocyanate compounds are specifically exemplified, examples of aliphatic isothiocyanate compounds include hexamethylene diisothiocyanate, 1,2-diisothiocyanatoethane, 1,3-diisothiocyanatopropane, 1,4-diisothiocyanatobutane, 1,6-diisothiocyanatohexane, 2,4,4-trimethylhexamethylene diisothiocyanate, thiobis(3-isothiocyanatopropane), thiobis(2-isothiocyanatoethane), and dithiobis(2-isothiocyanatoethane).

[0113] Examples of the alicyclic isothiocyanate compound and the aromatic isothiocyanate compound include p-phenylene diisopropylidene diisocyanate, 1,2-diisothiocyanatobenzene, 1,3-diisothiocyanatobenzene, 1,4-diisothiocyanatobenzene, 2,4-diisothiocyanatotoluene, isophorone diisothiocyanate, xylene diisothiocyanate (o-, m-, p-), 2,4-toluene diisothiocyanate, 2,6-toluene diisothiocyanate, and cyclohexane diisothiocyanate. Examples of the alicyclic isothiocyanate compound and the aromatic isothiocyanate compound include 1,1'-methylenebis(4-isothiocyanatobenzene), 1,1'-methylenebis(4-isothiocyanato-2-methylbenzene), and 1,1'-methylenebis(4-isothiocyanato-3-methylbenzene).

[0114] Preferred alicyclic isothiocyanate compounds include 2,4-bis(isothiocyanatomethyl)norbornane, 2,5-bis(isothiocyanatomethyl)norbornane, 2,6-bis(isothiocyanatomethyl)norbornane, 3,5-bis(isothiocyanatomethyl)norbornane, and norbornane diisocyanate.

[0115] Preferred sulfur-containing heterocyclic isocyanate compounds include thiophene-2,5-diisothiocyanate, 1,4-dithiane-2,5-diisothiocyanate, 2,5-bis(isothiocyanatomethyl)-1,4-dithiane, and 4,5-bis(isothiocyanatomethyl)-1,3-dithiolane.

[0116] As compounds having both isocyanate groups and isothiocyanate groups, the following compounds can be cited. For example, compounds in which at least one isocyanate group in the polyisocyanate compounds specifically exemplified above is changed to an isothiocyanate group. In addition, compounds in which at least one isothiocyanate group in the polyisothiocyanate compounds specifically exemplified above is changed to an isocyanate group.

[0117] The compound having an iso(thio)cyanate group blocked by a blocking agent (hereinafter also referred to as a blocked iso(thio)cyanate compound) can be obtained by reacting at least one blocking agent selected from the group consisting of alcohols, lactams, phenols, oximes, pyrazoles, thiols, active methylene compounds, malonic acid diester compounds and acetoacetate compounds with the iso(thio)cyanate group of the aforementioned polyiso(thio)cyanate compound. The conditions for reacting the blocking agent with the iso(thio)cyanate group vary depending on the type of the blocking agent, and therefore, can be appropriately determined according to the selected blocking agent. It should be noted that the protection of the iso(thio)cyanate group based on the blocking agent can be confirmed by Fourier transform infrared spectroscopy (FT-IR).

[0118] By using a blocked iso(thio)cyanate compound, the usable time of the urethane curable composition can be further prolonged.

[0119] Preferred examples of the isocyanate compound include pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, isophorone diisocyanate, norbornane diisocyanate, 2,5-bis(isocyanatomethyl)-bicyclo〔2,2,1〕-heptane, 2,6-bis(isocyanatomethyl)-bicyclo〔2,2,1〕-heptane, 1,2-bis(2-isocyanatoethylthio)ethane, xylene diisocyanate (o-, m-, p-), 2,4-toluene diisocyanate, 2,6-toluene diisocyanate and 4,4′-diphenylmethane diisocyanate, which may be used alone or in the form of a mixture thereof.

[0120] (Compounds containing active hydrogen)

[0121] Examples of the active hydrogen-containing compound include aliphatic poly(thiol) compounds and aromatic poly(thiol) compounds.

[0122] The amount of the active hydrogen-containing compound in the composition for an optical material is preferably 20% by mass or more and 60% by mass or less.

[0123] When the optical material composition contains a polyiso(thio)cyanate compound, the amount of the active hydrogen-containing compound is preferably 10 parts by mass or more and 200 parts by mass or less, and more preferably 80 parts by mass or more and 150 parts by mass or less, based on 100 parts by mass of the polyiso(thio)cyanate compound.

[0124] Among the poly(thiol) compounds, compounds suitable for forming optical articles having excellent transparency and heat resistance, and particularly suitable for producing optical articles containing a photochromic compound, include compounds represented by the following formulae (IX) to (XVII).

[0125] (Aliphatic poly(thiol) compounds)

[0126] Preferred aliphatic poly(thiol) compounds include compounds represented by the following formula (IX).

[0127]

[0128] In the formula, R 108 is a hydrogen atom or the following formula (X). 109 R is a hydrogen atom, a methyl group or an ethyl group, which may be the same or different. 110is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and when there are two or more of them, they may be the same or different. 100 0~2, p 100 1~6, q 100 is 0~10, r 100 2~4, o 100 +r 100 is 4.

[0129]

[0130] In the formula, R 111 It is an alkylene group having 1 to 6 carbon atoms.

[0131] R 111 is an alkyl group having 1 to 6 carbon atoms, which may be a straight-chain group or a branched-chain group. 111 Particularly preferred are a methyl group, an ethyl group, a trimethyl group and a propyl group.

[0132] Specific examples of the compound represented by formula (IX) include trimethylolpropane, pentaerythritol, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), and the like.

[0133] Among the preferred aliphatic poly(thiol) compounds, examples of the polyfunctional poly(thiol) compound having an ether bond include compounds represented by the following formula (XI).

[0134]

[0135] In the formula, F 100 At least two of them are groups represented by formula (XII). In addition, other groups include 1 to 6 alkyl groups, which may be straight-chain groups or branched groups. 100 Particularly preferred are methyl, ethyl, trimethyl and propyl. 100 If two or more of the groups are groups represented by formula (XII), they may be the same groups or different groups.

[0136]

[0137] R 112 is a hydrogen atom or a group having the same meaning as that of the above formula (X), and may be the same group or different groups. 113 They are hydrogen atoms, methyl groups or ethyl groups, which may be the same groups or different groups. 100 1~6, t 100 It ranges from 0 to 10.

[0138] Specific examples of the compound represented by formula (XI) include ditrimethylolpropane, dipentaerythritol, ditrimethylolpropane tetrakis(3-mercaptopropionate), and dipentaerythritol hexakis(3-mercaptopropionate).

[0139] Among the preferred aliphatic poly(thiol) compounds, it is preferred to use a compound represented by the following formula (XIII) as a polyfunctional polythiol compound.

[0140]

[0141] R 114 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a group in which a part of the methylene groups of an alkyl group having 1 to 6 carbon atoms is substituted with a sulfur atom, and in the presence of a plurality of R 114 In the case of , they may be the same group or different groups.

[0142] R 115 is an alkylene group having 1 to 10 carbon atoms, a group in which a part of the methylene groups in the aforementioned alkylene group having 1 to 10 carbon atoms is substituted by a sulfur atom, or a group in which a part of the hydrogen atoms in the aforementioned alkylene group having 1 to 10 carbon atoms is substituted by a thiol group, and in the presence of a plurality of R 115 In the case of , they may be the same group or different groups.

[0143] u 100 is an integer from 2 to 4, v 100 is an integer from 0 to 2, u 100 +v 100 is 4.

[0144] In R 114 In the example, the alkyl group having 1 to 6 carbon atoms may be a linear group or a branched group, wherein R 114 Preferred are hydrogen atoms, methyl groups and ethyl groups. Specific examples of groups in which a part of the methylene groups in an alkyl chain having 1 to 6 carbon atoms is substituted with a sulfur atom include -CH2SCH3 and the like.

[0145] In R 115 In the formula (a), the alkylene group having 1 to 10 carbon atoms may be a straight chain group or a branched chain group. 115 Particularly preferred are methylene, ethylene, trimethylene, and propylene. In addition, specific groups in which a part of the methylene groups in an alkylene chain having 1 to 10 carbon atoms is substituted with a sulfur atom include -CH2S-, -CH2CH2S-, -CH2CH2CH2S-, and the like. Furthermore, groups in which a part of the hydrogen atoms in an alkyl chain having 1 to 6 carbon atoms is substituted with a thiol group include groups such as -CH2SCH(SCH2SH)-.

[0146] If the compound represented by formula (XIII) is specifically exemplified, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiooctane, 1,1,1,1-tetrakis(mercaptomethyl)methane, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 4,7-dimercaptomethyl-3,6,9-trithio-1,11-undecanedithiol, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithioundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithioundecane, and the like can be cited.

[0147] Among the preferred aromatic polythiol compounds, examples of polythiol compounds containing a phenyl group include compounds represented by the following formula (XIV).

[0148]

[0149] R 116 is an alkylene group having 1 to 6 carbon atoms, or a group in which a part of the methylene groups in the alkylene group having 1 to 6 carbon atoms is substituted with a sulfur atom, 100 is 3.

[0150] In R 116 In the formula (a), the alkylene group having 1 to 6 carbon atoms may be a straight chain group or a branched chain group. 116 Preferred are methylene, ethylene, trimethylene, and propylene. Specifically, groups in which a part of the methylene groups in the alkylene chain having 1 to 6 carbon atoms is substituted by sulfur atoms include -CH2CH2CH2SCH2-, -CH2CH2SCH2-, and -CH2SCH2-. If the compound represented by formula (XIV) is specifically exemplified, 1,3,5-tris(mercaptopropylthiomethyl)benzene can be cited.

[0151] Among the preferred poly(thiol) compounds other than those mentioned above, examples of the poly(thiol) compound having a triazine ring include compounds represented by the following formula (XV).

[0152]

[0153] R 117 are alkyl groups having 1 to 6 carbon atoms or groups represented by the following formula (XVI). 117 At least two of them are groups represented by formula (XVI), R 117 They may be the same group or different groups.

[0154]

[0155] R 118 and R119 is an alkylene group having 1 to 6 carbon atoms. 120 is an oxygen atom or a sulfur atom.

[0156] In R 118 and R 119 In the formula (a), the alkylene group having 1 to 6 carbon atoms may be a straight chain group or a branched chain group. 118 and R 119 Preferred are methylene, ethylene, trimethylene and propylene. Specific examples of the compound represented by formula (XV) include 2-mercaptomethanol and tris{(3-mercaptopropionyloxy)-ethyl}isocyanurate.

[0157] Among the poly(thiol) compounds other than those mentioned above, compounds having a silsesquioxane structure can be preferably used. The compound having a silsesquioxane structure has various molecular structures such as cage, ladder, and random structures, and is a compound represented by the following formula (XVII).

[0158]

[0159] In the formula, there are multiple R 500 They may be the same or different and are hydrogen atoms, alkyl groups, cycloalkyl groups, alkoxy groups, phenyl groups, and organic groups containing at least two hydroxyl groups and / or thiol groups in one molecule. 100 An integer from 3 to 100.

[0160] The poly(thiol) compounds can be used without particular limitation, and multiple types can be used in combination in consideration of the functionality and mechanical properties of the resulting cured product. Among them, in order to produce photochromic optical articles with excellent properties and curable compositions with excellent moldability and good handling, poly(thiol) compounds preferably have 3 to 6 active hydrogen-containing groups in one molecule.

[0161] Preferred poly(thiol)ol compounds include trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate), 4-mercaptomethyl-1,8-dimercapto-3,6-dithiooctane, and tris-{(3-mercaptopropionyloxy)-ethyl}-isocyanurate. Among them, at least one of trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), and dipentaerythritol hexa(3-mercaptopropionate) is more preferably used.

[0162] Among these, dipentaerythritol hexa(3-mercaptopropionate) is particularly preferred because it can improve the photochromicity and mechanical properties of the obtained cured product. From the viewpoint of photochromicity, dipentaerythritol hexa(3-mercaptopropionate) is preferably used alone as the poly(thiol) compound, but dipentaerythritol hexa(3-mercaptopropionate) has a high viscosity. When a cured product is obtained by injection molding polymerization, other poly(thiol) compounds may be mixed for viscosity adjustment. Preferred examples of other poly(thiol) compounds include trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), 1,6-hexanediol bis(3-mercaptopropionate), 1,2-bis[(2-mercaptoethyl)thio]-3-mercaptopropane, 2,2-bis(mercaptomethyl)-1,4-butanedithiol, 2,5-bis(mercaptomethyl)-1,4-dithiane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiooctane, 1,1,1,1-Tetrakis(mercaptomethyl)methane, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 4,6-bis(mercaptomethylthio)-1,3-dithiane, tris-{(3-mercaptopropionyloxy)-ethyl}-isocyanurate, and particularly trimethylolpropane tris(3-mercaptopropionate) are particularly preferred because they can maintain excellent photochromic properties and improve workability.

[0163] (Polyamine)

[0164] The compound containing active hydrogen may include polyamines. Polyamines can function as chain extenders for polymers or prepolymers having carbamate bonds. If polyamines are used, polymers or prepolymers having (thio)carbamate urea bonds can be obtained. The molar mass of the polyamine is preferably 50 or more and 500 or less. If a polyamine having a molar mass within this range is used, there is a tendency to obtain a polymer having a desired number average molecular weight. The molar mass of the polyamine is more preferably 50 or more and 300 or less. The polyamine includes diamines and triamines, preferably diamines.

[0165] Examples of the polyamine include isophoronediamine, ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,2-diaminobutane, 1,3-diaminobutane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, piperazine, N,N-bis-(2-aminoethyl)piperazine, bis-(4-aminocyclohexyl)methane, bis-(4-amino-3-butylcyclohexyl)methane, 1,2- Diaminocyclohexane, 1,3-diaminocyclohexane and 1,4-diaminocyclohexane, norbornanediamine, hydrazine, adipic acid dihydrazide, phenylenediamine, 4,4'-diphenylmethanediamine, N,N'-diethylethylenediamine, N,N'-dimethylethylenediamine, N,N'-dipropylethylenediamine, N,N'-dibutylethylenediamine, N-methylethylenediamine, N-ethylethylenediamine, bis(hexamethylene)triamine, 1,2,5-pentanetriamine, etc.

[0166] The polyamine preferably contains at least one selected from the group consisting of isophoronediamine, ethylenediamine, bis-(4-aminocyclohexyl)methane, and 1,6-diaminohexane.

[0167] (Monofunctional active hydrogen compound)

[0168] The active hydrogen-containing compound may include a monofunctional active hydrogen compound. The monofunctional active hydrogen compound has one active hydrogen group. The monofunctional active hydrogen compound reacts with an iso(thio)cyanate group to stop further reaction. The active hydrogen group includes at least one selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, and a thiol group.

[0169] The monofunctional active hydrogen compound includes, for example, at least one selected from the group consisting of a monoalcohol compound containing one hydroxyl group, a monoamine compound containing one amino group, a carboxylic acid containing one carboxyl group, and a monothiol compound containing one thiol group. As the monofunctional active hydrogen compound, a single type may be used, or a plurality of types may be mixed and used.

[0170] The monofunctional active hydrogen compound is preferably a monoamine compound. When a monoamine compound is used, a polymer or prepolymer having a (thio)urea bond can be obtained.

[0171] The monofunctional active hydrogen compound preferably contains an amine having a 2,2,6,6-pentamethyl-4-piperidinyl moiety as shown in the following formula (3). The amine having a 2,2,6,6-pentamethyl-4-piperidinyl moiety can function as a hindered amine, and thus can improve the light stability of the cured product.

[0172]

[0173] In formula (3), R 21 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. 22is an alkylene group having 1 to 3 carbon atoms. a is 0 or 1.

[0174] The monofunctional active hydrogen compound is preferably R 21 1,2,2,6,6-pentamethyl-4-aminopiperidine wherein a is 0 and methyl is 1,2,2,6,6-pentamethyl-4-aminopiperidine.

[0175] (Prepolymer)

[0176] The optical material composition may include a prepolymer. The prepolymer is a reaction product of the above-mentioned polyiso(thio)cyanate compound and a compound containing an active hydrogen group, and includes a carbamate prepolymer having one or more iso(thio)cyanate groups or active hydrogen groups. In addition, the prepolymer is a reaction product of the carbamate prepolymer and polyamines, and includes a carbamate prepolymer having one or more iso(thio)cyanate groups or active hydrogen groups. The prepolymer may have two or more iso(thio)cyanate groups or active hydrogen groups.

[0177] ((Meth)acrylate compound)

[0178] As the (meth)acrylate compound, for example, a difunctional (meth)acrylic polymerizable compound, a multifunctional (meth)acrylic polymerizable compound, a monofunctional (meth)acrylic polymerizable compound, etc. can be used, and preferably a difunctional (meth)acrylic polymerizable compound is included. Specific examples of the difunctional (meth)acrylic polymerizable compound include compounds represented by the following formulas (5), (6) and (7).

[0179]

[0180] In the formula, R 14’ and R 15’ Each is a hydrogen atom or a methyl group, j and k are each independently an integer greater than or equal to 0, and j+k is 2 or more and 50 or less in average value.

[0181] It should be noted that the polymerizable compound represented by the above formula (5) is usually obtained as a mixture of molecules having different molecular weights. Therefore, j and k are represented by average values.

[0182] Specific examples of the compound represented by the above formula (5) are shown below.

[0183] diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, pentaethylene glycol dimethacrylate, pentapropylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, pentaethylene glycol diacrylate, tripropylene glycol diacrylate, tetrapropylene glycol diacrylate, pentapropylene glycol diacrylate, dimethacrylate formed from a mixture of polypropylene glycol and polyethylene glycol (having two repeating units of polyethylene and two repeating units of polypropylene), polyethylene glycol dimethacrylate (especially having an average molecular weight of 330), polyethylene glycol dimethacrylate (especially having an average molecular weight of 330), It is an average molecular weight of 536), polyethylene glycol dimethacrylate (especially an average molecular weight of 736), tripropylene glycol dimethacrylate, tetrapropylene glycol dimethacrylate, polypropylene glycol dimethacrylate (especially an average molecular weight of 536), polyethylene glycol diacrylate (especially an average molecular weight of 258), polyethylene glycol diacrylate (especially an average molecular weight of 308), polyethylene glycol diacrylate (especially an average molecular weight of 508), polyethylene glycol diacrylate, (especially an average molecular weight of 708), polyethylene glycol methacrylate acrylate (especially an average molecular weight of 536).

[0184]

[0185] In the formula, R 16 and R 17 are hydrogen atoms or methyl groups,

[0186] R 18 and R 19 are hydrogen atoms or methyl groups,

[0187] R 20 is a hydrogen atom or a halogen atom,

[0188] B is -O-, -S-, -(SO2)-, -CO-, -CH2-, -CH=CH-, -C(CH3)2-, -C

[0189] (CH3)(C6H5)-,

[0190] l and m are each an integer greater than or equal to 1, and l+m is greater than or equal to 2 and less than or equal to 30 as an average value.

[0191] It should be noted that the polymerizable compound represented by the above formula (6) is usually obtained as a mixture of molecules having different molecular weights. Therefore, l and m are represented by average values.

[0192] Specific examples of the compound represented by the above formula (6) include the following bisphenol A di(meth)acrylate.

[0193] 2,2-bis[4-methacryloyloxy·ethoxy)phenyl]propane (l+m=2), 2,2-bis[4-methacryloyloxy·diethoxy)phenyl]propane (l+m=4), 2,2-bis[4-methacryloyloxy·polyethoxy)phenyl]propane (l+m=7), 2,2-bis(3,5-dibromo-4-methacryloyloxyethoxyphenyl)propane (l+m=2), 2,2-bis(4-methacryloyloxydipropoxyphenyl)propane (l+m=4), 2,2-bis[4-acryloyloxy·diethoxy)phenyl]propane (l+m=4), 2,2-bis[4-acryloyloxy·polyethoxy)phenyl]propane 2,2-bis[4-methacryloyloxy(polyethoxy)phenyl]propane (l+m=10), 2,2-bis[4-methacryloyloxy(polyethoxy)phenyl]propane (l+m=17), 2,2-bis[4-methacryloyloxy(polyethoxy)phenyl]propane (l+m=30), 2,2-bis[4-acryloyloxy(polyethoxy)phenyl]propane (l+m=10), 2,2-bis[4-acryloyloxy(polyethoxy)phenyl]propane (l+m=20).

[0194]

[0195] In the formula, R 21 and R 22 are hydrogen atoms or methyl groups,

[0196] n is a number from 1 to 20, calculated as the average value.

[0197] A and A' may be the same or different and are each a linear or branched alkylene group having 2 to 15 carbon atoms. When there are a plurality of A's, they may be the same group or different groups.

[0198] The compound represented by the above formula (7) can be produced by reacting polycarbonate diol with (meth)acrylic acid.

[0199] Here, examples of the polycarbonate diol used include the following: polycarbonate diols (having a number average molecular weight of 500 to 2,000) obtained by phosgene chlorination of polyalkylene glycols such as trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, octamethylene glycol, and nonamethylene glycol;

[0200] A polycarbonate diol (number average molecular weight of 500 to 2,000) obtained by phosgene chlorination of a mixture of two or more polyalkylene glycols, for example, a mixture of trimethylene glycol and tetramethylene glycol, a mixture of tetramethylene glycol and hexamethylene glycol, a mixture of pentamethylene glycol and hexamethylene glycol, a mixture of tetramethylene glycol and octamethylene glycol, a mixture of hexamethylene glycol and octamethylene glycol, etc.;

[0201] Polycarbonate diol (number average molecular weight 500 to 2,000) obtained by phosgene chlorination of 1-methyltrimethylene glycol.

[0202] As the (meth)acrylate compound, a bifunctional (meth)acrylic polymerizable compound having a urethane bond can be used.

[0203] The difunctional (meth) acrylic polymerizable compound having a urethane bond is, for example, a reaction product of a polyol and a polyisocyanate. Here, as the polyisocyanate, for example, hexamethylene diisocyanate, isophorone diisocyanate, lysine diisocyanate, 2,2,4-hexamethylene diisocyanate, dimer acid diisocyanate, isopropylidene bis-4-cyclohexyl isocyanate, dicyclohexylmethane diisocyanate, norbornene diisocyanate, norbornene methane diisocyanate or methylcyclohexane diisocyanate can be cited.

[0204] On the other hand, examples of polyols include polyalkylene glycols having repeating units of ethylene oxide, propylene oxide, and hexylene oxide having 2 to 4 carbon atoms, or polyester glycols such as polycaprolactone glycol. In addition, examples include polycarbonate glycols, polybutadiene glycols, or ethylene glycol, propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 1,8-nonanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanediol, and 1,4-cyclohexanedimethanol.

[0205] In addition, urethane (meth) acrylates and the like may also be used. The urethane (meth) acrylates are reaction mixtures obtained by further reacting a urethane prepolymer obtained by the reaction of these polyisocyanates with polyols with 2-hydroxy (meth) acrylate; and reaction mixtures obtained by directly reacting the aforementioned diisocyanate with 2-hydroxy (meth) acrylate.

[0206] Examples of difunctional (meth)acrylic polymerizable compounds having a urethane bond include U-2PPA (molecular weight 482), UA-122P (molecular weight 1,100), U-122P (molecular weight 1,100), U-108A, U-200PA, UA-511, U-412A, UA-4100, UA-4200, UA-4400, UA-2235PE, UA-160TM, UA-6100, UA-6200, U-108, UA-4000, and UA-512 manufactured by Shin-Nakamura Chemical Co., Ltd.; EB4858 (molecular weight 454) manufactured by DAICEL-ALLNEX; and UX-2201, UX3204, UX4101, 6101, 7101, and 8101 manufactured by Nippon Kayaku Co., Ltd.

[0207] As the (meth)acrylate compound, a difunctional (meth)acrylic polymerizable compound other than the above can be used. As such a (meth)acrylate compound, a compound having a (meth)acryloyl group at both ends of an alkylene group which may have a substituent can be cited. As such a (meth)acrylate compound, an alkylene group having 6 to 20 carbon atoms is preferred. Specifically, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol diacrylate, 1,9-nonanediol dimethacrylate, 1,10-decanediol diacrylate, 1,10-decanediol dimethacrylate, etc. can be cited.

[0208] As other (meth) acrylate compounds, difunctional (meth) acrylate monomers including sulfur atoms can be listed. The sulfur atom preferably forms a part of the molecular chain in the form of a thioether group. Specifically, bis(2-methacryloyloxyethylthioethyl) sulfide, bis(methacryloyloxyethyl) sulfide, bis(acryloyloxyethyl) sulfide, 1,2-bis(methacryloyloxyethylthio) ethane, 1,2-bis(acryloyloxyethyl) ethane, bis(2-methacryloyloxyethylthioethyl) sulfide, bis(2-acryloyloxyethylthioethyl) sulfide, 1,2-bis(methacryloyloxyethylthioethylthio) ethane, 1,2-bis(acryloyloxyethylthioethylthio) ethane, 1,2-bis(acryloyloxyethylthioethylthio) ethane, 1,2-bis(methacryloyloxyisopropylthioisopropyl) sulfide, 1,2-bis(acryloyloxyisopropylthioisopropyl) sulfide.

[0209] In the (meth)acrylate compound, one of the components may be used, or a plurality of the components described above may be used.

[0210] Next, the polyfunctional (meth)acrylic polymerizable compound will be described.

[0211] Examples of the polyfunctional (meth)acrylic polymerizable compound include compounds represented by the following formula (8).

[0212]

[0213] In the formula, R 23 is a hydrogen atom or a methyl group,

[0214] R 24 is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms,

[0215] R 25 is a trivalent to hexavalent organic group having 1 to 10 carbon atoms,

[0216] o is a number from 0 to 3 as the average value, and p is a number from 3 to 6.

[0217] As R 24 The alkyl group having 1 to 2 carbon atoms represented by is preferably a methyl group. 25 Examples of the organic group include groups derived from polyols, tri- to hexavalent hydrocarbon groups, and tri- to hexavalent organic groups containing a urethane bond.

[0218] The compounds represented by the above formula (8) are shown below in detail: trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, tetramethylolmethane trimethacrylate, tetramethylolmethane triacrylate, tetramethylolmethane tetramethacrylate, tetramethylolmethane tetraacrylate, trimethylolpropane triethylene glycol trimethacrylate, trimethylolpropane triethylene glycol triacrylate, ditrimethylolpropane tetramethacrylate, ditrimethylolpropane tetraacrylate.

[0219] Moreover, as a polyfunctional (meth)acrylic polymerizable compound, the polyfunctional (meth)acrylic polymerizable compound which has a urethane bond is mentioned.

[0220] The polyfunctional (meth) acrylic polymerizable compound having a carbamate bond is obtained by reacting the polyisocyanate compound described in the difunctional (meth) acrylic polymerizable compound having a carbamate bond with a polyol compound such as glycerol, trimethylolpropane, pentaerythritol, and dipentaerythritol, and is a compound having three or more (meth) acrylic ester groups in the molecule. Commercially available products include U-4HA (molecular weight of 596, number of functional groups 4), U-6HA (molecular weight of 1,019, number of functional groups 6), U-6LPA (molecular weight of 818, number of functional groups 6), and U-15HA (molecular weight of 2,300, number of functional groups 15) manufactured by Shin-Nakamura Chemical Industry Co., Ltd.

[0221] In addition, as a multifunctional (meth) acrylic polymerizable compound, compounds other than the above can be used. As such a multifunctional (meth) acrylic polymerizable compound, a compound obtained by modifying the terminal of a polyester compound with a (meth) acryloyl group can be cited. Depending on the molecular weight of the polyester compound used as the raw material and the modification amount of the (meth) acryloyl group, various polyester (meth) acrylate compounds can use commercial products. Specifically, tetrafunctional polyester oligomers (molecular weight of 2,500 to 3,500, DAICEL-ALLNEX, EB80, etc.), hexafunctional polyester oligomers (molecular weight of 6,000 to 8,000, DAICEL-ALLNEX, EB450, etc.), hexafunctional polyester oligomers (molecular weight of 45,000 to 55,000, DAICEL-ALLNEX, EB1830, etc.), tetrafunctional polyester oligomers (especially those with a molecular weight of 10,000, Daiichi Kogyo Seiyaku, GX8488B, etc.) can be cited.

[0222] By using the polyfunctional (meth) acrylic polymerizable compounds exemplified above, the crosslinking density can be increased by polymerization, and the surface hardness of the obtained cured product can be increased. Therefore, in particular, when the obtained photochromic cured product (laminated body) is prepared by a coating method, it is preferred to use a polyfunctional (meth) acrylic polymerizable compound.

[0223] The polyfunctional (meth)acrylic polymerizable compound may be used alone or in combination of the components described above.

[0224] Next, the monofunctional (meth)acrylic polymerizable compound will be described.

[0225] Examples of the monofunctional (meth)acrylic polymerizable compound include compounds represented by the following formula (9).

[0226]

[0227] In the formula, R 26 is a hydrogen atom or a methyl group,

[0228] R 27 is a hydrogen atom, an isocyanate group, an isothiocyanate group, a methyldimethoxysilyl group, a trimethoxysilyl group or a glycidyl group,

[0229] q is an integer from 0 to 10,

[0230] r is an integer from 0 to 20.

[0231] The compound represented by the above formula (9) is specifically shown below.

[0232] Methoxypolyethylene glycol methacrylate (especially having an average molecular weight of 293), methoxypolyethylene glycol methacrylate (especially having an average molecular weight of 468), methoxypolyethylene glycol acrylate (especially having an average molecular weight of 218), methoxypolyethylene glycol acrylate, (especially having an average molecular weight of 454), stearyl methacrylate, lauryl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, octyl acrylate, lauryl acrylate, 2-isocyanatoethyl methacrylate, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, glycidyl methacrylate.

[0233] (Functional pigment)

[0234] The functional dye includes, for example, at least one selected from the group consisting of a photochromic compound, an ultraviolet light absorber, a blue light absorber, an infrared absorber, and an electrochromic compound.

[0235] As the photochromic compound, at least one selected from the group consisting of, for example, a chromene compound, a fulgide compound and a spirooxazine compound is used. As the photochromic compound, a chromene compound is preferably used. The chromene compound includes a compound having a 1-benzopyran skeleton, a spiropyran compound including a spiropyran skeleton and a naphthopyran compound having a naphthopyran skeleton. The naphthopyran compound includes an indenonaphthopyran compound having an indenonaphthopyran skeleton. The chromene compound preferably includes an indenonaphthopyran compound having an indeno〔2,1-f〕naphtho〔1,2-b〕pyran skeleton. The cured product containing the chromene compound having an indeno〔2,1-f〕naphtho〔1,2-b〕pyran skeleton tends to have excellent durability.

[0236] The indenonaphthopyran compound preferably includes a compound represented by the following formula (IIIa).

[0237]

[0238] In formula (IIIa), Q 11 , Q 12 , Q 13 , Q 14 , Q 15 , Q 16 and Q 17Each is independently a hydrogen atom, a hydroxyl group, a methoxycarbonyl group, an ethoxycarbonyl group, an alkyl group, a cycloalkyl group, a haloalkyl group, an alkoxy group, an amino group, a substituted amino group, a heterocyclic group optionally having a substituent, a halogen atom, an alkylthio group, an arylthio group optionally having a substituent, a nitro group, a formyl group, a hydroxycarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aralkyl group optionally having a substituent, an aralkyloxy group optionally having a substituent, an aryloxy group optionally having a substituent, an aryl group optionally having a substituent, a heteroaryl group optionally having a substituent, a thiol group, an alkoxyalkylthio group, a haloalkylthio group, a cycloalkylthio group optionally having a substituent, or an oligomer group.

[0239] The number of carbon atoms in the alkyl group is preferably 1 to 10. Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl and hexyl.

[0240] The number of carbon atoms in the haloalkyl group is preferably 1 to 10. The haloalkyl group is preferably an alkyl group substituted with a fluorine atom, a chlorine atom or a bromine atom. Suitable examples of the haloalkyl group include trifluoromethyl, tetrafluoroethyl, chloromethyl, 2-chloroethyl and bromomethyl.

[0241] The number of ring carbon atoms of the cycloalkyl group is preferably 3 to 8. Examples of the cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. It should be noted that the cycloalkyl group may have a substituent, and the number of carbon atoms (3 to 8 carbon atoms) does not include the number of carbon atoms of the substituent.

[0242] The number of carbon atoms of the alkoxy group is preferably 1 to 10, more preferably 1 to 6. Preferred examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, and a tert-butoxy group.

[0243] The amino group is a primary amino group (-NH2), and the substituted amino group is a secondary or tertiary amino group in which one or two hydrogen atoms are substituted. As the substituent possessed by the substituted amino group, there can be listed an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 7 carbon atoms, an aryl group having 6 to 14 carbon atoms, and a heteroaryl group having 4 to 14 carbon atoms. Suitable examples of the amino group include amino, methylamino, dimethylamino, ethylamino, diethylamino, phenylamino, diphenylamino, and the like.

[0244] The number of atoms in the heterocyclic group is preferably 3 to 10. The heterocyclic group may be an aliphatic heterocyclic group or an aromatic heterocyclic group. Specific examples of the aliphatic heterocyclic group include morpholinyl, piperidinyl, pyrrolidinyl, piperazinyl, and N-methylpiperazinyl. Specific examples of the aromatic heterocyclic group include indolinyl. The heterocyclic group may optionally have a substituent. As a preferred substituent, an alkyl group having 1 to 10 carbon atoms may be listed. As suitable heterocyclic groups having a substituent, for example, 2,6-dimethylmorpholinyl, 2,6-dimethylpiperidinyl, and 2,2,6,6-tetramethylpiperidinyl may be listed.

[0245] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0246] The number of carbon atoms of the alkylthio group is preferably 1 to 10. Examples of the alkylthio group include a methylthio group, an ethylthio group, an n-propylthio group, an isopropylthio group, an n-butylthio group, a sec-butylthio group and a tert-butylthio group.

[0247] The number of carbon atoms of the arylthio group is preferably 6 to 10. Examples of the arylthio group include a phenylthio group, a 1-naphthylthio group and a 2-naphthylthio group.

[0248] The number of carbon atoms in the alkylcarbonyl group is preferably 2 to 10. Examples of the alkylcarbonyl group include an acetyl group and an ethylcarbonyl group.

[0249] The number of carbon atoms in the alkoxycarbonyl group is preferably 2 to 10. Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group.

[0250] The number of carbon atoms of the aralkyl group is preferably 7 to 11. Examples of the aralkyl group include a benzyl group, a phenylethyl group, a phenylpropyl group, a phenylbutyl group, and a naphthylmethyl group.

[0251] The number of carbon atoms of the aralkyloxy group is preferably 7 to 11. Examples of the aralkyloxy group include a benzyloxy group and a naphthylmethoxy group.

[0252] The number of carbon atoms of the aryl group is preferably 6 to 12. Examples of the aryl group include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.

[0253] The number of carbon atoms of the aryloxy group is preferably 6 to 12. Examples of the aryloxy group include a phenoxy group and a naphthoxy group.

[0254] The number of carbon atoms in the heteroaryl group is preferably 3 to 12. Examples of the heteroaryl group include a thienyl group, a furyl group, a pyrrolinyl group, a pyridyl group, a benzothienyl group, a benzofuranyl group, and a benzopyrrolinyl group.

[0255] The number of carbon atoms in the alkoxyalkylthio group is preferably 2 to 10. Examples of the alkoxyalkylthio group include a methoxymethylthio group, a methoxyethylthio group, a methoxy-n-propylthio group, a methoxy-n-butylthio group, an ethoxyethylthio group, and a n-propoxypropylthio group.

[0256] The number of carbon atoms of the halogenoalkylthio group is preferably 1 to 10. Examples of the halogenoalkylthio group include a trifluoromethylthio group, a tetrafluoroethylthio group, a chloromethylthio group, a 2-chloroethylthio group and a bromomethylthio group.

[0257] The number of carbon atoms in the cycloalkylthio group is preferably 3 to 8. Examples of the cycloalkylthio group include cyclopropylthio, cyclobutylthio, cyclopentylthio and cyclohexylthio. The cycloalkylthio group may have a substituent, and the number of carbon atoms (3 to 8 carbon atoms) does not include the number of carbon atoms in the substituent.

[0258] The oligomer group comprises an oligomer chain, a linking group and a terminal group.

[0259] The oligomer chain may include at least one selected from the group consisting of a polyalkylene oxide chain, a polysiloxane chain, and a polyester chain. The oligomer chain is a divalent group.

[0260] The polyalkylene oxide chain has a linear or branched polyalkylene oxide having a carbon number of 1 to 10 as a repeating unit. The number of repetitions of the repeating unit is, for example, 3 to 1000. The repeating unit is, for example, -CH2O-, -CH2CH2O-, -CH(CH3)CH2O-, -CH2CH(CH3)O-, -CH2CH2CH2O-, or -CH2CH2C(CH3)O-.

[0261] The polysiloxane chain has, for example, a dimethylsilylideneoxy group (-Si(CH3)2O-) as a repeating unit. The number of repetitions of the repeating unit is, for example, 3 or more and 1,000 or less.

[0262] The polyester chain has, for example, -OC(=O)CH2-, -OC(=O)CH2CH2CH2CH2C(=O)O- or -OC(=O)CH2CH2CH2CH2C(=O)OCH2CH2-) as a repeating unit. The number of repetitions of the repeating unit is, for example, 3 or more and 1,000 or less.

[0263] The linking group bonds the photochromic compound to one end of the oligomer chain. The linking group is, for example, -O-, -O-CH2CH2-O-, -O-CH2CH2-OC(=O)CH2CH2C(=O)-O-, or -O-CH2CH2-OC(=O)CH2CH2C(=O)-O-CH2-. The linking group may be a divalent group or a group having a valence of more than 2.

[0264] The terminal group is bonded to the other end of the oligomer chain. The terminal group is, for example, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms, or a linear or branched alkenyl group having 2 to 30 carbon atoms. The terminal group is preferably a methyl group.

[0265] The oligomer group may include a first linking group, an oligomer chain, and a second linking group. The first linking group and the second linking group may have the same structure as each other, or may have structures different from each other. The first linking group is connected to the first photochromic compound. The second linking group is connected to the second photochromic compound. The first photochromic compound and the second photochromic compound may have the same structure as each other, or may have structures different from each other.

[0266] The above-mentioned cycloalkyl group, arylthio group, aralkyl group, aralkyloxy group, aryloxy group, aryl group, heteroaryl group and cycloalkylthio group may be unsubstituted or may have a substituent.

[0267] The substituents which the cycloalkyl group, arylthio group, arylalkyl group, arylalkyloxy group, aryloxy group, aryl group, heteroaryl group and cycloalkylthio group may have may be selected from the group consisting of a primary amino group, a secondary amino group, a tertiary amino group, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a haloalkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, a hydroxyl group, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkylaryl group having 1 to 20 carbon atoms, a heterocycloalkyl group having 1 to 8 carbon atoms containing 1 to 5 hetero atoms, a heteroaryl group having 1 to 8 carbon atoms containing 1 to 5 hetero atoms, an aryloxy group having 6 to 12 carbon atoms, an arylthio group having 6 to 12 carbon atoms, a cyano group, a nitro group, a halogen atom and an oligomer group. The number of substituents may be 1 or 2 or more.

[0268] Q 13 With Q 14 , Q 14 With Q 15 , and Q 15 With Q 16 They may be bonded to each other to form an aliphatic ring having 2 to 5 carbon atoms, an aliphatic heterocyclic ring having 1 to 4 carbon atoms containing 1 to 3 heteroatoms, an aromatic ring having 4 to 12 carbon atoms, or an aromatic heterocyclic ring having 3 to 11 carbon atoms containing 1 to 6 heteroatoms. The aliphatic ring, aliphatic heterocyclic ring, aromatic ring, and aromatic heterocyclic ring may be unsubstituted or may have at least one substituent selected from the above substituent group.

[0269] Q 18 With Q 19 Preferably, they are bonded to each other to form a substituted spiro ring or an unsubstituted spiro ring with the carbon atom at position 13 as a spiro atom. The spiro ring may be an aliphatic ring, a condensed polycyclic ring, a heterocyclic ring or a heterocyclic aromatic ring. The spiro ring is preferably an aliphatic ring having 5 to 16 ring carbon atoms. The aliphatic ring also preferably has an alkyl group having 1 to 3 carbon atoms as a substituent.

[0270] Q 18 and Q 19 Each independently can be of the formula: -Q 100 -(X 100 Q 101 ) θ -X 101 Q 102 The group shown in the formula (a) is a substituted or unsubstituted halogenated alkyl group having 1 to 20 carbon atoms, or a linear or branched alkyl group having 1 to 10 carbon atoms.

[0271] Q 100 The alkylene group is an alkylene group which optionally contains a halogen atom as a substituent. The number of carbon atoms in the alkylene group is preferably 1 to 20, more preferably 1 to 12, further preferably 1 to 7, and most preferably 2 to 6. As the halogen atom, at least one selected from the group consisting of I, Cl, Br and F can be used.

[0272] Q 101 The preferred embodiment of the number of carbon atoms and halogen atoms of the alkylene group is the same as that of Q 1 same.

[0273] Q 102 The alkyl group is an alkyl group which may contain a halogen atom as a substituent. The number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 12, further preferably 1 to 7, and most preferably 2 to 6.

[0274] X 100 and X 101 Each is independently O, S, N or P. X 101 and X 102 It is preferably O, S or N, more preferably O or S, and most preferably O.

[0275] θ is 0 or 1.

[0276] Specific examples of the formula include -CH2OCH3, -CH2SCH3, -CH2CH2OCH3, -CH2CH2OCH2CH3, -CH2CH2SCH3, -CH2CH2CH2OCH3, -CH2CH2CH2SCH 3、-CH2CH2OCH2CH2OCH 3、 And, -CH2CH2OCH2CH2OCH2CH3.

[0277] The number of carbon atoms in the halogenated alkyl group is more preferably 1 to 12, further preferably 1 to 7, and most preferably 2 to 6. As the halogen atom, at least one selected from the group consisting of I, Cl, Br and F can be used. The halogen atom is preferably at least one of Cl and F, and more preferably F.

[0278] The haloalkyl group preferably has one or more halogen atoms bonded to the terminal carbon, and preferably has three halogen atoms bonded to the terminal carbon. When a haloalkyl group having a halogen atom bonded to the terminal carbon is used, stereo hindrance tends to be more likely to occur.

[0279] The haloalkyl group is represented by, for example, the following formula (A).

[0280] -C α H β Z γ (A)

[0281] In formula (A), α is the number of carbon atoms. α is preferably 1 or more and 10 or less, and more preferably 2 or more and 6 or less.

[0282] β is the number of hydrogen atoms. β is, for example, 1 to 20, preferably 2 to 12, and more preferably 4 to 10. However, β+γ=2α+1.

[0283] Z represents a halogen atom. γ represents the number of halogen atoms. γ is, for example, 1 to 20, preferably 2 to 12, and more preferably 3 to 6.

[0284] The ultraviolet light absorber has an absorption wavelength in the ultraviolet (UV) region below 400nm. The ultraviolet light absorber may have a maximum absorption wavelength in a region above 330nm and below 380nm, or may have a maximum absorption wavelength in a region above 250nm and less than 330nm. As the ultraviolet light absorber, an organic compound may be used. As the ultraviolet light absorber, for example, at least one selected from the group consisting of benzophenone derivatives, ethylhexyl methoxycinnamate, benzotriazole derivatives and triazine derivatives is used. The ultraviolet light absorber preferably includes at least one selected from the group consisting of benzophenone derivatives, ethylhexyl methoxycinnamate and benzotriazole derivatives.

[0285] As the blue light absorber, a compound having an absorption peak in a wavelength region of more than 400 nm and less than 450 nm in the absorption spectrum can be used. Such a compound is, for example, at least one selected from the group consisting of perylene compounds, porphyrin compounds, carotenoid compounds, and cyanine compounds. As the blue light absorber, a porphyrin compound is preferably used, and a porphyrin tetraza compound is more preferably used.

[0286] The high-energy visible light absorber is a blue light absorber having an absorption peak in a wavelength region exceeding 400 nm and not more than 420 nm. As the high-energy visible light absorber, the same absorber as the blue light absorber can be used.

[0287] Dye is preferably included in the compound with absorption peak in the wavelength region of more than 540nm and below 650nm in the absorption spectrum, more preferably included in the compound with absorption peak in the wavelength region of more than 550nm and below 600nm.If comprise this compound, then can improve the anti-glare property of solidified material.As this compound, can list nitro series compound, azo series compound, anthraquinone series compound, threne series compound, porphyrin series compound, rare earth metal compound etc.As this compound, preferably use at least one selected from the group consisting of tetraazoporphyrin compound and neodymium compound.

[0288] Examples of the electrochromic compound include organic substances such as viologen, polymers having electrochromic properties, and metal salt complexes having d atoms.

[0289] The proportion of the functional dye in the solid content of the optical material composition is, for example, 0.1 mass % to 10 mass %, or preferably 1 mass % to 5 mass %.

[0290] (Other additives)

[0291] The composition for optical materials may contain various additives within the range that does not impair the effect. Additives such as polymerization accelerators, polymerization initiators, functional pigments, ultraviolet absorbers, antistatic agents, infrared absorbers, ultraviolet stabilizers, antioxidants, anti-coloring agents, antistatic agents, fluorescent dyes, dyes, pigments, fragrances, etc., and polymerization regulators such as solvents, leveling agents, internal mold release agents, and mercaptans such as tert-dodecyl mercaptan may be mixed as needed.

[0292] (Curing accelerator)

[0293] The urethane optical material composition may further contain various polymerization curing accelerators to rapidly promote the polymerization curing, depending on the types of the above-mentioned components. Reaction catalysts and condensation agents for urethane or urea used in the reaction of hydroxyl and thiol groups with isocyanate groups and isothiocyanate groups are used as polymerization curing accelerators.

[0294] The carbamate or urea reaction catalyst is used when generating poly (thio) carbamate bond by the reaction of polyiso (thio) cyanate and polyol or polymercaptan. These carbamate or urea reaction catalysts can be listed as tertiary amines and inorganic salts or organic salts corresponding to them, phosphines, quaternary ammonium salts, quaternary phosphonium salts, Lewis acids or organic sulfonic acids. As its specific example, the following materials can be illustrated. In addition, according to the type of the above-mentioned compound selected, when the catalytic activity is too high, by mixing tertiary amine with Lewis acid, the catalytic activity can be suppressed.

[0295] Tertiary amines: triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, triethylamine, hexamethylenetetramine, N,N-dimethyloctylamine, N,N,N′,N′-tetramethyl-1,6-diaminohexane, 4,4′-trimethylenebis(1-methylpiperidine), 1,8-diazabicyclo-(5,4,0)-7-undecene.

[0296] Phosphines: trimethylphosphine, triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tribenzylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,2-bis(dimethylphosphino)ethane.

[0297] Quaternary ammonium salts: tetramethylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bromide.

[0298] Quaternary phosphonium salts: tetramethyl phosphonium bromide, tetrabutyl phosphonium chloride, tetrabutyl phosphonium bromide.

[0299] Lewis Acid: triphenylaluminum, dimethyltin dichloride, dimethyltin bis(isooctylmercaptoacetate), dibutyltin dichloride, dibutyltin dilaurate, dibutyltin maleate, dibutyltin maleate polymer, dibutyltin diricinoleate, dibutyltin bis(dodecylmercaptan), dibutyltin bis(isooctylmercaptoacetate), dioctyltin dichloride, dioctyltin maleate, dioctyltin maleate polymer, dioctyltin bis(butylmaleate), dioctyltin dilaurate, dioctyltin diricinoleate, dioctyltin dioleate, dioctyltin di(6-hydroxy)hexanoate, dioctyltin bis(isooctylmercaptoacetate), didodecyltin diricinoleate.

[0300] Organic sulfonic acids: methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid.

[0301] As specific examples of the condensing agent, the following can be illustrated.

[0302] Inorganic acids: hydrogen chloride, hydrogen bromide, sulfuric acid, phosphoric acid, etc.

[0303] Organic acids: p-toluenesulfonic acid, camphorsulfonic acid, etc.

[0304] Acidic ion exchange resins; Amberlite, Amberlyst, etc.

[0305] Carbodiimide: dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylaminopyrrolyl)carbodiimide.

[0306] The above-mentioned various polymerization accelerators can be used alone or in combination of two or more, and their usage amount can be a so-called catalytic amount, for example, a small amount in the range of 0.001 to 10 parts by mass, especially 0.01 to 5 parts by mass, relative to 100 parts by mass of the total of the above-mentioned polyiso(thio)cyanate compounds and polyol compounds.

[0307] (Polymerization initiator)

[0308] As the polymerization initiator, at least one of a thermal polymerization initiator and a photopolymerization initiator is used.

[0309] Examples of the thermal polymerization initiator include diacyl peroxides such as benzoyl peroxide, p-chlorobenzoyl peroxide, decanoyl peroxide, lauroyl peroxide, and acetyl peroxide.

[0310] Examples of the peroxyester include t-butyl peroxy-2-ethylhexanoate, t-butyl peroxyneodecanoate, cumyl peroxyneodecanoate, and t-butyl peroxybenzoate.

[0311] Examples of the percarbonate ester include diisopropyl peroxydicarbonate and di-sec-butyl peroxydicarbonate.

[0312] Examples of the azo compound include azobisisobutyronitrile and 2,2′-azobis(2,4-dimethylvaleronitrile).

[0313] Examples of the photopolymerization initiator include acetophenone compounds such as 1-phenyl-2-hydroxy-2-methylpropane-1-one, 1-hydroxycyclohexyl phenyl ketone, and 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one.

[0314] Examples of the α-dicarbonyl compounds include 1,2-diphenylethanedione and methylphenylglyoxylate.

[0315] Examples of the acylphosphine oxide compounds include 2,6-dimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, methyl 2,4,6-trimethylbenzoyldiphenylphosphinate, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide.

[0316] When a photopolymerization initiator is used, a known polymerization curing accelerator such as a tertiary amine may be used in combination.

[0317] (Antioxidant)

[0318] As the antioxidant, 2,6-di-tert-butyl-4-methylphenol, IRGANOX 245 manufactured by BASF JAPAN: ethylenebis(oxyethylene)bis[3,5-tert-butyl-4-hydroxy-m-toluoyl]propionate, IRGANOX 1076 manufactured by BASF JAPAN: octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, IRGANOX 1010 manufactured by BASF JAPAN: pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, IRGANOX 1035, 1075, 104, 3790, 5057, 565 manufactured by BASF JAPAN, etc. can be used.

[0319] As the leveling agent, silicone surfactants, fluorine-containing surfactants, etc. can be used. Specifically, L-7001, L-7002, L-7604, FZ-2123 manufactured by DOW·TORAY; Megafac F-470, Megafac F-1405, Megafac F-479 manufactured by DIC; Fluorad FC-430 manufactured by 3M JAPAN, etc. can be used.

[0320] (Light Stabilizer)

[0321] As the light stabilizer, it is preferred to use a hindered amine compound having a 2,2,6,6-tetramethyl-4-piperidinyl skeleton, and commercially available products can be used. Examples thereof include bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, 1-[2-{3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy}ethyl]-4-{3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy}-2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, methyl(1,2,2,6,6-pentamethyl-4-piperidinyl)sebacate, dicarboxylic acid ester, 1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate, 2-[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]-2-butylmalonic acid [1,2,2,6,6-pentamethyl-4-piperidinyl] ester, poly[{6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl}{(2,2,6,6-tetramethyl-4-piperidinyl)imino}hexamethylene{(2,2,6,6-tetramethyl-4-piperidinyl)imino}], 1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate, and the like. As product names, there can be listed ADEKASTAB (registered trademark) LA series (LA-52, LA-57, LA-63P, LA-68, LA-72, LA-77Y, LA-81, LA-82, etc.) manufactured by ADEKA Corporation, TINUVIN (registered trademark) series (TINUVIN123, TINUVIN171, TINUVIN249, TINUVIN292, TINUVIN765, TINUVIN622SF, etc.) manufactured by BASF JAPAN, and Chimassorb (registered trademark) series (Chimassorb2020FDL, Chimassorb944FDL).

[0322] (Organic Solvent)

[0323] The composition for an optical material may contain an organic solvent in order to adjust its viscosity. The organic solvent may contain at least one selected from the group consisting of tetrahydrofuran, diethyl ketone, tert-butyl alcohol, isopropyl alcohol, propylene glycol monomethyl ether, toluene, ethyl acetate, and cyclohexanone.

[0324] In the composition for an optical material, the ratio of the organic solvent is, for example, 30% by mass or more and 80% by mass or less.

[0325] (Internal release agent)

[0326] In addition, in the case where the demoulding property of the optical article is poor, an internal mold release agent can be used. As such an internal mold release agent, any material can be used as long as it has a demoulding effect and does not damage the physical properties such as the transparency of the resin, and preferably a surfactant is used. Among them, a phosphate surfactant is preferably used. The internal mold release agent mentioned here also includes substances that show a demoulding effect among the various catalysts mentioned above, for example, sometimes also quaternary ammonium salts and quaternary phosphonium salts. These internal mold release agents are appropriately selected according to their combination with the monomer, polymerization conditions, economy, and ease of handling. The specific example of the internal mold release agent of phosphate is shown below.

[0327] Examples include: alkyl acid phosphates; mono-n-butyl phosphate, mono-2-ethylhexyl phosphate, mono-n-octyl phosphate, mono-n-butyl phosphate, bis(2-ethylhexyl) phosphate, di(2-ethylhexyl) phosphate, di-n-octyl phosphate, di-n-butyl phosphate, acid phosphoric acid (monobutyl and dibutyl mixture), acid phosphoric acid (monoethyl and diethyl mixture), acid phosphoric acid (monobutoxyethyl and dibutoxyethyl mixture), acid phosphoric acid (mono-2-ethylhexyl and di(2-ethylhexyl) mixture), acid phosphoric acid (monoisotridecyl and di(isotridecyl) mixture), acid phosphoric acid (monotetracosyl and di(tetracosyl) mixture), acid phosphoric acid (monostearyl and distearyl mixture);

[0328] Other phosphates; acid phosphoric acid (monooleyl ester, dioleyl ester mixture), dibutyl pyrophosphate, acid phosphoric acid (monoethylene glycol ester, diethylene glycol ester mixture), acid phosphoric acid (monobutoxyethyl ester, dibutoxyethyl ester mixture), etc.

[0329] [cured material]

[0330] The optical material composition described in the embodiment is cured to obtain a cured product. The curing method includes, for example, irradiation with active energy rays such as ultraviolet rays, α rays, β rays, γ rays, heat, or a combination of both, thereby performing free radical polymerization, ring-opening polymerization, anionic polymerization, or polycondensation.

[0331] The curing method is appropriately determined according to the type of the matrix-forming compound. For example, when the matrix-forming compound includes a compound having a free radical polymerizable group, photopolymerization is suitable. In addition, when the matrix-forming compound includes a compound having an addition polymerization reactive group and a compound having a reactive group that reacts with the addition polymerization reactive group, thermal polymerization is suitable.

[0332] It should be noted that, when the matrix-forming compound includes a compound having an addition-polymerization reactive group, a compound having a reactive group that reacts with the addition-polymerization reactive group is mixed into the optical material composition, and the resulting curable composition is subjected to thermal polymerization. When the matrix-forming compound includes a compound having a reactive group that reacts with the addition-polymerization reactive group, a compound having an addition-polymerization reactive group is mixed into the optical material composition, and the resulting curable composition is subjected to thermal polymerization.

[0333] In the optical material composition comprising the addition-polymerization reactive group and the reactive group that reacts therewith, the number of moles of the addition-polymerization reactive group and the number of moles of the reactive group may be equal, or one of them may be in excess. For example, by setting the number of moles of the isocyanate group in excess, an optical material composition comprising a urethane prepolymer can be obtained.

[0334] In addition, the optical material composition containing the urethane urea prepolymer is obtained by, for example, the following method. First, a polyol is reacted with a polyisocyanate compound in an excess of isocyanate groups to obtain a urethane prepolymer. The urethane prepolymer is reacted with a polyamine in an excess of isocyanate groups to obtain a urethane urea prepolymer.

[0335] The composition for an optical material including at least one of a urethane prepolymer and a urethane urea prepolymer can be suitably used as the composition for forming an adhesive layer.

[0336] [Optical article and method of manufacturing the same]

[0337] The optical article includes a cured product of the optical material composition described in the embodiment. Examples of the optical article include lenses, window glass for houses or cars, liquid crystal displays, sun visors, clocks, etc. The lens includes semi-finished lenses and finished lenses.

[0338] The optical article described in the embodiment is particularly suitable for photochromic optical articles. The photochromic optical article includes a cured product of a curable composition containing a photochromic compound. As the photochromic optical article, a photochromic lens can be cited. The photochromic lens can be manufactured by a known method such as a kneading method, a coating method, a glass pasting method, and an adhesive method.

[0339] Optical articles based on the kneading method can be manufactured by, for example, injection molding polymerization. First, the optical material composition is injected between glass molds maintained by an elastomer gasket or a spacer, and fully degassed. Then, it is heated in an air furnace or in water to obtain a cured product.

[0340] The optical material composition for the mixing method is suitable for comprising an optical material compound, an isocyanate compound, an active hydrogen compound, an antioxidant, an ultraviolet absorber and a curing accelerator shown in formula (I). From the viewpoint of transparency, the optical material compound shown in formula (I) is preferably a dithiol type. The isocyanate compound preferably comprises a diisocyanate. In addition, the isocyanate compound preferably comprises at least one of an alicyclic isocyanate compound and an aromatic isocyanate compound, and more preferably comprises both. The active hydrogen compound preferably comprises a thiol, and more preferably comprises a polythiol. In the optical material composition for the mixing method, the proportions of the optical material compound, the isocyanate compound and the active hydrogen compound shown in formula (I) are preferably 5% by mass or more and 30% by mass or less, 30% by mass or more and 45% by mass or less, and 40% by mass or more and 50% by mass or less, respectively.

[0341] An optical article by a coating method can be obtained by coating the optical material composition on an optical substrate such as a lens substrate by spin coating or the like, and curing the coating film.

[0342] The composition for optical materials used in the coating method is suitable for comprising a compound for optical materials represented by formula (I), (meth)acrylate, rotaxane, antioxidant, light stabilizer, leveling agent and photopolymerization initiator. The compound for optical materials represented by formula (I) is preferably a diacrylate type or a dimethacrylate type. (Meth)acrylate preferably comprises at least two compounds selected from the group consisting of a monofunctional (meth)acrylic polymerizable compound, a difunctional (meth)acrylate compound, a trifunctional (meth)acrylic polymerizable compound and a tetrafunctional (meth)acrylic polymerizable compound, and more preferably all of them are included. In the optical material composition for coating method, the proportions of the optical material compound represented by formula (I), the monofunctional (meth)acrylic polymerizable compound, the difunctional (meth)acrylate compound, the trifunctional (meth)acrylic polymerizable compound and the tetrafunctional (meth)acrylic polymerizable compound are preferably 30% by mass or more and 50% by mass or less, 5% by mass or more and 20% by mass or less, 10% by mass or more and 25% by mass or less, and 5% by mass or more and 20% by mass or less, respectively.

[0343] As the optical substrate, there is no particular limitation, and known plastic substrates can be used. Specifically, plastic materials such as (meth) acrylic resins, polycarbonate resins, allyl resins, thiocarbamate resins, carbamate resins, thioepoxy resins, and polyvinyl alcohol resins can be cited. As the optical substrate, a polarizing film can be used.

[0344] In order to improve the adhesion with the coating film, the surface of the optical substrate may be subjected to chemical treatment with an alkaline solution, an acid solution, etc., corona discharge, plasma discharge, physical treatment by polishing, etc. In addition, a transparent adhesive resin layer may be provided on the surface of the optical substrate.

[0345] Optical articles based on the glass bonding method are manufactured by, for example, the following method. First, a pair of glass substrates are prepared. The optical material composition is coated on a glass substrate provided with a spacer, and another glass substrate is laminated on the coating. The coating is cured to bond the pair of glass substrates.

[0346] The optical material composition for glass pasting method is suitable for comprising the optical material compound shown in formula (I), isocyanate compound, active hydrogen compound, antioxidant, ultraviolet absorber and curing accelerator. From the viewpoint of transparency, the optical material compound shown in formula (I) is preferably a dithiol type. The isocyanate compound preferably comprises a diisocyanate. In addition, the isocyanate compound preferably comprises at least one of an alicyclic isocyanate compound and an aromatic isocyanate compound, and more preferably comprises both. The active hydrogen compound preferably comprises a thiol, and more preferably comprises a polythiol. In the optical material composition for glass pasting method, the proportions of the optical material compound, isocyanate compound and active hydrogen compound shown in formula (I) are preferably 20% by mass or more and 40% by mass or less, 20% by mass or more and 40% by mass or less, and 20% by mass or more and 40% by mass or less, respectively.

[0347] Optical articles based on the adhesive method are manufactured by, for example, the following method. First, a composition for optical materials is applied to an optical substrate, and the coating is dried to form an adhesive layer. The obtained adhesive layer is clamped between two transparent optical sheets to obtain a laminate. The optical substrate can be removed from the adhesive layer, and only the coating is laminated. The laminate is heat-treated to polymerize the coating. In this way, an adhesive sheet having two optical sheets bonded together by an adhesive layer is obtained. Instead of using an adhesive layer, a coating can be directly formed on at least one optical sheet. The adhesive sheet is installed in, for example, a mold, and then, a thermoplastic resin such as polycarbonate is injection molded to obtain an optical article of a specified shape. Alternatively, the adhesive sheet can be embedded in the resin by an injection molding polymerization method.

[0348] The composition for optical materials used in the adhesive sheet method is suitable for comprising a carbamate urea prepolymer, an antioxidant and a leveling agent. The carbamate urea prepolymer is a reaction product of a carbamate prepolymer and a polyamine. The carbamate prepolymer is a reaction product of an optical material compound represented by formula (I) and an isocyanate compound. The composition for carbamate prepolymer preferably comprises an optical material compound represented by formula (I), an isocyanate compound and a solvent. From the viewpoint of transparency, the optical material compound represented by formula (I) is preferably a dithiol type.

[0349] The semi-finished lens obtained by the above method may be dyed, or may be laminated with a functional layer such as an antireflection film, a hard coat layer, a polarizing layer, or a polarizing film.

[0350] Example

[0351] The present invention will be described in more detail with reference to several examples shown below. These examples are merely for illustrating the present invention, and the spirit and scope of the present invention are not limited to these examples.

[0352] [Synthesis of compounds for optical materials]

[0353] (Synthesis of Compound 1)

[0354] 1,4-Butanediol (70 g) and potassium hydroxide (1.2 g) as a catalyst were added to the autoclave, and the air in the autoclave was replaced with nitrogen. The catalyst was dissolved at 120°C while stirring to obtain a first solution. The first solution was set to 120°C and 0.2-0.5 MPa (gauge pressure), and propylene oxide (550 g) was added dropwise and stirred for 3 hours to obtain a second solution. Ethylene oxide (440 g) was added dropwise to the second solution at 120°C and 0.2-0.5 MPa (gauge pressure) and stirred for 1 hour. Thereafter, the reaction product was taken out of the autoclave, the pH was adjusted to 6-7 using hydrochloric acid, and it was dried under reduced pressure at 110°C for 1 hour (gauge pressure: 0.095 MPa) to remove the contained water. Thereafter, filtration was performed to remove the generated salt, thereby obtaining compound 1 represented by the following formula (I-1).

[0355]

[0356] The number average molecular weight of the obtained compound 1 was calculated based on the hydroxyl value obtained by the hydroxyl value measurement based on JIS K1557-1:2007, and the values ​​of a, m+n and p+q in formula (I-1) were determined based on the value. The values ​​of each addition mole number a, m+n and p+q are shown in Table 1.

[0357] The obtained compound was dissolved in deuterated chloroform and then 1The measurement was performed using a H-NMR spectrometer (JNM-ECA400II, 400 MHz, manufactured by JEOL Ltd., reference material: TMS). The ratio of the number average molecular weight of the polyethylene oxide chain obtained by calculating the number average molecular weight of each unit to the number average molecular weight of the compound, R 1 The number average molecular weight of the chain and the number average molecular weight of the compound R 1 The ratio of the number average molecular weight of the chains and thus R 11 The number average molecular weight of O chain is relative to R 1 The ratios of the number average molecular weights of the chains are shown in Table 1.

[0358] (Synthesis of Compounds 2 to 5)

[0359] Except for changing the starting materials and the addition amounts of propylene oxide and ethylene oxide, the compounds 2, 4 and 5 represented by the above formula (I-1) and the compound 3 represented by the following formula (I-2) were synthesized by the same method as compound 1. The values ​​of the addition molar numbers a, m+n and p+q are shown in Table 1.

[0360]

[0361] (Synthesis of Compound 6)

[0362] 1,4-Butanediol (70 g) and potassium hydroxide (1.4 g) as a catalyst were added to an autoclave, and the air in the autoclave was replaced with nitrogen. The catalyst was dissolved at 120°C while stirring to obtain a first solution. Next, the first solution was set to 120°C and 0.2-0.5 MPa (gauge pressure), and a mixture of propylene oxide (135 g) and tetrahydrofuran (560 g) was added dropwise, and stirred for 5 hours to obtain a second solution. Next, ethylene oxide (550 g) was added dropwise to the second solution at 120°C and 0.2-0.5 MPa (gauge pressure), and stirred for 1 hour. Thereafter, the reaction product was taken out of the autoclave, the pH was adjusted to 6-7 with hydrochloric acid, and it was dried under reduced pressure at 110°C for 1 hour (gauge pressure: 0.095 MPa) to remove the contained water. Thereafter, it was filtered to remove the generated salt, thereby obtaining compound 6 represented by the following formula (I-3). Table 1 shows the values ​​of each of the added molar numbers b, c and p+q.

[0363]

[0364] (Synthesis of Compound 7)

[0365] Compound 5 (50 g), p-toluenesulfonic acid monohydrate (0.68 g), 60 mL of toluene, and 3-mercaptopropionic acid (7.6 g) were added to a 100 mL flask, and the mixture was heated to reflux for 10 hours while removing water using a Dean Stark tube. After cooling to room temperature, 1% ammonia water was added for washing and separation, and the organic layer was distilled off under reduced pressure. Thereafter, dichloromethane was added to dissolve the reaction product and washed with water 3 times. After the organic layer was dried using magnesium sulfate, the solvent was distilled off under reduced pressure to obtain compound 7 (yield: 90%) shown in the following formula (I-4).

[0366]

[0367] The proton nuclear magnetic resonance spectrum of Compound 7 was measured and the following peaks were shown.

[0368] δ1.08-1.17(m,33H),1.62(quint,4H),2.66-2.80(m,8H),3.29-3.73(m,97H),4.31(m,4H).

[0369] (Synthesis of Compound 8)

[0370] Compound 5 (50 g), p-toluenesulfonyl chloride (14 g) and 40 mL of dichloromethane were added to a 100 mL flask and cooled to 10° C. Then, triethylamine (7.2 g) was added dropwise and stirred at room temperature for 8 hours. The reaction solution was washed with water three times, the organic layer was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure.

[0371] Next, thiourea (5.5 g) and water (280 g) were added to the obtained reaction product, and the mixture was heated under reflux for 3 hours. Thereafter, the reaction solution was cooled to room temperature, hydrazine monohydrate (8.9 g) was added, and the mixture was further stirred for 18 hours. Thereafter, hydrochloric acid was added to make the mixture acidic, and extraction was performed using dichloromethane. The obtained organic layer was washed with water 3 times, and after the organic layer was dried over magnesium sulfate, the solvent was distilled off under reduced pressure to obtain compound 8 represented by the following formula (I-5) (yield: 75%).

[0372]

[0373] The proton nuclear magnetic resonance spectrum of Compound 8 was measured and the following peaks were shown.

[0374] δ1.08-1.17(m,33H),1.62(quint,4H),3.29-3.73(m,101H).

[0375] (Synthesis of Compound 9)

[0376] Compound 1 (50 g) and 40 mL of dichloromethane were added to a 100 mL flask, and after cooling to 10°C, purified acryloyl chloride (13 g) and triethylamine (15 g) were added dropwise, and stirred at room temperature for 5 hours. Thereafter, the reaction solution was washed 3 times with 3% hydrochloric acid, 3 times with water, 3 times with 10% aqueous sodium hydroxide solution, and 3 times with water. After the organic layer was dried over magnesium sulfate, the solvent was distilled off under reduced pressure to obtain compound 9 represented by the following formula (I-6) (yield: 90%).

[0377]

[0378] The proton nuclear magnetic resonance spectrum of Compound 9 was measured and the following peaks were shown.

[0379] δ1.08-1.17(m,21H),1.62(quint,4H),3.29-3.73(m,49H),4.31(m,4H),5.84(d,2H),6.16(dd,2H),6.43(d,2H).

[0380] (Synthesis of Compound 10)

[0381] Compound 1 (50 g), 60% sodium hydride (7.5 g), and 30 mL of dry tetrahydrofuran were added to a 100 mL flask, and stirred at room temperature for 1 hour. Allyl bromide (15 g) was added dropwise, and stirred at room temperature for further 18 hours. After the solvent was distilled off under reduced pressure, dichloromethane was added and washed with water 3 times. After the organic layer was dried over magnesium sulfate, the solvent was distilled off under reduced pressure to obtain compound 10 (yield: 88%) represented by the following formula (I-7).

[0382]

[0383] The proton nuclear magnetic resonance spectrum of Compound 10 was measured and the following peaks were shown.

[0384] δ1.08-1.17(m,21H),1.62(quint,4H),3.29-3.73(m,53H),4.10(m,4H),5.17(d,2H),5.33(d,2H),6.00(m,2H).

[0385] [Table 1]

[0386] Table 1

[0387]

[0388] [Table 2]

[0389] Table 2

[0390]

[0391] In Table 2, the number average molecular weight of each optical material compound is recorded in the column labeled "Number Average Molecular Weight", the ratio of the number average molecular weight of the polyethylene oxide chain to the number average molecular weight of the optical material compound is recorded in the column labeled "EO (%, Mn / Mn)", and the ratio of the number average molecular weight of the polyethylene oxide chain to the number average molecular weight of the optical material compound is recorded in the column labeled "R 1 R is recorded in the column of "Number Average Molecular Weight" 1 The number average molecular weight of the base is expressed as "R 1 R is recorded in the column of "Basis (%), Mn / Mn" 1 The ratio of the number average molecular weight of the group to the number average molecular weight of the compound for optical material is expressed as "R 11 O chain / R 1 R is recorded in the column of "Basis (%), Mn / Mn" 11 The number average molecular weight of O chain is relative to R 1 The ratio of the number average molecular weight of the base.

[0392] [Optical material composition and cured product]

[0393] Photochromic optical articles were produced using Compounds 1 to 10. The materials used and the evaluation methods are shown below.

[0394] <Production of urethane optical material composition and cured product>

[0395] <Functional pigments>

[0396] PC1: Compound represented by the following formula

[0397]

[0398] PC2: Compound represented by the following formula

[0399]

[0400] PC3: Compound represented by the following formula

[0401]

[0402] PC4: a compound represented by the following formula

[0403]

[0404] <Polyisocyanate Compound>

[0405] NBDI: Norbornane diisocyanate

[0406] 1,3-H6XDI: 1,3-bis(isocyanatomethyl)cyclohexane

[0407] 1,4-H6XDI: 1,3-bis(isocyanatomethyl)cyclohexane

[0408] <Compounds containing active hydrogen>

[0409] TMMP: Trimethylolpropane tris(3-mercaptopropionate)

[0410] PEMP: Pentaerythritol tetrakis (3-mercaptopropionate)

[0411] DPMP: Dipentaerythritol hexa(3-mercaptopropionate)

[0412] <Compounds for Optical Materials>

[0413] Compounds (1) to (8)

[0414] L-31: diol shown below having an average molecular weight of 1100. The average values ​​of x and z are 1, and the average value of y is 17.

[0415]

[0416] <Additives>

[0417] Antioxidant: Irganox 245 manufactured by BASF JAPAN (0.1 parts by mass)

[0418] Ultraviolet absorber: Uvinul MC80 manufactured by BASF JAPAN (0.6 parts by mass)

[0419] Curing accelerator: dimethyltin chloride (0.05 parts by mass)

[0420] The above additives are blending ratios based on 100 parts by mass of the total of the polyisocyanate compound, the active hydrogen-containing compound, and the compound for an optical material.

[0421] (Example 1)

[0422] As shown in Table 3, curable compositions in which the respective components were mixed were prepared.

[0423] After the prepared curable composition was fully degassed, it was injected into a glass mold with a gap of 2 mm, and the curable composition was polymerized by injection molding polymerization. The polymerization was carried out for 18 hours while slowly heating from 27° C. to 120° C. using an air furnace. After the polymerization, the cured product was removed from the glass mold to obtain a cured product (optical article) with a thickness of 2 mm.

[0424] (Examples 2 to 8, Comparative Example 1)

[0425] A cured product was produced by the same method as in Example 1 except that the composition was changed to that shown in Table 3.

[0426] (Example 9, Comparative Example 2)

[0427] Except for changing the compounding shown in Table 4, a photochromic cured product (photochromic optical article) was produced by the same method as in Example 1.

[0428] [Evaluation Method]

[0429] 〈White turbidity〉

[0430] The degree of turbidity of the obtained photochromic cured product was evaluated by visual observation. The results are shown in Table 3.

[0431] 1: In the evaluation based on the light collector, no white turbidity was observed.

[0432] 2: In the evaluation based on the light collector, white turbidity was observed, but transparency was maintained.

[0433] 3: In the evaluation based on the light collector, white turbidity was observed and there was no transparency.

[0434] 4: No transparency in visual evaluation under fluorescent light.

[0435] 〈Photochromic properties〉

[0436] The photochromic cured products obtained in Example 9 and Comparative Example 2 were evaluated by the following method.

[0437] The following values ​​were measured using a spectrophotometer (Mini-Channel Photodetector MCPD3000) manufactured by Otsuka Electronics Co., Ltd.

[0438] Maximum absorption wavelength (λmax): the maximum absorption wavelength after color development.

[0439] Color concentration: absorbance at the above-mentioned maximum absorption wavelength after irradiation with light at 23°C for 300 seconds (A 300 ) is the difference between the absorbance when the light is not irradiated (A0).

[0440] Fading half-life 1 / 2 (sec)]: After irradiation with light for 300 seconds at 23°C, when the light irradiation is stopped, the absorbance of the sample at the aforementioned maximum absorption wavelength decreases to {A 300 -A0}.

[0441] Durability

[0442] Residual rate (%) = (A 96) / (A0)×100〕: Using a xenon arc lamp weathering machine X25 manufactured by Suga Test Instruments, the photochromic cured product was subjected to accelerated degradation for 96 hours. The color density was evaluated before and after the accelerated degradation test, and the color density (A0) of the photochromic cured product after the test was calculated. 96 ) to the color concentration (A0) of the photochromic cured product before the test (A 96 / A0) is set as the residual rate as an indicator of color development durability. The higher the residual rate, the higher the color development durability. The results are shown in Table 4.

[0443] [Table 3]

[0444] Table 3

[0445]

[0446] [Table 4]

[0447]

[0448] (Examples 16 to 28, Comparative Example 3)

[0449] A photochromic cured product was prepared by the same method as in Example 1 except that the composition was changed to that shown in Table 5. Table 5 shows the evaluation results.

[0450] [Table 5]

[0451]

[0452] <Manufacturing of acrylic optical material composition and cured product>

[0453] <Functional pigments>

[0454] PC1~PC4

[0455] <(Meth)acrylate compound>

[0456] TMPT: Trimethylolpropane trimethacrylate

[0457] A400: Polyethylene glycol diacrylate (average value of ethyleneoxy repeating units: 9)

[0458] DTMP: ditrimethylolpropane tetramethacrylate

[0459] GMA: Glycidyl Methacrylate

[0460] PR1: An acrylic modified polyrotaxane synthesized by the method described in International Publication No. 2018 / 235771. The axis molecule is formed by polyethylene glycol with a molecular weight of 11,000, the bulky groups at both ends are adamantyl groups, the cyclic molecule is α-cyclodextrin, and an average of 3.5 molecules of ε-caprolactone are ring-opening polymerized through oxypropylene groups.

[0461] The characteristics of pr2 are shown below.

[0462] The inclusion amount of α-cyclodextrin: 0.25.

[0463] Side chain modification degree: 0.5.

[0464] The molecular weight of the side chain is about 100 on average.

[0465] Molecular weight of the chain containing the polymerizable group (acryloyl group): about 650 on average (excluding the polymerizable group).

[0466] Weight average molecular weight: 200,000.

[0467] The results show that pr2 is a structure in which acryloyl groups as polymerizable groups are introduced into 50% of the side chains, and 50% of the side chains have OH groups at the ends. 1 H-NMR measurement revealed that chains having an average of about 140 polymerizable groups (acryloyl groups) were introduced per molecule.

[0468] <Compounds for Optical Materials>

[0469] Compounds (9) to (10)

[0470] <Additives>

[0471] Antioxidant: Irganox 245 manufactured by BASF Japan (1 part by mass)

[0472] Light stabilizer: Tinuvin 765 manufactured by BASF Japan (3 parts by mass)

[0473] Leveling agent: L7001 manufactured by DOW TORAY CO., LTD. (0.1 parts by mass)

[0474] Photopolymerization initiator: Omnirad 819 manufactured by IGM Resins BV (0.3 parts by mass)

[0475] In addition, the said additive is the compounding ratio when the sum of the (meth)acrylate compound and the compound for optical materials is 100 parts by mass.

[0476] (Examples 29 to 33, Comparative Example 4)

[0477] An optical material composition was prepared by mixing the components according to the formulation shown in Table 6. Next, a thiourethane plastic lens having a center thickness of 2 mm and a refractive index of 1.60 was prepared as an optical substrate. The thiourethane plastic lens was previously alkali-etched using a 10% sodium hydroxide aqueous solution at 50° C. for 5 minutes, and then thoroughly washed with distilled water.

[0478] On the surface of the plastic lens, a moisture curing primer (product name: TR-SC-P, manufactured by TOKUYAMA) was applied at 70 rpm for 15 seconds using a spin coater (1H-DX2, manufactured by MIKASA) and then at 1000 rpm for 10 seconds. Thereafter, about 2 g of the optical material composition obtained above was spin-coated at 60 rpm for 40 seconds in a manner such that the film thickness of the coating layer was 40 μm, and then at 600 rpm for 10 to 20 seconds.

[0479] In nitrogen atmosphere, the output power was 200mW / cm 2 The lens having the coating agent applied on the surface was irradiated with light for 90 seconds using a metal halide lamp to cure the coating film. Thereafter, the lens was further heated at 110° C. for 1 hour to obtain a photochromic optical article having the photochromic cured product applied on the surface of the plastic lens.

[0480] The obtained photochromic optical article was evaluated by the same method as in Example 15. The evaluation results are shown in Table 6.

[0481] [Table 6]

[0482]

[0483] <Production of urethane urea prepolymer and laminate>

[0484] <Functional pigments>

[0485] PC1

[0486] <Polyisocyanate Compound>

[0487] IPDI: Isophorone diisocyanate

[0488] <Compounds containing active hydrogen>

[0489] PCD: DURANOL manufactured by Asahi Kasei Corporation (Mn: 1000, hydroxyl value: 114.1)

[0490] MBCHA: 4,4'-methylenebis(cyclohexylamine)

[0491] <Compounds for Optical Materials>

[0492] Compound (5)

[0493] <Solvent>

[0494] DEK: Diethyl Ketone

[0495] TBA: tert-butyl alcohol

[0496] <Additives>

[0497] Antioxidant: Irganox 245 manufactured by BASF JAPAN (0.35 parts by mass)

[0498] Leveling agent: L7001 manufactured by DOW TORAY CO., LTD. (0.05 parts by mass)

[0499] In addition, the said additive is the compounding ratio when making a prepolymer 100 mass parts.

[0500] (Example 34)

[0501] Production of urethane urea prepolymers:

[0502] 100 g of IPDI, 470 g of compound 5 and 60 g of DEK were added to a 2 L reaction vessel to obtain a mixture. The mixture was stirred at 150 rpm for 5 hours at 100° C. under a nitrogen atmosphere to obtain a reaction solution containing a urethane prepolymer. The reaction endpoint was confirmed by back titration of the isocyanate group.

[0503] Next, the obtained reaction liquid was cooled to 10° C., and then 760 g of DEK and 200 g of TBA were added, and the liquid temperature was maintained at 15° C. 21.3 g of MBCHA was added dropwise to the reaction liquid, and the mixture was reacted at 15° C. for 1 hour, thereby obtaining the target urethane urea prepolymer PRE1. It should be noted that the obtained PRE1 had a solid content concentration of 37.4% by mass, a number average molecular weight of 16,000, and a softening point of 96° C.

[0504] Next, 100 g of PRE1, 1.00 g of PC1, 0.35 g of Irganox 245, and 0.05 g of L7001 were mixed and stirred at room temperature to obtain an adhesive optical material composition AC1 containing PRE1.

[0505] Manufacturing of laminates:

[0506] Using a rod coater, the adhesive optical material composition AC1 containing PRE1 is applied to a PET (polyethylene terephthalate) film (manufactured by DuPont Teijin Films, PUREX FILM, with a silicone coating) to obtain a coating. After the coating is dried at 100°C for 5 minutes, the PET film is peeled off to obtain a photochromic adhesive sheet with a thickness of about 30 μm. Next, the obtained photochromic adhesive sheet is sandwiched and bonded with two polyvinyl alcohol films (thickness 75 μm) to obtain a laminate. It should be noted that the laminate is in the shape of a rectangular strip. The adhesive composition is not applied to one end of the long side direction of the laminate, which serves as an uncoated portion.

[0507] The laminate was heated at 100° C. for 6 hours while pressing the four corners to prevent shrinkage. The heated laminate was vacuum dried at room temperature and 13 Torr for 5 hours to obtain a photochromic adhesive sheet 1 .

[0508] The obtained photochromic optical article was evaluated by the same method as in Example 15. The evaluation results are shown in Table 6.

[0509] (Comparative Example 5)

[0510] Production of urethane urea prepolymers:

[0511] The target prepolymer PRE2 was prepared in the same manner as in Example 34 except that PCD (315 g) was used instead of Compound 5. The obtained PRE2 had a solid content concentration of 37.6% by mass, a number average molecular weight of 13,000, and a softening point of 98°C.

[0512] In addition, in the same manner as in Example 34, an adhesive optical material composition AC2 containing PRE2 according to the formulation shown in Table 6 was prepared.

[0513] Manufacturing of laminates:

[0514] A photochromic adhesive sheet 2 was obtained by the same method as in Example 34 using the adhesive optical material composition AC2 containing PRE2.

[0515] The evaluation results of the obtained photochromic optical article are shown in Table 7 in the same manner as in Example 34.

[0516] [Table 7]

[0517]

[0518] 〈Manufacturing of glass-bonded photochromic optical articles〉

[0519] (Example 35)

[0520] As shown in Table 8, a composition for an optical material in which each component was mixed was prepared.

[0521] Next, the prepared optical material composition was used as an adhesive to bond a pair of optical glass plates (thickness 0.8 mm) to produce a photochromic optical article. First, the optical material composition was applied to a glass plate for optical articles provided with a 0.1 mm thick spacer, and another glass plate for optical articles was placed thereon, and then the optical material composition was polymerized. The polymerization was performed using an air furnace, and the temperature was slowly raised from 27°C to 120°C while being cured for 18 hours, and a pair of optical plates were bonded to obtain a glass-bonded photochromic optical article having a 0.1 mm thick photochromic layer.

[0522] The obtained photochromic optical article was evaluated by the same method as in Example 15. The evaluation results are shown in Table 8.

[0523] [Table 8]

[0524]

[0525] In addition, in Table 3 - Table 8, the numbers in parentheses mean parts by mass.

Claims

1. A composition for an optical material, comprising: A compound for an optical material represented by the following formula (I); and at least one compound selected from the group consisting of a compound having a radical polymerizable group, a compound having an addition polymerizable group, and a compound having a reactive group that reacts with the addition polymerizable group, In the formula (I), p and q are each independently 1 or more and 43 or less, p+q is greater than or equal to 2 and less than or equal to 44, X 1 and X 2 are each independently hydrogen, mercaptoethyl, 3-mercaptopropionyl, allyl, acryloyl or methacryloyl, R 1 is a divalent group represented by the following formula (Ia) or (Ib), R 2 and R 3 is methylene or ethylene, In the formula (Ia), R 11 is a linear or branched alkylene group having 2 to 10 carbon atoms, R 12 and R 13 For the 11 a linear or branched alkylene group having 3 or more and 10 or less carbon atoms of a different structure, a is greater than or equal to 1 and less than or equal to 27, m and n are each independently 1 or more and 32 or less, m+n is greater than or equal to 2 and less than or equal to 32, In the formula (Ib), R 14 is a linear or branched alkylene group having 3 or more and 10 or less carbon atoms, R 15 For the 14 a linear or branched alkylene group having 3 or more and 10 or less carbon atoms of a different structure, b is greater than or equal to 1 and less than or equal to 25, c is greater than or equal to 1 and less than or equal to 31.

2. The composition for optical material according to claim 1, wherein The optical material compound has a number average molecular weight calculated from a hydroxyl value based on Japanese Industrial Standard K 1557-1:2007 or a number average molecular weight calculated by a nuclear magnetic resonance (NMR) method of 500 or more and 2000 or less.

3. The composition for optical material according to claim 1, wherein With respect to the number average molecular weight of the compound for optical material, R 2 Number average molecular weight of O chain and R by NMR method 3 The ratio of the sum of the number average molecular weights of the O chains determined by the NMR method is 4% or more and 97% or less.

4. The composition for optical material according to claim 1, wherein With respect to the number average molecular weight of the compound for optical material, R 1 The ratio of the number average molecular weight of the base by the NMR method is 3% or more and 96% or less. Composition for optical material.

5. The composition for optical material according to claim 1, wherein The radical polymerizable group includes at least one functional group selected from the group consisting of an acryloyl group, a methacryloyl group, and an allyl group.

6. The composition for optical material according to claim 1, wherein The polyaddition reactive group includes at least one functional group selected from the group consisting of an isocyanate group, an isothiocyanate group, and an epoxy group.

7. The composition for optical material according to claim 1, wherein The reactive group includes at least one functional group selected from the group consisting of a hydroxyl group, an amino group, a mercapto group, and a carboxyl group.

8. The composition for optical material according to claim 1, wherein The ratio of the compound for optical material is 5 mass % or more and 60 mass % or less. 9 . The composition for an optical material according to claim 1 , further comprising a functional pigment. 10 . The composition for an optical material according to claim 1 , further comprising a photochromic compound. 11 . The composition for an optical material according to claim 1 , comprising the compound having the radical polymerizable group, or comprising the compound having the addition polymerizable group and a compound having a reactive group that reacts with the addition polymerizable group. 12 . A cured product, which is a cured product of the composition for an optical material according to claim 1 .

13. An optical article comprising the cured product according to claim 12.

14. A lens comprising the cured product according to claim 12.

15. Spectacles comprising the lens according to claim 14.

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