Polymerizable composition for optical materials and method for producing the same, and optical materials

Abstract

This polymerizable composition for an optical material contains: a polyisocyanate (a) that contains an aliphatic polyisocyanate (a1) and a modified aliphatic polyisocyanate (a2); a polythiol composition (b) that contains a polythiol compound; and a compound (c) that is represented by formula (1). R1 through R8 each independently represent a group represented by formula (2), a C1 to C20 alkyl group, a C1 to C20 alkoxy group, a hydroxy group, or a polysiloxy group. However, at least one of R1 through R8 is a group represented by formula (2). m and n each independently represent an integer of zero or higher. R25 represents a C1 to C20 alkylene group or the like, k represents an integer of one or higher, and * represents a binding position.

Description

[Technical Field]

[0001] This disclosure relates to polymerizable compositions for optical materials, methods for producing the same, and optical materials. [Background technology]

[0002] Traditionally, glass optical materials have been used as optical materials (for example, lenses). In recent years, the use of resin-based optical materials has also expanded due to their lightweight properties and moldability.

[0003] For example, Patent Document 1 discloses a polymerizable composition for optical materials containing a polyisocyanate and a polythiol, as a polymerizable composition for optical materials for manufacturing resin-based optical materials. Specifically, Patent Document 1 discloses a polymerizable composition for optical materials containing a polyisocyanate (a) including an aliphatic polyisocyanate (a1) and a modified aliphatic polyisocyanate (a2), and a polythiol (b) having two or more functional thiol groups. Patent Document 1 states that, according to the polymerizable composition for optical materials described in the document, optical materials with excellent physical properties such as transparency, refractive index, heat resistance, and strength can be obtained.

[0004] Patent Document 1: International Publication No. 2015 / 119220 [Overview of the project] [Problems that the invention aims to solve]

[0005] However, in cases where it is desired to further reduce striations in resins for optical materials obtained from polymerizable compositions for optical materials containing a polyisocyanate (a) including an aliphatic polyisocyanate (a1) and a modified aliphatic polyisocyanate (a2), and a polythiol composition (b) including a polythiol compound, it is sometimes required. An object of one aspect of this disclosure is to provide a polymerizable composition for optical materials that can produce a resin with reduced striations, and an optical material containing a resin with reduced striations.

Means for Solving the Problem

[0006] The means for solving the above problems include the following aspects. <1> A polyisocyanate (a) containing an aliphatic polyisocyanate (a1) and a modified product (a2) of an aliphatic polyisocyanate, a polythiol composition (b) containing a polythiol compound, a polyether-modified silicone compound (c) represented by the following formula (1), and a polymerizable composition for optical materials.

[0007]

Chemical Formula

[0008] In formula (1), R1 to R8 each independently represent a polyether group represented by formula (2), an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a hydroxy group, or a polysiloxy group. However, at least one of R1 to R8 is a polyether group represented by formula (2). In formula (1), m and n each independently represent an integer of 0 or more. In formula (1), when there are plural R2 to R5, each of the plural R2 to R5 may be the same or different. In formula (2), R 25 represents an alkylene group having 1 to 20 carbon atoms, R 26 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an alkynyl group having 2 to 20 carbon atoms, k represents an integer of 1 or more, and * represents a bonding position. In formula (2), when there are plural R 25 , each of the plural R 25 may be the same or different.

[0009] <2> The polymerizable composition for optical materials according to <1>, wherein the modified product (a2) contains a mononuclear isocyanurate of an aliphatic polyisocyanate. <3> At least one of the aliphatic polyisocyanate in the aliphatic polyisocyanate (a1) and the modified product (a2) contains at least one selected from the group consisting of pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, lysine diisocyanate, lysine triisocyanate, dimer acid diisocyanate, octamethylene diisocyanate, and decamethylene diisocyanate. <1> The polymerizable composition for an optical material according to <1> or <2>. <4> The polymerizable composition for an optical material according to any one of <1> to <3>, wherein at least one of the aliphatic polyisocyanate in the aliphatic polyisocyanate (a1) and the modified product (a2) contains an aliphatic polyisocyanate obtained from a plant-derived raw material. <5> The polythiol compound is 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, pentaerythritol tetrakis(2-mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionate), 2,5-dimercaptomethyl-1,4-dithiane, bis(2-mercaptoethyl) sulfide, and diethylene glycol bis(3-mercaptopropionate) The polymerizable composition for an optical material according to any one of <1> to <4>, which is at least one selected from the group consisting of. <6> The polymerizable composition for an optical material according to any one of <1> to <5>, wherein the polythiol compound contains a polythiol compound obtained from a plant-derived raw material. <7> The proportion of the modified material (a2) in the polyisocyanate (a) is 60% by mass or less. <1> ~ <6> A polymerizable composition for optical materials as described in any one of the following. <8> The total content of the polyisocyanate (a) and the polythiol composition (b) is 80% by mass or more based on the total amount of the polymerizable composition for optical materials. <1> ~ <7> A polymerizable composition for optical materials as described in any one of the following. <9> The content of the polyether-modified silicone compound (c) is 0.001% to 5% by mass relative to the total amount of the polymerizable composition for optical materials. <1> ~ <8> A polymerizable composition for optical materials as described in any one of the following. <10> Furthermore, it contains an acidic phosphate ester as an ultraviolet absorber, polymerization catalyst, and internal mold release agent. <1> ~ <8> A polymerizable composition for optical materials as described in any one of the following. <11> The amount of the UV absorber is 0.1% to 5% by mass relative to the total amount of the polymerizable composition for optical materials. The content of the polymerization catalyst is 0.001% to 5% by mass relative to the total amount of the polymerizable composition for optical materials. The content of the acidic phosphate ester as the internal release agent is 0.001% to 5% by mass relative to the total amount of the polymerizable composition for optical materials. <10> Polymerizable composition for optical materials as described above. <12> <1> ~ <11> An optical material comprising a resin which is a cured product of a polymerizable composition for optical materials described in any one of the above. <13> The biomass content of the aforementioned resin is 25% or more. <12> Optical materials as described above. <14> <10> or <11> A method for producing the polymerizable composition for optical materials described above, The process involves adding the polyether-modified silicone compound (c) and the acidic phosphate ester to the aliphatic polyisocyanate (a1) to obtain solution A1. A step of dissolving the ultraviolet absorber and the polymerization catalyst in the aliphatic polyisocyanate (a1) to obtain solution A2, A step of mixing solution A1, solution A2, and the modified substance (a2) to obtain solution A3, The steps include adding the polythiol composition (b) to the solution A3 to obtain the polymerizable composition for optical materials, including, A method for producing polymerizable compositions for optical materials. [Effects of the Invention]

[0010] According to one aspect of this disclosure, a polymerizable composition for optical materials that can produce a resin with reduced striations, and an optical material comprising a resin with reduced striations are provided. [Modes for carrying out the invention]

[0011] In this disclosure, a numerical range represented by "~" means a range that includes the numbers written before and after "~" as the lower and upper limits, respectively. In this disclosure, the amount of each component in a composition means the total amount of any multiple substances present in the composition, unless otherwise specified, if there are multiple substances corresponding to each component in the composition. In numerical ranges described in stages within this disclosure, the upper or lower limit of one numerical range may be replaced with the upper or lower limit of another numerical range described in stages. Furthermore, in numerical ranges described within this disclosure, the upper or lower limit of that range may be replaced with the values ​​shown in the examples.

[0012] [Polymerizable composition] The polymerizable composition for optical materials disclosed herein (hereinafter also simply referred to as "polymerizable composition") A polyisocyanate (a) comprising an aliphatic polyisocyanate (a1) and a modified aliphatic polyisocyanate (a2), A polythiol composition (b) containing a polythiol compound with two or more functions, A polyether-modified silicone compound (c) represented by the following formula (1), Includes.

[0013] [ka]

[0014] In formula (1), R1 to R8 each independently represent a polyether group represented by formula (2), an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a hydroxyl group, or a polysiloxy group. However, at least one of R1 to R8 is a polyether group represented by formula (2). In equation (1), m and n each independently represent a non-negative integer. In equation (1), if there are multiple instances of each of R2 to R5, each of the multiple instances of R2 to R5 may be the same or different. In formula (2), R 25 R represents an alkylene group with 1 to 20 carbon atoms. 26 * represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an alkynyl group having 2 to 20 carbon atoms; k represents an integer of 1 or more; and * represents the bond position. In formula (2), R 25 If there are multiple instances, then there are multiple R 25 They may be the same or different.

[0015] As mentioned above, in some cases, it is desirable to further reduce the striations in resins obtained from polymerizable compositions containing a polyisocyanate (a) including an aliphatic polyisocyanate (a1) and a modified aliphatic polyisocyanate (a2), and a polythiol composition (b) containing a bifunctional or more polythiol compound. According to the polymerizable composition of this disclosure, a resin with suppressed striations can be obtained. This effect is thought to be brought about by the polyether-modified silicone compound (c).

[0016] The following describes the components that may be included in the polymerizable composition of this disclosure.

[0017] <Polyisocyanate (a)> The polymerizable composition of this disclosure contains polyisocyanate (a). Polyisocyanate (a) includes aliphatic polyisocyanate (a1) and modified aliphatic polyisocyanate (a2).

[0018] The polyisocyanate (a) preferably contains aliphatic polyisocyanate (a1) and a modified aliphatic polyisocyanate (a2) as its main components.

[0019] In this disclosure, "main component" means a component whose content is 50% by mass or more. In this disclosure, the content of the "main component" is preferably 60% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more.

[0020] That is, the proportion of aliphatic polyisocyanate (a1) and modified polyisocyanate (a2) in polyisocyanate (a) is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, and even more preferably 80% by mass or more. The proportion of aliphatic polyisocyanate (a1) and modified polyisocyanate (a2) in polyisocyanate (a) may be 100% by mass or less than 100% by mass.

[0021] (Aliphatic polyisocyanate (a1)) Examples of aliphatic polyisocyanates (a1) include trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate methyl ester, lysine diisocyanate, lysine triisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, bis(isocyanate methyl)naphthalene, mesityl Examples include relentriisocyanates, bis(isocyanate methyl) sulfide, bis(isocyanate ethyl) sulfide, bis(isocyanate methyl) disulfide, bis(isocyanate ethyl) disulfide, bis(isocyanate methylthio) methane, bis(isocyanate ethylthio) methane, bis(isocyanate ethylthio) ethane, bis(isocyanate methylthio) ethane, diisocyanate dimer acid, octamethylene diisocyanate, decamethylene diisocyanate, etc. As an aliphatic polyisocyanate (a1), Preferably, it is an acyclic aliphatic polyisocyanate such as pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, lysine diisocyanate, lysine triisocyanate, dimer acid diisocyanate, octamethylene diisocyanate, decamethylene diisocyanate, etc. More preferably, the material is a linear aliphatic polyisocyanate such as pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, lysine diisocyanate, lysine triisocyanate, octamethylene diisocyanate, or decamethylene diisocyanate. These aliphatic polyisocyanates (a1) can be used alone or in combination of two or more.

[0022] The aliphatic polyisocyanate (a1) preferably contains at least one selected from the group consisting of pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, lysine diisocyanate, lysine triisocyanate, dimer acid diisocyanate, octamethylene diisocyanate, and decamethylene diisocyanate.

[0023] The proportion of aliphatic polyisocyanate (a1) in polyisocyanate (a) is preferably 10% by mass or more, more preferably 20% by mass or more, even more preferably 30% by mass or more, even more preferably 40% by mass or more, even more preferably 45% by mass or more, and even more preferably 50% by mass or more, from the viewpoint of ensuring the functionality of the resulting resin as an optical material (for example, from the viewpoint of suppressing bubbles and distortion).

[0024] (Aliphatic polyisocyanate variant (a2)) Examples of aliphatic polyisocyanates in modified aliphatic polyisocyanates (a2) include compounds similar to those in aliphatic polyisocyanate (a1). (i.e., the aliphatic polyisocyanate before modification to form modified aliphatic polyisocyanate (a2); the same applies hereinafter.) The aliphatic polyisocyanate (a1) and the modified polyisocyanate (a2) may be the same or different, but it is preferable that they be the same.

[0025] Examples of modified aliphatic polyisocyanates (a2) (hereinafter also simply referred to as "modified a2") include aliphatic polyisocyanate polymers, aliphatic polyisocyanate biuret modified compounds, aliphatic polyisocyanate allophanate modified compounds, aliphatic polyisocyanate oxadiazinetrione modified compounds, and aliphatic polyisocyanate polyol modified compounds.

[0026] Examples of aliphatic polyisocyanate polymers include dimers of urethione, uretoimine, and carbodiimide, and polymers of trimers or more of isocyanurates and iminooxadiandione.

[0027] Isocyanurates of aliphatic polyisocyanates can be obtained by reacting aliphatic polyisocyanates in the presence of a known isocyanuration catalyst.

[0028] Biuret-modified aliphatic polyisocyanates can be obtained by reacting an aliphatic polyisocyanate with, for example, water, a tertiary alcohol (e.g., t-butyl alcohol), or a secondary amine (e.g., dimethylamine, diethylamine), followed by further reaction in the presence of a known biuretization catalyst.

[0029] Allophanate-modified aliphatic polyisocyanates can be obtained by reacting an aliphatic polyisocyanate with a monoalcohol (a monohydric alcohol, e.g., an alcohol with 1 to 10 carbon atoms), followed by further reaction in the presence of a known allophanate catalyst. Oxadiazinetrione-modified aliphatic polyisocyanates can be obtained by reacting an aliphatic polyisocyanate with carbon dioxide. Imino-oxadianedione modified aliphatic polyisocyanates can be obtained by further reacting aliphatic polyisocyanates in the presence of known imino-oxadianedione catalysts. Polyol-modified aliphatic polyisocyanates can be obtained by the reaction of aliphatic polyisocyanates with alcohols. Examples of alcohols used to obtain modified aliphatic polyisocyanates include tertiary alcohols, monoalcohols, and polyhydric alcohols, preferably trihydric alcohols such as glycerin and trimethylolpropane. From the perspective of utilizing non-fossil resources, plant-derived alcohols are preferred as the alcohols used to obtain modified aliphatic polyisocyanates.

[0030] Modified aliphatic polyisocyanates (a2) can be used alone or in combination of two or more.

[0031] The modified product (a2) preferably contains a polymer of aliphatic polyisocyanate, and more preferably contains an isocyanurate mononuclear of aliphatic polyisocyanate (i.e., an isocyanurate which is a trimer of aliphatic polyisocyanate).

[0032] The proportion of the modified material (a2) in the polyisocyanate (a) is preferably 60% by mass or less, from the viewpoint of improving the functionality of the resulting resin as an optical material (for example, from the viewpoint of suppressing bubbles and distortion). On the other hand, the modified material (a2) contributes to the physical properties of the resulting resin (e.g., transparency, refractive index, heat resistance, strength, etc.). From the viewpoint of further improving the physical properties of the resulting resin, the proportion of the modified material (a2) in the polyisocyanate (a) is preferably 1% by mass or more. The proportion of the modified product (a2) in the polyisocyanate (a) is more preferably 1% to 60% by mass, even more preferably 5% to 55% by mass, even more preferably 10% to 50% by mass, and even more preferably 30% to 50% by mass.

[0033] As the polyisocyanate (a), the reaction solution obtained when preparing the modified aliphatic polyisocyanate (a2) may be used. In this case, the reaction solution contains an aliphatic polyisocyanate (a1) and a modified form (a2) which is a modified form of the aliphatic polyisocyanate (a1). Furthermore, polyisocyanate (a) can also be obtained by mixing the prepared mutant (a2) with aliphatic polyisocyanate (a1), which is the same as or different from the aliphatic polyisocyanate used in preparing the modified product (a2).

[0034] From the viewpoint of more effectively exhibiting the effects of the polymerizable composition of this disclosure, it is preferable that at least one of the aliphatic polyisocyanates in the aliphatic polyisocyanate (a1) and the modified product (a2) contains at least one selected from the group consisting of pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, lysine diisocyanate, lysine triisocyanate, dimer acid diisocyanate, octamethylene diisocyanate, and decamethylene diisocyanate.

[0035] Furthermore, from the viewpoint of utilizing non-fossil resources, it is preferable that in the polymerizable composition of this disclosure, at least one of the aliphatic polyisocyanates in the aliphatic polyisocyanate (a1) and the modified product (a2) contains an aliphatic polyisocyanate obtained from plant-derived raw materials. Examples of plant-derived aliphatic polyisocyanates include pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, lysine diisocyanate, lysine triisocyanate, dimer acid diisocyanate, octamethylene diisocyanate, and decamethylene diisocyanate, which can be used alone or in combination of two or more. Preferably, the plant-derived aliphatic polyisocyanate is pentamethylene diisocyanate, and particularly preferably 1,5-pentamethylene diisocyanate.

[0036] Plant-derived aliphatic polyisocyanates can be obtained, for example, by acid amidating a plant-derived divalent carboxylic acid, reducing it to a terminal amino group, and then reacting it with phosgene to convert the terminal amino group into an isocyanate group. Furthermore, plant-derived polyisocyanates can also be obtained by using plant-derived amino acids as raw materials and converting the amino groups in the plant-derived amino acids into isocyanate groups. For example, plant-derived pentamethylene diisocyanate can be obtained by decarboxylating the carboxyl group of lysine and then converting the amino group to an isocyanate group. 1,5-pentamethylene diisocyanate is particularly preferred as the pentamethylene diisocyanate.

[0037] By curing a polymerizable composition in which at least one of the aliphatic polyisocyanates in aliphatic polyisocyanate (a1) and modified product (a2) is an aliphatic polyisocyanate obtained from plant-derived raw materials, a resin with a biomass content of 25% or more, as described later, is easily obtained. Examples of aliphatic polyisocyanates obtained from plant-derived raw materials include pentamethylenediisocyanates obtained by phosgenating pentamethylenediamine or its salts obtained by biochemical methods, as described in International Publication No. 2012 / 121291.

[0038] The polymerizable compositions of this disclosure may also be used in combination with polyisocyanate (a) and at least one selected from alicyclic polyisocyanates, aromatic polyisocyanates, and heterocyclic polyisocyanates. For alicyclic polyisocyanates, aromatic polyisocyanates, and heterocyclic polyisocyanates, please refer to the description in International Publication No. 2015 / 119220.

[0039] <Polythiol composition (b)> The polymerizable composition of this disclosure contains a polythiol composition (b) comprising a polythiol compound. The polythiol composition (b) preferably contains a polythiol compound as its main component.

[0040] (Polythiol compounds) The polythiol compound in polythiol composition (b) may be any compound having two or more thiol groups. For information regarding the polythiol compound in polythiol composition (b), please refer to the description in International Publication No. 2015 / 119220.

[0041] Polythiol composition (b) is 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8-Dimercaptomethyl-1,11-Dimercapto-3,6,9-Trithiaundecane, 4,7-Dimercaptomethyl-1,11-Dimercapto-3,6,9-Trithiaundecane, 5,7-Dimercaptomethyl-1,11-Dimercapto-3,6,9-Trithiaundecane, Pentaerythritol tetrakis (2-mercaptoacetate), Pentaerythritol tetrakis (3-mercaptopropionate), 2,5-Dimercaptomethyl-1,4-Dithiane, Bis(2-mercaptoethyl) sulfide, and Diethylene glycol bis(3-mercaptopropionate) It is preferable to include at least one selected from the group consisting of (hereinafter also referred to as "polythiol component S"). The polythiol composition (b) more preferably contains polythiol component S as its main component. In this case, the polythiol composition (b) may contain at least one other component besides the polythiol component S (for example, other polythiol compounds, components other than polythiol compounds, etc.).

[0042] A more specific embodiment of the polythiol composition (b) is, for example; An embodiment comprising pentaerythritol tetrakis(3-mercaptopropionate) (hereinafter also referred to as "polythiol component S1") as the main component; Embodiments comprising 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (hereinafter, these three compounds are collectively referred to as "polythiol component S2") as the main components; An embodiment comprising 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (hereinafter also referred to as "polythiol component S3") as the main component; Embodiments comprising polythiol component S1 and polythiol component S2 as main components; Embodiments comprising polythiol component S2 and polythiol component S3 as main components; These are some examples. Each embodiment of the polythiol composition (b) may contain at least one other component besides the main component (for example, other polythiol compounds, components other than polythiol compounds, etc.).

[0043] The polythiol compound in the polythiol composition (b) preferably includes a polythiol compound obtained from plant-derived raw materials. Examples of polythiol compounds obtained from plant-derived raw materials include polythiol compounds synthesized using epichlorohydrin, which is produced from glycerin obtained from plant-derived raw materials through chlorination and epoxidation (for example, the aforementioned polythiol component S). Glycerin obtained from plant-derived raw materials includes, for example, glycerin obtained by hydrolysis and / or transesterification of glycerin fatty acid esters contained in vegetable oils such as rapeseed oil, palm oil, castor oil, and olive oil.

[0044] In the polythiol composition (b), the polythiol compound is obtained by curing a polymerizable composition containing a polythiol compound obtained from plant-derived raw materials, which makes it easier to obtain a resin with a biomass content of 25% or more, as described later. However, a resin having a biomass content of 25% or more can be produced without using a polymerizable composition of an embodiment containing a polythiol compound obtained from a plant-derived raw material.

[0045] There is no particular limitation on the total content of the polyisocyanate (a) and the polythiol composition (b) in the polymerizable composition of the present disclosure, but the total content of the polyisocyanate (a) and the polythiol composition (b) is preferably 80% by mass or more based on the total amount of the polymerizable composition of the present disclosure.

[0046] In the polymerizable composition of the present disclosure, the molar ratio of the total thiol groups in the polythiol composition (b) to the total isocyanate groups in the polyisocyanate (a) is preferably 0.8 to 1.2, more preferably 0.85 to 1.15, and even more preferably 0.9 to 1.1.

[0047] <Polyether-modified silicone compound (c)> The polymerizable composition of the present disclosure contains a polyether-modified silicone compound (c) represented by the following formula (1) (hereinafter, also referred to as "the compound represented by formula (1)").

[0048]

Chemical formula

[0049] In formula (1), R1 to R8 each independently represent a polyether group represented by formula (2), an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a hydroxy group, or a polysiloxy group. However, at least one of R1 to R8 is a polyether group represented by formula (2). In formula (1), m and n each independently represent an integer of 0 or more. In formula (1), when there are a plurality of each of R2 to R5, each of the plurality of R2 to R5 may be the same or different. In formula (2), R 25 represents an alkylene group having 1 to 20 carbon atoms, and R 26* represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an alkynyl group having 2 to 20 carbon atoms; k represents an integer of 1 or more; and * represents the bond position. In formula (2), R 25 If there are multiple instances, then there are multiple R 25 They may be the same or different.

[0050] In formula (2), R 25 The alkylene group having 1 to 20 carbon atoms represented by is preferably a linear alkylene group having 1 to 20 carbon atoms (i.e., a straight-chain or branched alkylene group). R 25 Examples of alkylene groups having 1 to 20 carbon atoms represented by include methylene group, ethylene group, n-propylene group, isopropylene group, n-butylene group, isobutylene group, t-butylene group, n-pentylene group, isopentylene group, t-pentylene group, n-hexylene group, n-heptylene group, isoheptylene group, n-octylene group, isooctylene group, n-nonylene group, isononylene group, n-decylene group, isodecylene group, n-undecylene group, isoundecylene group, n-dodecylene group, isododecylene group, cyclopentylene group, cyclohexylene group, cycloheptylene group, cyclooctylene group, cyclononylene group, methylcyclopentylene group, and methylcyclohexylene group. R 25 The alkylene group having 1 to 20 carbon atoms represented by the formula is more preferably a linear or branched alkylene group having 1 to 8 carbon atoms.

[0051] In equations (1) and (2), R1 to R8 or R 26 The alkyl group having 1 to 20 carbon atoms represented by is preferably a linear alkyl group having 1 to 20 carbon atoms (i.e., a linear or branched alkyl group). R1~R8 or R 26Examples of alkyl groups having 1 to 20 carbon atoms represented by include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, isopentyl group, t-pentyl group, n-hexyl group, n-heptyl group, isoheptyl group, n-octyl group, isooctyl group, n-nonyl group, isononyl group, n-decyl group, isodecyl group, n-undecyl group, isoundecyl group, n-dodecyl group, isododecyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, methylcyclopentyl group, and methylcyclohexyl group. R1~R8 or R 26 As an alkyl group having 1 to 20 carbon atoms, more preferably a linear or branched alkyl group having 1 to 8 carbon atoms.

[0052] In equations (1) and (2), R1 to R8 or R 26 The alkoxy group having 1 to 20 carbon atoms represented by is preferably a linear alkoxy group having 1 to 20 carbon atoms (i.e., a straight-chain or branched alkoxy group). R1~R8 or R 26 Examples of alkoxy groups having 1 to 20 carbon atoms represented by include methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, t-butyloxy group, n-pentyloxy group, isopentyloxy group, t-pentyloxy group, n-hexyloxy group, n-heptyloxy group, isoheptyloxy group, n-octyloxy group, isooctyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, isodecyloxy group, n-undecyloxy group, isoundecyloxy group, n-dodecyloxy group, isododecyloxy group, cyclopentyloxy group, cyclohexyloxy group, cycloheptyloxy group, cyclooctyloxy group, cyclononyloxy group, methylcyclopentyloxy group, and methylcyclohexyloxy group. R1~R8 or R 26 As the alkoxy group having 1 to 20 carbon atoms represented by , more preferably it is a linear or branched alkoxy group having 1 to 8 carbon atoms.

[0053] In formula (2), R 26 The alkenyl group having 2 to 20 carbon atoms represented by is preferably a linear alkenyl group having 2 to 20 carbon atoms (i.e., a straight-chain or branched alkenyl group). R 26 Examples of alkenyl groups having 2 to 20 carbon atoms, represented by , include vinyl group, 1-propenyl group, 2-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, 6-heptenyl group, 7-octenyl group, 8-nonenyl group, 9-dekenyl group, 2-methyl-1-propenyl group, 2-methyl-2-propenyl group, 3-methyl-3-butenyl group, 4-methyl-4-pentenyl group, and 2-cyclohexyl-2-propenyl group. R 26 As an alkenyl group having 2 to 20 carbon atoms, more preferably a linear or branched alkenyl group having 2 to 8 carbon atoms, the formula is used.

[0054] In formula (2), R 26 The alkynyl group having 2 to 20 carbon atoms represented by is preferably a linear alkynyl group having 2 to 20 carbon atoms (i.e., a straight-chain or branched alkynyl group). R 26 Examples of alkynyl groups having 2 to 20 carbon atoms, represented by , include ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 2-methyl-2-propynyl group, 3-methyl-1-butynyl group, 4-pentynyl group, 5-hexynyl group, 6-heptynyl group, 7-octinyl group, 8-noninyl group, and 9-decinyl group. R 26 As the alkynyl group having 2 to 20 carbon atoms represented by , more preferably it is a linear or branched alkynyl group having 2 to 8 carbon atoms.

[0055] Examples of compounds represented by formula (1) include: Polyflow KL-100, Polyflow KL-600, Granol 410 (product names manufactured by Kyoeisha Chemical Co., Ltd.); BYK-302, BYK-307, BYK-322, BYK-323, BYK-331, BYK-333, BYK-347, BYK-348, BYK-349 (product name manufactured by BYK-Chemie Co., Ltd.); KF-351, KF-352, KF-353, KF-354L, KF-355, KF-355A, KF-615A, KF-618 (product names manufactured by Shin-Etsu Chemical Co., Ltd.) SH3746, SH3771, SH8400, SF8410 (product names manufactured by Toray Dow Corning Co., Ltd.); Examples include TSF4440, TSF4445, TSF4446, and TSF4452 (product names manufactured by Toshiba Silicone Co., Ltd.). Particularly preferred examples are the Polyflow KL-100 and Polyflow KL-600 (product names manufactured by Kyoeisha Chemical Co., Ltd.). Furthermore, from the viewpoint of extending the pot life of the polymerizable composition while improving the balance between the effect of suppressing pulverization of the resulting molded article and the effect of improving the transparency of the molded article, the compound represented by formula (1) is preferably one or more selected from Polyflow KL-100 and Polyflow KL-600 (product names manufactured by Kyoeisha Chemical Co., Ltd.), and more preferably Polyflow KL-100. Here, Polyflow KL-100 contains the compound represented by formula (1A) and the compound represented by formula (1B) described below.

[0056] Furthermore, from the viewpoint of extending the pot life of the polymerizable composition while improving the balance between the effect of suppressing pulverization in the resulting resin and the effect of improving the transparency of the resin, the compound represented by formula (1) is Preferably, the R of the polyether group represented by formula (2) 26 Compounds in which is a hydrogen atom and the R of a polyether group represented by formula (2) 26 It comprises at least one compound selected from the group consisting of compounds having a linear or branched alkenyl group with 2 to 20 carbon atoms, More preferably, the R of the polyether group represented by formula (2)26 Compounds in which is a hydrogen atom and the R of a polyether group represented by formula (2) 26 It comprises at least one compound selected from the group consisting of compounds having a linear or branched alkenyl group with 2 to 8 carbon atoms, More preferably, the compound comprises at least one selected from the group consisting of compounds represented by the following formula (1A) and compounds represented by the following formula (1B).

[0057] [ka]

[0058] In equation (1A), a+c is between 1 and 100, b is between 1 and 100, d is between 10 and 1000, and e is between 1 and 100. In equation (1B), f+h is between 1 and 100, and g is between 1 and 100.

[0059] From the viewpoint of further suppressing pulverization in the resulting resin, a+c in formula (1A) is preferably 5 to 50. From a similar viewpoint, in formula (1A), b is preferably 5 to 50. From a similar viewpoint, in formula (1A), e is preferably between 5 and 50. From a similar viewpoint, the molecular weight of the compound represented by formula (1A) is preferably 100 to 10000, and more preferably 1000 to 5000.

[0060] From the viewpoint of further suppressing pulverization in the resulting resin, f+h in formula (1B) is preferably 1 to 20. From a similar viewpoint, in formula (1B), g is preferably 1 to 10. From a similar viewpoint, the molecular weight of the compound represented by formula (1B) is preferably 100 to 10000, and more preferably 500 to 5000.

[0061] When the polyether-modified silicone compound (c) contains both the compound represented by formula (1A) and the compound represented by formula (1B), from the viewpoint of further suppressing pulverization in the resulting resin, the mass ratio of the compound represented by formula (1A) to the total mass of the compounds represented by formula (1A) and formula (1B) is preferably 50% to 90%, and more preferably 60% to 80%.

[0062] From the viewpoint of further suppressing pulverization in the resulting resin, the content of the polyether-modified silicone compound (c) (i.e., the compound represented by formula (1)) is preferably 0.001% to 5% by mass, more preferably 0.005% to 3% by mass, and even more preferably 0.01% to 2% by mass, based on the total amount of the polymerizable composition of the present disclosure.

[0063] <Polymerization catalyst> The polymerizable composition of this disclosure may contain at least one polymerization catalyst. The polymerization catalyst functions, for example, as a catalyst for the polymerization reaction when curing the polymerizable composition of this disclosure to obtain a resin. As polymerization catalysts, known polymerization catalysts such as organometallic compounds, amines, and quaternary onium salts can be used. Examples of organometallic compounds include compounds containing tin, zinc, copper, and the like. Specifically, as organometallic compounds, for example; Organotin compounds such as tin acetate, tin octoate, tin oleate, tin laurate, dibutyltin diacetate, dimethyltin dilaurate, dibutyltin dilaurate, dibutyltin dimercaptide, dibutyltin maleate, dibutyltin dineodecanoate, dioctyltin dimercaptide, dioctyltin dilaurate, dimethyltin dichloride, and dibutyltin dichloride; Organozinc compounds such as zinc naphthenate; Organocopper compounds such as copper octenate; These are some examples.

[0064] Examples of amines include: Tertiary amines such as triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, trioctylamine, triallylamine, N,N-dimethylbenzylamine, N-methylmorpholine, N,N-dimethylcyclohexylamine, dimethyldipropylenetriamine, pentamethyldiethylenetriamine, bis(2-dimethylaminoethyl) ether, N-methylmorpholine, N,N'-dimethylpiperazine, triethylenediamine, N,N,N',N'-tetramethylethylenediamine, bicyclooctanediamine (DABCO), 2-methylpyrazine, pyridine, α-picoline, β-picoline, γ-picoline, 2,6-lutidine, 3,5-lutidine, 2,4,6-trimethylpyridine, and 3-chlorpyridine; Imidazoles such as imidazole, 1,2-dimethylimidazole, N-benzyl-2-methylimidazole, and 2-ethyl-4-imidazole; Pyrazoles such as pyrazoles and 3,5-dimethylpyrazole; These are some examples.

[0065] Examples of quaternary onium salts include quaternary ammonium salts and phosphonium salts. Examples of quaternary ammonium salts include tetrabutylammonium bromide and tetraethylammonium hydroxide. Examples of phosphonium salts include tetramethylphosphonium chloride, tetraethylphosphonium chloride, tetrapropylphosphonium chloride, tetrabutylphosphonium chloride, tetrahexylphosphonium chloride, tetraoctylphosphonium chloride, ethyltriphenylphosphonium chloride, tetraphenylphosphonium chloride, butyltriphenylphosphonium chloride, benzyltriphenylphosphonium chloride, methoxymethyltriphenylphosphonium chloride, tetramethylphosphonium bromide, tetraethylphosphonium bromide, tetrapropylphosphonium bromide, tetrabutylphosphonium bromide, and tetrahexylphosphonium bromide. Examples of phosphonium salt compounds include tetraoctylphosphonium bromide, ethyltriphenylphosphonium bromide, tetraphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium bromide, methoxymethyltriphenylphosphonium bromide, ethyltriphenylphosphonium acetate, ethyltriphenylphosphonium iodide, tetraethylphosphonium hydroxide, tetrabutylphosphonium hydroxide, tetraphenylphosphonium tetrakis(4-methylphenyl) borate, tetraphenylphosphonium tetraphenyl borate, and tetrabutylphosphonium-o,o-diethylphosphorodithioate.

[0066] <Internal release agent> The polymerizable composition of this disclosure may contain at least one internal mold release agent. As an internal release agent, for example, an acidic phosphate ester can be used. A specific example of an acidic phosphate ester is the compound represented by the following formula (P1).

[0067] [ka]

[0068] In formula (P1), m represents 1 or 2, n represents an integer from 0 to 18, R1 represents an alkyl group having 1 to 20 carbon atoms, and R2 and R3 each independently represent a hydrogen atom, a methyl group, or an ethyl group. The number of carbon atoms in the parentheses with the subscript "m" is preferably 4 to 20.

[0069] For example, R1 in equation (P1) is: Organic residues derived from linear aliphatic compounds such as methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tetradecane, and hexadecane; Organic residues derived from branched-chain aliphatic compounds such as 2-methylpropane, 2-methylbutane, 2-methylpentane, 3-methylpentane, 3-ethylpentane, 2-methylhexane, 3-methylhexane, 3-ethylhexane, 2-methylheptane, 3-methylheptane, 4-methylheptane, 3-ethylheptane, 4-ethylheptane, 4-propylheptane, 2-methyloctane, 3-methyloctane, 4-methyloctane, 3-ethyloctane, 4-ethyloctane, and 4-propyloctane; Organic residues derived from alicyclic compounds such as cyclopentane, cyclohexane, 1,2-dimethylcyclohexane, 1,3-dimethylcyclohexane, and 1,4-dimethylcyclohexane; These are some examples.

[0070] Commercially available acidic phosphate esters include ZelecUN from STEPAN, the JP series from Johoku Chemical Industry, the Phosphanol series from Toho Chemical Industry, and the AP and DP series from Daihachi Chemical Industry. Furthermore, from the viewpoint of solubility in polymerizable compositions and transparency of the resin, ZelecUN and JP-506H are preferred, with JP-506H being particularly preferred.

[0071] If the polymerizable composition of this disclosure contains an acidic phosphate ester as an internal release agent, the content of the acidic phosphate ester as an internal release agent is preferably 0.001% to 10% by mass, more preferably 0.001% to 5% by mass, even more preferably 0.005% to 3% by mass, and even more preferably 0.01% to 2% by mass, based on the total amount of the polymerizable composition.

[0072] <Polymerization catalyst> The polymerizable composition of this disclosure may contain at least one polymerization catalyst. While there are no particular limitations on the polymerization catalyst, a non-metallic catalyst may be used from the perspective of reducing environmental impact. Examples of nonmetallic catalysts include amines (particularly preferably imidazoles), phosphonium salts, and acids. These polymerization catalysts themselves may be plant-derived compounds.

[0073] The polymerizable composition of this disclosure contains a polymerization catalyst, preferably 0.001% to 10% by mass, more preferably 0.001% to 5% by mass, even more preferably 0.005% to 3% by mass, and even more preferably 0.01% to 2% by mass, based on the total amount of the polymerizable composition.

[0074] <UV absorber> The polymerizable composition of this disclosure may contain at least one ultraviolet absorber. Examples of UV absorbers include: Benzophenone-based UV absorbers such as 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-acryloyloxybenzophenone, 2-hydroxy-4-acryloyloxy-5-tert-butylbenzophenone, and 2-hydroxy-4-acryloyloxy-2',4'-dichlorobenzophenone; 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-(2'-ethyl)hexyl)oxy] Triazine-based UV absorbers such as -2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-butyloxyphenyl)-6-(2,4-bis-butyloxyphenyl)-1,3,5-triazine, and 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine; 2-(2H-benzotriazol-2-yl)-4-methylphenol, 2-(2H-benzotriazol-2-yl)-4-tert-octylphenol, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl)-4,6-di-tert-pentylphenol, 2-(5-chloro-2H-benzotriazol-2-yl)-4-methyl-6- Benzotriazole-based UV absorbers such as tert-butylphenol, 2-(5-chloro-2H-benzotriazol-2-yl)-2,4-tert-butylphenol, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], and 2-(2H-benzotriazol-2-yl)-4-methyl-6-(3,4,5,6-tetrahydrophthalimidylmethyl)phenol; These are some examples.

[0075] The amount of ultraviolet absorber in the polymerizable composition of this disclosure is preferably 0.001% to 10% by mass, more preferably 0.01% to 5% by mass, and even more preferably 0.1% to 5% by mass, based on the total amount of the polymerizable composition.

[0076] One preferred embodiment of the polymerizable composition of this disclosure is a polymerizable composition containing an acidic phosphate ester as an ultraviolet absorber, a polymerization catalyst, and an internal mold release agent. The preferred range for the content of each component in this case is as described above, for example, The amount of ultraviolet absorber is 0.1% to 5% by mass relative to the total amount of the polymerizable composition for optical materials. The polymerization catalyst content is 0.001% to 5% by mass relative to the total amount of the polymerizable composition for optical materials. The content of the acidic phosphate ester as an internal release agent is 0.001% to 5% by mass relative to the total amount of the polymerizable composition for optical materials.

[0077] <Other ingredients> The polymerizable compositions of this disclosure may contain other components besides those described above. Other ingredients include, for example, light stabilizers, antioxidants, color inhibitors, dyes, bluing agents, and resin modifiers.

[0078] Hindered amine compounds can be used as light stabilizers. Examples of hindered amine compounds include: Lowilite 76 and Lowilite 92 manufactured by Chemtura; BASF's Tinuvin 123, Tinuvin 144, Tinuvin 292, Tinuvin 765, and Tinuvin 770DF; ADEKA LA-52 and LA-72 stubs manufactured by ADEKA Corporation; JF-90 and JF-95 manufactured by Johoku Chemical Industry Co., Ltd. These are some examples.

[0079] Examples of bluing agents include those that have an absorption band in the orange to yellow wavelength range within the visible light spectrum and have the function of adjusting the hue of optical materials. More specifically, bluing agents contain substances that exhibit a blue to purple color.

[0080] <Method for producing polymerizable compositions> The polymerizable composition of this disclosure is obtained by mixing the above-mentioned components (raw materials). There are no particular restrictions on the order in which the ingredients (raw materials) are mixed. All raw materials may be added to the container at once and mixed, or they may be added to the container in multiple stages and mixed. Furthermore, during the mixing process, some of the monomers in the polymerizable composition of this disclosure (i.e., polyisocyanate (a) and polythiol composition (b)) may polymerize to form a prepolymer.

[0081] A preferred embodiment of the polymerizable composition of this disclosure (hereinafter referred to as "Method A") will be described below. Method A is a preferred method for producing a polymerizable composition containing an ultraviolet absorber, a polymerization catalyst, and an acidic phosphate ester. Method A is, A step to obtain solution A1 by adding a polyether-modified silicone compound (c) and an acidic phosphate ester to an aliphatic polyisocyanate (a1), A step of dissolving an ultraviolet absorber and a polymerization catalyst in an aliphatic polyisocyanate (a1) to obtain solution A2, The process involves mixing solution A1, solution A2, and modified material (a2) to obtain solution A3. A step of adding a polythiol composition (b) containing a polythiol compound to solution A3 to obtain the polymerizable composition of the present disclosure, Includes. According to manufacturing method A, a polymerizable composition containing an ultraviolet absorber, a polymerization catalyst, and an acidic phosphate ester as an internal mold release agent can be produced while suppressing the formation of gel-like insoluble matter. The process of mixing solution A1, solution A2, and the modified product (a2) to obtain solution A3 does not need to be done all at once. For example, the operation of mixing solution A1, solution A2, and modified product (a2) is: First, solution A2 is mixed with the modified substance (a2) to obtain solution A2X, and then solution A2X is mixed with solution A1; First, solution A2 and solution A1 are mixed to obtain solution A12, and then solution A12 is mixed with the modified substance (a2); These are some examples.

[0082] [Optical materials] The optical materials of this disclosure include resins. The resin in the optical material of this disclosure is a cured product of the polymerizable composition of this disclosure described above. The resin in the optical material of this disclosure can be produced by curing the polymerizable composition of this disclosure described above, or more specifically, by polymerizing and curing the monomers in the polymerizable composition of this disclosure. An example of a method for producing the resin is casting polymerization, which will be described later.

[0083] The optical material of this disclosure may consist of the resin of this disclosure, or may include the resin of this disclosure and other elements. Other elements include other components, a coating layer applied to the resin of this disclosure, and so on.

[0084] Examples of optical materials in this disclosure include lenses (e.g., eyeglass lenses, camera lenses, polarizing lenses, etc.), light-emitting diodes (LEDs), and the like.

[0085] A method for polymerizing the monomers in the polymerizable composition of this disclosure (i.e., a method for curing the polymerizable composition of this disclosure) is, for example, casting polymerization. By casting polymerization, a molded article of the resin (i.e., a cured product of the polymerizable composition of the optical material of the present disclosure) can be obtained.

[0086] In casting polymerization, first, a polymerizable composition according to an example of this disclosure is injected between a pair of molding molds held together by a gasket or tape. At this time, degassing, filtration, etc. may be performed as necessary. Next, the monomers in the composition injected between the molding molds are polymerized, causing the composition to harden between the molding molds and obtain a cured product. Then, the cured product is removed from the molding molds to obtain a cured product. Polymerization of the above monomers may be carried out by heating the polymerizable composition of this disclosure. This heating can be carried out, for example, using a heating device equipped with a mechanism for heating the object to be heated in an oven, water, or the like.

[0087] The polymerization conditions (e.g., polymerization temperature, polymerization time, etc.) for polymerizing the monomers in the polymerizable composition of this disclosure are set appropriately, taking into consideration the composition of the composition, the type and amount of monomers used in the composition, the type and amount of polymerization catalyst used in the composition, the shape of the mold, etc. Examples of polymerization temperatures include -50°C to 150°C and 10°C to 150°C. Polymerization times can range from 1 hour to 200 hours, 1 hour to 80 hours, and so on.

[0088] The resin in the optical material of this disclosure may be obtained by polymerizing monomers and then subjecting them to treatments such as annealing. Typical annealing temperatures include 50°C to 150°C, 90°C to 140°C, and 100°C to 130°C.

[0089] (Desired properties of resin) The glass transition temperature (Tg) of the resin in the optical material of this disclosure is preferably 60°C or higher, more preferably 70°C or higher, and even more preferably 80°C or higher. The Tg of the resin may be 130°C or lower, 120°C or lower, or 110°C or lower.

[0090] The refractive index (ne) of the resin in the optical material of this disclosure is preferably 1.500 or higher, more preferably 1.540 or higher, and even more preferably 1.590 or higher. There is no particular upper limit to the refractive index (ne) mentioned above, but a possible upper limit is 1.750.

[0091] The Abbe number of the resin in the optical material of this disclosure is preferably 28 or higher, more preferably 30 or higher. There is no particular upper limit to the Abbe number mentioned above, but the upper limit is, for example, 50, preferably 45.

[0092] The specific gravity d of the resin in the optical material of this disclosure is preferably 1.10 or higher, more preferably 1.20 or higher. There is no particular upper limit to the specific gravity d mentioned above, but the upper limit is, for example, 1.50, preferably 1.40.

[0093] The yellow index (YI) of the resin in the optical material of this disclosure is preferably 2.10 or less, more preferably 2.00 or less, even more preferably 1.90 or less, and even more preferably 1.80 or less. There are no particular restrictions on the lower limit of YI mentioned above, but the lower limit is, for example, 1.30, and preferably 1.50.

[0094] The resin haze in the optical material of this disclosure is preferably 0.30 or less, more preferably 0.25 or less, and even more preferably 0.20 or less. There are no particular restrictions on the lower limit of the haze mentioned above, but the lower limit is, for example, 0.05, and preferably 0.10.

[0095] (Biomass content of resin) From the viewpoint of utilizing non-fossil resources, the biomass content of the resin in the optical material of this disclosure is preferably 25% or more, more preferably 30% or more, and even more preferably 50% or more.

[0096] In this disclosure, the biomass content is determined by a carbon-based calculation method and is a value calculated based on the following formula. Biomass percentage (%) = {(Number of plant-derived carbons) / (Number of plant-derived carbons + Number of petroleum-derived carbons)} × 100 Here, plant-derived carbon is... 14 C stands for petroleum-derived carbon. 14 Carbon atoms other than C (mostly) 12 C) means "number of plant-derived carbons + number of petroleum-derived carbons," which represents the total number of carbon atoms in the substance being measured.

[0097] In this disclosure, the biomass content (%) of the resin is determined in accordance with the ASTM (United States Standard Test Method) D6866-21 (Standard Test Method for Determining the Biobased Content of Natural Range Materials Using Radiocarbon and Isotope Ratio Mass Spectrometry Analysis), by burning the resin as a measurement sample to generate CO2, and then analyzing the generated CO2 by accelerator mass spectrometry (AMS). 14 C content and 14 It is calculated by measuring the content of carbon atoms other than C.

[0098] 〔lens〕 The lenses of this disclosure are an example of the optical materials of this disclosure, and include the resins of this disclosure as described above. The lenses of this disclosure may be manufactured, for example, by the casting polymerization described above.

[0099] The lenses of this disclosure may consist of the resin of this disclosure, or may include the resin of this disclosure and other elements. Other elements include other components, a coating layer applied to the resin of this disclosure, and so on.

[0100] Examples of lenses in this disclosure include eyeglass lenses, camera lenses, polarized lenses, and the like. Below, we will describe eyeglass lenses as an example of the lenses described herein. The spectacle lens comprises a resin of the present disclosure molded into a desired lens shape. The spectacle lens preferably further includes a coating layer provided on one or both sides of the resin.

[0101] Examples of coating layers include primer layers, hard coat layers, anti-reflective layers, anti-fogging layers, anti-stain layers, and water-repellent layers. These coating layers can be used individually or in multiple layers. When applying coating layers to both sides of a cured object, the same coating layer may be applied to each surface, or different coating layers may be applied to each surface.

[0102] The components of the coating layer can be selected as appropriate depending on the purpose. The components of the coating layer include, for example, resins (e.g., urethane resin, epoxy resin, polyester resin, melamine resin, polyvinyl acetal resin, etc.), infrared absorbers, light stabilizers, antioxidants, photochromic compounds, dyes, pigments, antistatic agents, and the like.

[0103] For eyeglass lenses and coating layers, you can refer to the descriptions in publicly available documents such as Japanese Patent Publication No. 2002-194083 and International Publication No. 2017 / 047745 as appropriate. [Examples]

[0104] The following are examples of the present disclosure, but the present disclosure is not limited to these examples. Unless otherwise specified, "parts" are based on mass.

[0105] [Example 1] <Preparation of polymerizable compositions> 12.00 parts by mass of 1,5-pentamethylene diisocyanate (hereinafter also referred to as "PDI") as an aliphatic polyisocyanate (a1) ("Stabio PDI" manufactured by Mitsui Chemicals, Inc.; biomass content 70%), 0.10 parts by mass of Polyflow KL-100 (manufactured by Kyoeisha Chemical Co., Ltd.) (hereinafter also referred to as "KL-100") as a polyether-modified silicone compound (c), 0.20 parts by mass of JP-506H (acidic phosphate ester manufactured by Johoku Chemical Industry Co., Ltd.) as an internal release agent, The two components were mixed and dissolved at 20°C to prepare solution A1. Here, KL-100 is a polyether-modified silicone compound (c) represented by formula (1) above, and more specifically, includes the compound represented by formula (1A) above and the compound represented by formula (1B) above.

[0106] next, 20.45 parts by mass of PDI (Mitsui Chemicals, Inc.'s "Stabio PDI"; biomass content 70%) as an aliphatic polyisocyanate (a1), 0.60 parts by mass of 2-(2H-benzotriazol-2-yl)-4-tert-octylphenol as an ultraviolet absorber, 0.60 parts by mass of 2-(2H-benzotriazol-2-yl)-4-methyl-6-(3,4,5,6-tetrahydrophthalimidylmethyl)phenol as an ultraviolet absorber, 0.03 parts by mass of dimethyltin dichloride (hereinafter also referred to as "DMC") as a polymerization catalyst, These were mixed and dissolved at 20°C to obtain solution A2. To the obtained solution A2, 28.15 parts by mass of 1,5-pentamethylene diisocyanate isocyanurate mononucleate (hereinafter also referred to as "PDI-nurate") (Mitsui Chemicals, Ltd. "Stabio D-370N"); biomass content 70%), which is a modified form of aliphatic polyisocyanate (a2), was added and mixed and dissolved at 20°C to obtain solution A2X. To the obtained solution A2X, the previously prepared solution A1 (3.08 parts by mass) was added and mixed and dissolved at 20°C to obtain solution A3 containing polyisocyanate (a) and polyether-modified silicone compound (c). The resulting solution A3 was degassed under reduced pressure of 600 Pa until no more foaming was observed. To the degassed solution A3, the polythiol composition (b) is: Pentaerythritol tetrakis(3-mercaptopropionate) (i.e., the aforementioned polythiol component S1) 14.65 parts by mass, 33.05 parts by mass of a polythiol composition containing 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (i.e., the aforementioned polythiol component S2) as the main components, The mixture was added and dissolved at 20°C. Based on the above, a polymerizable composition containing polyisocyanate (a), a polythiol composition (b), and a polyether-modified silicone compound (c) was obtained.

[0107] <Fabrication of resin molded products> The polymerizable composition obtained above was degassed under a reduced pressure of 600 Pa until no more foaming was observed. The degassed polymerizable composition was filtered through a 1 μm filter and injected between a pair of glass molds fixed with tape. Next, the pair of glass molds containing the polymerizable composition were placed in an oven, and the oven temperature was gradually increased from 20°C to 120°C over 20 hours. Through this process, the monomers in the degassed polymerizable composition (i.e., polyisocyanate (a) and polythiol composition (b)) were polymerized, and a resin molded body (i.e., a resin molded body which is the cured product of the polymerizable composition) was formed between the pair of glass molds. Next, the oven was cooled, and after cooling, the pair of glass molds were removed from the oven. Then, the resin molded bodies were removed from the pair of glass molds to obtain the resin molded bodies. The resulting resin molded body was annealed at 120°C for 1 hour to obtain a lens containing resin.

[0108] <Rating> The following evaluations were performed on the resin molded product (i.e., the lens) after the annealing described above. The results are shown in Table 1.

[0109] ·Mold releasability In the production of the above-mentioned resin molded product, the release properties when removing the resin molded product from a pair of glass molds were evaluated according to the following evaluation criteria. In the following evaluation criteria, rank A represents the best release properties. -Evaluation Criteria for Mold Release Properties- A: By cooling the oven to room temperature, the resin molded body naturally detached from the pair of glass molds. B: By inserting wedges into the edges of the resin molded body, the resin molded body could be peeled off the pair of glass molds. C: The glass mold cracked during demolding, or the glass peeled off and stuck to the resin. Alternatively, the resin could not be demolded from the glass mold.

[0110] ·Heat resistance Aside from appropriately selecting the shape and size of a pair of glass molds, the same procedure as described in <Preparation of Resin Molded Body> was used to obtain a test piece with a length of 10 mm, a width of 10 mm, and a thickness of 2.5 mm. Using a Shimadzu TMA-60 thermomechanical analyzer, the glass transition temperature (Tg) of the above sample was measured by the TMA penetration method (50g load, 0.5mmφ pin tip, heating rate 10℃ / min) and used as an indicator of heat resistance. The higher the glass transition temperature (Tg), the better the heat resistance.

[0111] ·specific gravity The specific gravity of the resin molded product was measured at 20°C using the Archimedes method.

[0112] • Optical properties (refractive index (n) e ) and Abbe number (ν e )) Except for appropriately selecting the shape and size of a pair of glass molds, a test specimen measuring 10 mm in length, 10 mm in width, and 2.5 mm in thickness was obtained by the same procedure as in the above-described procedure for "Preparation of Resin Molded Body". The refractive index of the obtained test specimen was measured at wavelengths of 546.1 nm (mercury e line), 480.0 nm (Cd F' line), and 643.9 nm (Cd C' line) using a Shimadzu KPR-30 Pulfrich refractometer, and based on these measurement results, the refractive index (n e ) and Abbe number (ν e We calculated each of the following:

[0113] • YI (Yellow Index; degree of yellowness), a * , and b * Except for appropriately selecting the shape and size of a pair of glass molds, a disc-shaped test specimen with a thickness of 2.5 mm and a diameter of 75 mm was obtained by the same procedure as in the above-described procedure for "Preparation of Resin Molded Body". The obtained test specimen was measured using a Konica Minolta CM-5 spectrophotometer to determine the YI (Yellow Index; yellowness), a * , and b * They sought it. The smaller the YI value, the better the lens's color reproduction.

[0114] Hayes Except for appropriately selecting the shape and size of a pair of glass molds, a disc-shaped test specimen with a thickness of 2.5 mm and a diameter of 75 mm was obtained by the same procedure as in the above-described procedure for "Preparation of Resin Molded Body". The haze value of the resin was measured using a haze meter (model number: NDH 2000) manufactured by Nippon Denshoku Industries, Ltd. for the obtained test specimen. The lower the haze value, the better the transparency of the lens.

[0115] ·Striae A 10mm thick semi-finished lens was fabricated using the same procedure as described in <Fabrication of Resin Molded Body>, except that a pair of 6-base curve glass molds were used. The obtained semi-finished lenses were visually inspected using a high-pressure mercury lamp (Optical ModuleX, manufactured by Ushio Inc.) to check for the presence or absence of striations. Based on the results of the inspection, the striations were evaluated according to the following evaluation criteria. In the following evaluation criteria, rank A represents the most suppressed pulse.

[0116] - Evaluation Criteria for Stratum - A: No striations are observed even when using a high-pressure mercury lamp. B: When a high-pressure mercury lamp is used, striations are observed, and the striations are observed only within a 10 mm range from the edge of the lens toward the center. C: When a high-pressure mercury lamp is used, striations are observed, and striations are observed within a 30 mm range from the edge of the lens toward the center. D: The striations can be easily confirmed visually without using high-pressure mercury lamps.

[0117] [Comparative Example 1] In preparing the polymerizable composition, the same procedure as in Example 1 was followed, except that polyether-modified silicone compound (c) was not used. The results are shown in Table 1.

[0118] [Comparative Example 2] In preparing the polymerizable composition, the same procedure as in Example 1 was followed, except that the polyether-modified silicone compound (c) was replaced with the same mass of an unmodified silicone compound (comparative compound). Here, as the unmodified silicone compound, we used "KF-96" (dimethyl silicone oil (unmodified dimethylpolysiloxane)) manufactured by Shin-Etsu Silicone Co., Ltd. The results are shown in Table 1.

[0119] [Table 1]

[0120] As shown in Table 1, the resin of Example 1, produced using a polymerizable composition for optical materials containing a polyisocyanate (a) including an aliphatic polyisocyanate (a1) and a modified polyisocyanate (a2), a polythiol composition (b), and a polyether-modified silicone compound (c), showed suppressed striations compared to the resin of Comparative Example 1, produced using a polymerizable composition for optical materials that did not contain the polyether-modified silicone compound (c), and the resin of Comparative Example 2, produced using a polymerizable composition for optical materials that contained an unmodified silicone compound (comparative compound) instead of the polyether-modified silicone compound (c).

[0121] The biomass content of the resin in Example 1 was measured by the method described above. As a result, the biomass content of the resin in Example 1 was 45%.

[0122] The disclosure of Japanese Patent Application No. 2022-158847, filed on 30 September 2022, is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards described herein are incorporated by reference to the same extent as if each individual document, patent application, and technical standard were specifically and individually noted to be incorporated by reference.

Claims

1. A polyisocyanate (a) comprising an aliphatic polyisocyanate (a1) and a modified aliphatic polyisocyanate (a2), A polythiol composition (b) containing a polythiol compound, A polyether-modified silicone compound (c) represented by the following formula (1), Includes, A polymerizable composition for optical materials, wherein the proportion of the modified material (a2) in the polyisocyanate (a) is 1% by mass or more and 60% by mass or less. 【Chemistry 1】 [In formula (1), R １ ~R ８ Each of these independently represents a polyether group, a C1-C20 alkyl group, a C1-C20 alkoxy group, a hydroxyl group, or a polysiloxy group represented by formula (2). However, R １ ~R ８ At least one of these is a polyether group represented by formula (2). In equation (1), m and n each independently represent a non-negative integer. In formula (1), R ２ ~R ５ If there are multiple instances of each of these, then there are multiple instances of R. ２ ~R ５ Each of these may be the same or different. In formula (2), R ２５ represents an alkylene group having 1 to 20 carbon atoms, and R ２６ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an alkynyl group having 2 to 20 carbon atoms, k represents an integer of 1 or more, and * represents a bonding position. In formula (2), R ２５ If there are multiple instances of R, then there are multiple instances of R ２５ They may be the same or different.

2. The polymerizable composition for optical materials according to claim 1, wherein the modified body (a2) comprises an isocyanurate mononuclear body of an aliphatic polyisocyanate.

3. The polymerizable composition for optical materials according to claim 1, wherein at least one of the aliphatic polyisocyanates in the aliphatic polyisocyanate (a1) and the modified product (a2) comprises at least one selected from the group consisting of pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, lysine diisocyanate, lysine triisocyanate, dimer acid diisocyanate, octamethylene diisocyanate, and decamethylene diisocyanate.

4. The polymerizable composition for optical materials according to claim 1, wherein at least one of the aliphatic polyisocyanates in the aliphatic polyisocyanate (a1) and the modified product (a2) comprises an aliphatic polyisocyanate obtained from a plant-derived raw material.

5. The aforementioned polythiol compound is 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8-Dimercaptomethyl-1,11-Dimercapto-3,6,9-Trithiaundecane, 4,7-Dimercaptomethyl-1,11-Dimercapto-3,6,9-Trithiaundecane, 5,7-Dimercaptomethyl-1,11-Dimercapto-3,6,9-Tritiaundecane, Pentaerythritol tetrakis (2-mercaptoacetate), Pentaerythritol tetrakis (3-mercaptopropionate), 2,5-Dimercaptomethyl-1,4-Dithiane, Bis(2-mercaptoethyl) sulfide, and Diethylene glycol bis(3-mercaptopropionate) A polymerizable composition for optical materials according to claim 1, which is at least one selected from the group consisting of the following.

6. The polymerizable composition for optical materials according to claim 1, comprising a polythiol compound obtained from a plant-derived raw material.

7. The total content of the polyisocyanate (a) and the polythiol composition (b) is 80% by mass or more based on the total amount of the polymerizable composition for optical materials. A polymerizable composition for optical materials according to claim 1.

8. The content of the polyether-modified silicone compound (c) is 0.001% by mass to 5% by mass based on the total amount of the polymerizable composition for optical materials. A polymerizable composition for optical materials according to claim 1.

9. Furthermore, the polymerizable composition for optical materials according to claim 1 further contains an ultraviolet absorber, a polymerization catalyst, and an acidic phosphate ester as an internal mold release agent.

10. The amount of the UV absorber is 0.1% to 5% by mass relative to the total amount of the polymerizable composition for optical materials. The content of the polymerization catalyst is 0.001% by mass to 5% by mass, relative to the total amount of the polymerizable composition for optical materials. The content of the acidic phosphate ester as the internal release agent is 0.001% by mass to 5% by mass, relative to the total amount of the polymerizable composition for optical materials. Polymerizable composition for optical materials according to claim 9.

11. An optical material comprising a resin which is a cured product of a polymerizable composition for optical materials according to any one of claims 1 to 10.

12. The optical material according to claim 11, wherein the biomass content of the resin is 25% or more.

13. A method for producing a polymerizable composition for optical materials according to claim 9 or claim 10, The process involves adding the polyether-modified silicone compound (c) and the acidic phosphate ester to the aliphatic polyisocyanate (a1) to obtain solution A1. A step of dissolving the ultraviolet absorber and the polymerization catalyst in the aliphatic polyisocyanate (a1) to obtain solution A2, A step of mixing the aforementioned solution A1, the aforementioned solution A2, and the modified substance (a2) to obtain solution A3, The steps include adding the polythiol composition (b) to the solution A3 to obtain the polymerizable composition for optical materials, including, A method for producing polymerizable compositions for optical materials.

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