Composition, composition kit, cured product, laminate, and method for producing the cured product

Abstract

A composition containing: a base generating agent (a); a polymerizable compound containing at least one selected from the group consisting of a polyiso(thio)cyanate compound (b1) and a polythiol compound (c1); and a stabilizing agent (S).

Description

[Technical Field]

[0001] This disclosure relates to compositions, composition kits, cured products, laminates, and methods for producing cured products. [Background technology]

[0002] High refractive index plastics are increasingly being used as optical components such as eyeglass lenses because they are lighter, less prone to breakage, and can be dyed compared to inorganic materials such as glass. Examples of plastic materials for optical components include acrylic resin, polycarbonate, and thiourethane resin, among which thiourethane resin is known as a plastic material that can obtain a high refractive index (see, for example, Patent Document 1).

[0003] Products made from thiourethane resin are generally manufactured by casting polymerization. Specifically, the raw material composition is injected between a pair of molds placed at a predetermined distance apart, and the composition is cured by heating to obtain the product.

[0004] Patent Document 1: Japanese Unexamined Patent Publication No. 2019-15922 [Overview of the project] [Problems that the invention aims to solve]

[0005] Conventional methods for manufacturing thiourethane resins require a long time to heat-cur the composition, and it is difficult to control the quality of the composition or cured product, leaving room for improvement in terms of handling. In view of the above circumstances, an object of one aspect of the present disclosure is to provide a composition that can form a thiourethane resin and has excellent handling properties, as well as a composition kit using this composition, a cured product, a laminate, and a method for producing the cured product. [Means for solving the problem]

[0006] The means for solving the above problems include the following embodiments. <1> Base generator (a), A polymerizable compound comprising at least one selected from the group consisting of polyiso(thio)cyanate compounds (b1) and polythiol compounds (c1), Stabilizer (S), A composition containing the following: <2> The polymerizable compound comprises a polyiso(thio)cyanate compound (b1) and a polythiol compound (c1). <1> The composition described above. <3> The mass ratio (b1 / c1) of the polyiso(thio)cyanate compound (b1) to the polythiol compound (c1) contained in the polymerizable compound is 99 / 1 to 1 / 99. <2> The composition described above. <4> The thiourethane compound is a reaction product of the polyiso(thio)cyanate compound (b1) and the polythiol compound (c1). <2> or <3> The composition described above. <5> The polyiso(thio)cyanate compound (b1) comprises at least one selected from the group consisting of pentamethylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, bis(isocyanatomethyl)cyclohexane, bis(isocyanatocyclohexyl)methane, 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and phenylene diisocyanate. <1> ~ <4> A composition according to any one of the items. <6> The aforementioned polythiol compound (c1) is 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(2-mercaptoacetate), 2,5- It comprises at least one selected from the group consisting of bis(mercaptomethyl)-1,4-dithiane, bis(2-mercaptoethyl) sulfide, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 4,6-bis(mercaptomethylthio)-1,3-dithiane, 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithiethane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 3-mercaptomethyl-1,5-dimercapto-2,4-dithiapentane, and tris(mercaptomethylthio)methane. <1> ~ <5> A composition according to any one of the items. <7> The base generator (a) comprises at least one compound selected from the group consisting of compounds represented by the following formulas (1) to (4). <1> ~ <6> A composition according to any one of the items. [ka] In formula (1), R1 to R4 each independently represent an alkyl group having 1 to 8 carbon atoms, and R5 to R8 each independently represent an alkyl group having 1 to 8 carbon atoms, a phenyl group, a naphthyl group, an anthracenyl group, or a phenanthryl group. In formula (2), R1 to R7 each independently represent an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 3 to 8 carbon atoms, and R8 to R 11 Each of these independently represents an alkyl group having 1 to 8 carbon atoms, a phenyl group, a naphthyl group, an anthracenyl group, or a phenanthyl group. In formula (3), n represents an integer from 1 to 3, and R1 to R4 each independently represent an alkyl group, phenyl group, naphthyl group, anthracenyl group, or phenanthryl group having 1 to 8 carbon atoms. In formula (4), R1 to R4 each independently represent an alkyl group having 1 to 8 carbon atoms, a phenyl group, a naphthyl group, an anthracenyl group, or a phenanthyl group. In formulas (1) to (4), the phenyl group, the naphthyl group, the anthracenyl group, and the phenanthrill group may be substituted with a halogen atom, an alkyl group, an aryl group, an alkenyl group, a cycloalkyl group, or a heterocyclic group. <8> The stabilizer (S) comprises either an acid or a phosphite ester compound having a pKa of 0.2 or more and less than 2.0. <1> ~ <7> A composition according to any one of the items. <9> The stabilizer (S) comprises at least one selected from the group consisting of acids and phosphite ester compounds having a pKa of less than 2.0. <1> ~ <8> A composition according to any one of the items. <10> The compound further contains a tin-containing metal catalyst, the content of which is 0.001 to 0.05 parts by mass when the total mass of the polymerizable compound is 100 parts by mass. <1> ~ <9> A composition according to any one of the items. <11> Further containing UV absorber (e), <1> ~ <10> A composition according to any one of the items. <12> Further comprising a polyether-modified silicone compound (d), <1> ~ <11> A composition according to any one of the items. <13> <1> ~ <12> A first composition which is a composition described in any one of the following items, It consists of a polyiso(thio)cyanate compound (b2) and a polythiol compound (c2). A second composition comprising a polymerizable compound containing at least one selected from the group, A composition kit containing the following: <14> The second composition comprises only one of either a polyiso(thio)cyanate compound (b2) or a polythiol compound (c2). <13> The composition kit described above. The cured product of the mixture of the first composition and the second composition contained in the composition kit described in <15> or <13> or <14>. The cured product described in <15>, having a refractive index of 1.50 to 1.80. A laminate comprising the cured product described in <17> or <15> or <16> and a substrate. The laminate described in <17>, further comprising a functional film. The laminate described in <18>, wherein the functional film comprises at least one selected from the group consisting of a polarizing film, a retardation film, a gas barrier film, a conductive film, an insulating film, and an optical guide film. The laminate described in <18> or <19>, wherein at least a part of the cured product and the functional film are in direct contact. Obtaining a mixture of the first composition and the second composition contained in the composition kit described in <13> or <14>, Irradiating the mixture with ultraviolet light or visible light, A method for producing a cured product comprising. The method for producing a cured product described in <21>, wherein the mixture is obtained using a two-component dispenser. The method for producing a cured product described in <21> or <22>, comprising storing the composition kit at room temperature.

Advantages of the Invention

[0007] According to one aspect of the present disclosure, there are provided a composition capable of forming a thiourethane resin and having excellent handleability, a composition kit using this composition, a cured product, a laminate, and a method for producing a cured product.

Modes for Carrying Out the Invention

[0008] In the present disclosure, a numerical range represented by "~" means a range including the numerical values described before and after "~" as the lower limit value and the upper limit value. 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.

[0009] [Composition] The arguments in this disclosure are, Base generator (a), A polymerizable compound comprising at least one selected from the group consisting of polyiso(thio)cyanate compounds (b1) and polythiol compounds (c1), Contains stabilizer (S).

[0010] The compositions of this disclosure include at least one polymerizable compound selected from the group consisting of polyiso(thio)cyanate compounds (b1) and polythiol compounds (c1). That is, the compositions of this disclosure are used to form cured products (i.e., thiourethane resins) obtained by a polymerization reaction between a polyiso(thio)cyanate compound and a polythiol compound. Thiourethane resins can be suitably used in applications requiring a high refractive index, such as optical components.

[0011] Furthermore, the composition of this disclosure contains a base generator. Conventional thiourethane resins are manufactured by inducing a polymerization reaction between a polyiso(thio)cyanate compound (b1) and a polythiol compound (c1) by heating. The composition of this disclosure, by containing a base generator, induces the polymerization reaction between the polyiso(thio)cyanate compound (b1) and the polythiol compound (c1) by light irradiation. In other words, the curing time of the composition of this disclosure is significantly reduced compared to conventional compositions in which the polymerization reaction is induced by heating.

[0012] Furthermore, the compositions of this disclosure contain stabilizers. Because the compositions of this disclosure contain base generators along with polymerizable compounds, there is a risk that the polymerization reaction of the polymerizable compounds may proceed during storage. The compositions of this disclosure suppress the polymerization reaction of the polymerizable compounds by including stabilizers along with base generators. In other words, the composition of this disclosure includes a stabilizer, which allows the polymerizable compound and the base generator to coexist within the composition. Because the composition already contains the polymerizable compound and the base generator, the user does not need to add the base generator to the polymerizable compound, and the handling of the composition is greatly improved.

[0013] The compositions of this disclosure may contain either a polyiso(thio)cyanate compound (b1) or a polythiol compound (c1) alone, or both, as polymerizable compounds. When the composition contains a polyiso(thio)cyanate compound (b1) and a polythiol compound (c1), the mass ratio (c1 / b1) of the polyiso(thio)cyanate compound (b1) to the polythiol compound (c1) contained in the composition is not particularly limited and can be selected from the range of 99 / 1 to 1 / 99.

[0014] If the composition contains a polyiso(thio)cyanate compound (b1) and a polythiol compound (c1) as polymerizable compounds, the mass ratio of the polymerizable compounds in the composition may be determined to satisfy either condition A or condition B below. Condition A: The mass ratio (b1 / c1) of the polyiso(thio)cyanate compound (b1) to the polythiol compound (c1) contained in the polymerizable compound of the composition is within the range of 99 / 1 to 70 / 30, 99 / 1 to 75 / 25, or 95 / 5 to 80 / 20. Condition B: The mass ratio (b1 / c1) of the polyiso(thio)cyanate compound (b1) to the polythiol compound (c1) contained in the polymerizable compound of the composition is within the range of 1 / 99 to 30 / 70, 1 / 99 to 25 / 75, or 5 / 95 to 20 / 80.

[0015] If the composition contains a polyiso(thio)cyanate compound (b1) and a polythiol compound (c1) as polymerizable compounds, the polyiso(thio)cyanate compound (b1) and the polythiol compound (c1) may partially react in the composition to produce a thiourethane compound. That is, the composition may contain a thiourethane compound, which is a reaction product of the polyiso(thio)cyanate compound (b1) and the polythiol compound (c1).

[0016] When using the composition of this disclosure as the first composition of a composition kit described later, the above mass ratio (c1 / b1) is preferably determined by considering the mass ratio (c1+b2 / b1+c2) of the polythiol compound (c1+c2) to the polyiso(thio)cyanate compound (b1+b2) in a mixture of the first composition and the second composition.

[0017] The total content of polymerizable compounds in the composition is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, particularly preferably 50% by mass or more, and even more preferably 60% by mass or more, based on the total mass of the composition, from the viewpoint of photocurability and the adhesion and bonding properties of the cured product. The total content of polymerizable compounds in the composition may be 99.9% by mass or less, or 99.8% by mass or less, based on the total mass of the composition.

[0018] <Base Generator (a)> The compositions of this disclosure include a base-generating agent (a). In this disclosure, "base-generating agent" means a compound that releases a base by at least one of light energy such as electromagnetic waves and thermal energy. The composition contains a base generator (a), which improves the photocurability of polymerizable compounds. Furthermore, if thermal curing is performed as needed, the thermosetting properties can also be improved.

[0019] Examples of base-generating agents (a) include compounds represented by the following formulas (1) to (4).

[0020] (The compound represented by formula (1)) [ka]

[0021] In formula (1), R1 to R4 each independently represent an alkyl group having 1 to 8 carbon atoms, and R5 to R8 each independently represent an alkyl group having 1 to 8 carbon atoms, a phenyl group, a naphthyl group, an anthracenyl group, or a phenanthrill group, and the phenyl group, naphthyl group, anthracenyl group, and phenanthrill group may be substituted with a halogen atom, an alkyl group, an aryl group, an alkenyl group, a cycloalkyl group, or a heterocyclic group.

[0022] In formula (1), R1 to R4 are preferably the same. R1 to R4 are preferably alkyl groups having 2 to 5 carbon atoms, more preferably linear alkyl groups, and even more preferably n-butyl groups.

[0023] In formula (1), R8 is preferably an alkyl group having 2 to 5 carbon atoms, more preferably a linear alkyl group, and even more preferably an n-butyl group. R5 to R7 are preferably the same. R5 to R7 are preferably a phenyl group, a butylphenyl group, or a naphthyl group, and more preferably a phenyl group, a 4-tert-butylphenyl group, a 1-naphthyl group, or a 4-methyl-1-naphthyl group. If R5 to R7 include an aromatic ring, the aromatic ring may be substituted with substituents such as alkyl groups or aryl groups.

[0024] The compound represented by formula (1) is preferably at least one selected from the group consisting of tetra(n-butyl)ammonium=n-butyltriphenyl borate, tetra(n-butyl)ammonium=n-butyltri(4-tert-butylphenyl) borate, tetra(n-butyl)ammonium=n-butyltri(1-naphthyl) borate, and tetra(n-butyl)ammonium=n-butyltri(4-methyl-1-naphthyl) borate. The "=" in the compound name indicates an ionic bond.

[0025] From the viewpoint of solubility, polymerizability, and pot life balance of the composition, it is more preferable that the compound represented by formula (1) is at least one selected from the group consisting of tetra(n-butyl)ammonium=n-butyltriphenylborate and tetra(n-butyl)ammonium=n-butyltri(1-naphthyl)borate.

[0026] Specific examples of compounds represented by formula (1) include, but are not limited to, the following compounds.

[0027] [ka]

[0028] (The compound represented by formula (2)) [ka]

[0029] In formula (2), R1 to R7 each independently represent an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 3 to 8 carbon atoms, and R8 to R 11 Each of these independently represents an alkyl group having 1 to 8 carbon atoms, a phenyl group, a naphthyl group, an anthracenyl group, or a phenanthrill group, and the phenyl group, naphthyl group, anthracenyl group, and phenanthrill group may be substituted with a halogen atom, an alkyl group, an aryl group, an alkenyl group, a cycloalkyl group, or a heterocyclic group.

[0030] In formula (2), R4 and R5 are preferably cycloalkyl groups having 3 to 8 carbon atoms, more preferably cycloalkyl groups having 4 to 7 carbon atoms. As the cycloalkyl group, a cyclohexyl group is preferred. R1 to R3, R6 and R7 are preferably alkyl groups having 1 to 8 carbon atoms, more preferably alkyl groups having 1 to 5 carbon atoms, and even more preferably a methyl group. R1 to R3, R6 and R7 are preferably linear alkyl groups.

[0031] In formula (2), R 11 is preferably an alkyl group having 2 to 5 carbon atoms, more preferably a linear alkyl group, and even more preferably an n-butyl group. R8 to R 10 are preferably the same. R8 to R 10 are preferably a phenyl group, a butylphenyl group or a naphthyl group, more preferably a phenyl group, a 4-tert-butylphenyl group, a 1-naphthyl group or a 4-methyl-1-naphthyl group. When R8 to R 10 contains an aromatic ring, the aromatic ring may be substituted with substituents such as an alkyl group, an aryl group, etc.

[0032] Also, R8 to R 11 in formula (2) are preferably the same. When R8 to R 11 are the same, R8 to R 11 are preferably a phenyl group, a butylphenyl group or a naphthyl group, more preferably a phenyl group, a 4-tert-butylphenyl group, a 1-naphthyl group or a 4-methyl-1-naphthyl group. When R8 to R 11 are the same and contain an aromatic ring, the aromatic ring may be substituted with a halogen atom, an alkyl group, an aryl group, etc., preferably substituted with a halogen atom, more preferably substituted with a fluorine atom.

[0033] The compound represented by formula (2) is preferably at least one selected from the group consisting of 1,2-dicyclohexyl-4,4,5,5-tetramethylbiguanidium=n-butyltriphenyl borate, 1,2-dicyclohexyl-4,4,5,5-tetramethylbiguanidium=tetrakis(3-fluorophenyl) borate, and 1,2-dicyclohexyl-4,4,5,5-tetramethylbiguanidium=butyltri(1-naphthyl) borate. The "=" in the compound name indicates an ionic bond.

[0034] From the viewpoint of solubility, polymerizability and pot life balance of the composition, it is more preferable that the compound represented by formula (2) is at least one selected from the group consisting of 1,2-dicyclohexyl-4,4,5,5-tetramethylbiguanidium=n-butyltriphenyl borate and 1,2-dicyclohexyl-4,4,5,5-tetramethylbiguanidium=tetrakis(3-fluorophenyl) borate.

[0035] Specific examples of compounds represented by formula (2) include, but are not limited to, the following compounds.

[0036] [ka]

[0037] (The compound represented by formula (3)) [ka]

[0038] In formula (3), n represents an integer from 1 to 3, and R1 to R4 each independently represent an alkyl group, phenyl group, naphthyl group, anthracenyl group, or phenanthrill group having 1 to 8 carbon atoms, and the phenyl group, naphthyl group, anthracenyl group, and phenanthrill group may be substituted with a halogen atom, alkyl group, aryl group, alkenyl group, cycloalkyl group, or heterocyclic group.

[0039] n is preferably 1 or 3.

[0040] R4 is preferably an alkyl group having 2 to 5 carbon atoms, more preferably a linear alkyl group, and even more preferably an n-butyl group. R1 to R3 are preferably the same. R1 to R3 are preferably a phenyl group, a butylphenyl group, or a naphthyl group, and more preferably a phenyl group, a 4-tert-butylphenyl group, a 1-naphthyl group, or a 4-methyl-1-naphthyl group. If R1 to R3 include an aromatic ring, the aromatic ring may be substituted with substituents such as alkyl groups or aryl groups.

[0041] Furthermore, it is preferable that R1 to R4 in equation (3) are the same. When R1 to R4 are the same, R1 to R4 are preferably a phenyl group, a butylphenyl group, or a naphthyl group, and more preferably a phenyl group, a 4-tert-butylphenyl group, a 1-naphthyl group, or a 4-methyl-1-naphthyl group. When R1 to R4 are the same and include an aromatic ring, the aromatic ring may be substituted with a halogen atom, alkyl group, aryl group, etc., and is preferably substituted with a halogen atom, and more preferably substituted with a fluorine atom.

[0042] The compounds represented by formula (3) are diazabicycloundecenium=n-butyltriphenylborate, diazabicycloundecenium=tetrakis(3-fluorophenyl)borate, diazabicycloundecenium=butyltri(1-naphthyl)borate, diazabicycloundecenium=tetraphenylborate, diazabicyclononenium=n-butyltriphenylborate, diazabicyclononenium=tetrakis(3-fluorophenyl It is preferable that the compound is at least one selected from the group consisting of 1-naphthyl tri(1-)borate, diazabicyclononenium-butyltri(1-naphthyl)borate, and diazabicyclononenium-tetraphenylborate. In the compound name, "=" indicates an ionic bond.

[0043] Among the above, it is more preferable that the compound represented by formula (3) is at least one selected from the group consisting of diazabicycloundecenium=tetraphenyl borate and diazabicyclononenium=tetraphenyl borate.

[0044] (The compound represented by formula (4)) [ka]

[0045] In formula (4), R1 to R4 each independently represent an alkyl group having 1 to 8 carbon atoms, a phenyl group, a naphthyl group, an anthracenyl group, or a phenanthrill group, and the phenyl group, naphthyl group, anthracenyl group, and phenanthrill group may be substituted with a halogen atom, an alkyl group, an aryl group, an alkenyl group, a cycloalkyl group, or a heterocyclic group.

[0046] R4 is preferably an alkyl group having 2 to 5 carbon atoms, more preferably a linear alkyl group, and even more preferably an n-butyl group. R1 to R3 are preferably the same. R1 to R3 are preferably a phenyl group, a butylphenyl group, or a naphthyl group, and more preferably a phenyl group, a 4-tert-butylphenyl group, a 1-naphthyl group, or a 4-methyl-1-naphthyl group. If R1 to R3 include an aromatic ring, the aromatic ring may be substituted with substituents such as alkyl groups or aryl groups.

[0047] Furthermore, it is preferable that R1 to R4 in equation (4) are the same. When R1 to R4 are the same, R1 to R4 are preferably a phenyl group, a butylphenyl group, or a naphthyl group, and more preferably a phenyl group, a 4-tert-butylphenyl group, a 1-naphthyl group, or a 4-methyl-1-naphthyl group. When R1 to R4 are the same and include an aromatic ring, the aromatic ring may be substituted with a halogen atom, alkyl group, aryl group, etc., and is preferably substituted with a halogen atom, and more preferably substituted with a fluorine atom.

[0048] The compound represented by formula (4) is preferably at least one selected from the group consisting of 1,1,3,3-tetramethylguanidinium=n-butyltriphenyl borate, 1,1,3,3-tetramethylguanidinium=tetrakis(3-fluorophenyl) borate, 1,1,3,3-tetramethylguanidinium=butyltri(1-naphthyl) borate, and 1,1,3,3-tetramethylguanidinium=tetraphenyl borate. The "=" in the compound name indicates an ionic bond.

[0049] Among the above, the compound represented by formula (4) is more preferably 1,1,3,3-tetramethylguanidinium=tetraphenyl borate.

[0050] From the viewpoint of promoting photocuring, the content of the base generator (a) is preferably 0.01 parts by mass or more, more preferably 0.03 parts by mass or more, and even more preferably 0.05 parts by mass or more, when the total mass of the polymerizable compound is 100 parts by mass. From the viewpoint of improving pot life, adhesion, and bonding properties, the content of the base generator (a) is preferably 5.00 parts by mass or less, more preferably 3.00 parts by mass or less, and even more preferably 1.00 part by mass or less, when the total mass of the polymerizable compound is 100 parts by mass.

[0051] <Polyiso(thio)cyanate compound (b1)> The compositions of this disclosure may also contain a polyiso(thio)cyanate compound (b1) as a polymerizable compound. In this disclosure, a polyiso(thio)cyanate compound means a compound having two or more isocyanate groups or isothiocyanate groups in one molecule. The polyiso(thio)cyanate compound (b1) contained in the composition may be one type or two or more types.

[0052] The polyiso(thio)cyanate compound (b1) may include dimers, trimers, or prepolymers. Examples of these polyiso(thio)cyanate compounds are those exemplified in International Publication No. 2011 / 055540.

[0053] Examples of polyiso(thio)cyanate compounds (b1) include aliphatic polyiso(thio)cyanate compounds, alicyclic polyiso(thio)cyanate compounds, aromatic polyiso(thio)cyanate compounds, and heterocyclic polyiso(thio)cyanate compounds. The polyiso(thio)cyanate compound (b1) contained in the composition may be one type or two or more types.

[0054] Alicyclic polyiso(thio)cyanate compounds refer to polyiso(thio)cyanate compounds that contain an alicyclic structure and may also contain a heterocyclic structure. Aromatic polyiso(thio)cyanate compounds refer to polyiso(thio)cyanate compounds that contain an aromatic structure and may also contain an alicyclic structure and a heterocyclic structure. Heterocyclic polyiso(thio)cyanate compounds refer to polyiso(thio)cyanate compounds that contain a heterocyclic structure and do not contain an alicyclic structure or an aromatic structure.

[0055] The polyiso(thio)cyanate compound (b1) preferably includes at least one selected from the group consisting of aliphatic polyiso(thio)cyanate compounds, alicyclic polyiso(thio)cyanate compounds, aromatic polyiso(thio)cyanate compounds, and heterocyclic polyiso(thio)cyanate compounds.

[0056] From the viewpoint of excellent adhesion and refractive index of the cured product, and excellent photocurability, the polyiso(thio)cyanate compound (b1) preferably contains at least one selected from the group consisting of pentamethylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, bis(isocyanatomethyl)cyclohexane, bis(isocyanatocyclohexyl)methane, 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and phenylene diisocyanate. It is more preferable to include at least one selected from the group consisting of 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, xylylene diisocyanate, and 1,3-bis(isocyanatomethyl)cyclohexane. It is even more preferable to include at least one selected from the group consisting of 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, and m-xylylene diisocyanate.

[0057] <Polythiol compound (c1)> The compositions of this disclosure may also contain a polythiol compound (c1) as a polymerizable compound. In this disclosure, a polythiol compound means a compound having two or more thiol groups in one molecule. The composition may contain only one polythiol compound (c1) or two or more compounds.

[0058] Specific examples of polythiol compounds (c1) include those exemplified in International Publication No. 2016 / 125736.

[0059] From the viewpoint of excellent photocurability, the polythiol compound (c1) is 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(2-mercaptoacetate), 2 Preferably, it contains at least one selected from the group consisting of ,5-bis(mercaptomethyl)-1,4-dithiane, bis(2-mercaptoethyl) sulfide, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 4,6-bis(mercaptomethylthio)-1,3-dithiane, 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithiethane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 3-mercaptomethyl-1,5-dimercapto-2,4-dithiapentane, and tris(mercaptomethylthio)methane. It is more preferable to include at least one selected from the group consisting of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, pentaerythritol tetrakiss (3-mercaptopropionate), and pentaerythritol tetrakiss (2-mercaptoacetate). It is even more preferable to include at least one selected from the group consisting of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane.

[0060] From the viewpoint of the refractive index of the resulting cured product, the polythiol compound (c1) preferably has a refractive index of 1.60 to 1.80 for sodium D-line light (i.e., light with a wavelength of 589.3 nm) at 20°C.

[0061] <Other polymerizable compounds> If necessary, the compositions of this disclosure may also contain polymerizable compounds other than polyiso(thio)cyanate compounds (b1) and polythiol compounds (c1). For example, the composition may include an episulfide compound as a polymerizable compound. Examples of episulfide compounds include those represented by the following formula (5).

[0062] [ka]

[0063] In formula (5), Y represents a straight-chain divalent hydrocarbon group having 1 to 4 carbon atoms, a branched divalent hydrocarbon group having 2 to 4 carbon atoms, a cyclic divalent hydrocarbon group having 3 to 6 carbon atoms, a 1,4-dithiane group, an arylene group, or an aralkylene group, m represents an integer from 0 to 2, and n represents an integer from 0 to 3. Y may contain substituents or may be unsubstituted.

[0064] Y preferably represents a straight-chain divalent hydrocarbon group having 1 to 4 carbon atoms, a branched divalent hydrocarbon group having 2 to 4 carbon atoms, or a cyclic divalent hydrocarbon group having 3 to 6 carbon atoms, and more preferably a straight-chain divalent hydrocarbon group having 1 to 4 carbon atoms. m preferably represents 0 or 1, and more preferably 0. n preferably represents 0 or 1, and more preferably 1.

[0065] The episulfide compound preferably contains at least one selected from the group consisting of bis(2,3-epithiopropyl)sulfide, bis(2,3-epithiopropyl)disulfide, and 2,5-bis(2,3-epithiopropylthiomethyl)-1,4-dithiane.

[0066] From the viewpoint of the refractive index of the resulting cured product, the episulfide compound is preferably such that the refractive index of the sodium D line (i.e., light with a wavelength of 589.3 nm) at 20°C is 1.60 to 1.80.

[0067] If the composition contains polymerizable compounds other than polyiso(thio)cyanate compound (b1) and polythiol compound (c1), the total content of polyiso(thio)cyanate compound (b1) and polythiol compound (c1) is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more of the total polymerizable compounds.

[0068] <Stabilizer (S)> The compositions of this disclosure include a stabilizer (S). Preferred examples of stabilizers (S) include acids with a pKa of less than 2.0, anhydrides of acids with a pKa of less than 2.0, and phosphite esters. The stabilizer (S) contained in the composition may be one type or two or more types.

[0069] Examples of acids with a pKa of less than 2.0 include hydrochloric acid (pKa: -3.7), sulfuric acid (pKa: -3.0), nitric acid (pKa: -1.4), and sulfonic acids with a pKa of less than 2.0. From the viewpoint of the pot life of the composition, sulfonic acids with a pKa of less than 2.0 are preferred. Examples of sulfonic acids with a pKa of less than 2.0 include 10-camphor sulfonic acid (pKa: 1.2), methanesulfonic acid (pKa: -2.6), p-toluenesulfonic acid (pKa: -2.8), vinylsulfonic acid (pKa: -2.7), and benzenesulfonic acid (pKa: 0.7). Acids with a pKa of less than 2.0 may also form hydrates. The pKa of an acid with a pKa less than 2.0 may be 0.2 or greater, 0.5 or greater, or 1.0 or greater.

[0070] Examples of acid anhydrides with a pKa of less than 2.0 include the acid anhydrides mentioned above. From the viewpoint of the pot life of the composition, sulfonic acid anhydrides with a pKa of less than 2.0 are preferred.

[0071] Examples of phosphite esters include triphenyl phosphite, tris(4-methoxyphenyl) phosphite, and tris(4-methylphenyl) phosphite. From the viewpoint of suppressing the self-polymerization of the polyiso(thio)cyanate compound (b1) in the presence of the base generator (a), triphenyl phosphite is preferred.

[0072] From the viewpoint of suppressing the self-polymerization of the polyiso(thio)cyanate compound (b1) in the presence of the base generator (a) and the pot life of the composition, the content of the stabilizer (S) is preferably 0.001 parts by mass or more, more preferably 0.005 parts by mass or more, and even more preferably 0.01 parts by mass or more, when the total mass of the polymerizable compound is 100 parts by mass. From the viewpoint of the polymerizability of the polymerizable compound, the content of the stabilizer (S) is preferably 1.0 part by mass or less, more preferably 0.5 parts by mass or less, and even more preferably 0.3 parts by mass or less, when the total mass of the polymerizable compound is 100 parts by mass.

[0073] <Polyether-modified silicone compound (d)> The compositions of this disclosure may include a polyether-modified silicone compound (d). The inclusion of a polyether-modified silicone compound (d) in the composition improves the release properties of the cured product.

[0074] From the viewpoint of release properties, the polyether-modified silicone compound (d) preferably contains at least one selected from the group consisting of a polyether-modified silicone compound (d1) represented by the following general formula (1) and a polyether-modified silicone compound (d2) represented by the following general formula (2).

[0075] [ka]

[0076] In general formula (1), m and n each independently represent an integer greater than or equal to 1. a and b each independently represent an integer greater than or equal to 0 (except when both a and b are 0). R1 represents a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched alkenyl group having 2 to 10 carbon atoms, an acryloyl group, a methacryloyl group, or a hydrogen atom. In general formula (2), p represents an integer of 1 or more, and c, d, e, and f each independently represent an integer of 0 or more (except when c, d, e, and f are all 0). R2 and R3 each independently represent a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched alkenyl group having 2 to 10 carbon atoms, an acryloyl group, a methacryloyl group, or a hydrogen atom.

[0077] In general formulas (1) and (2), the unit represented by (OC3H6) represents an oxypropylene group (O-CH(CH3)-CH2), and the C3H6 in the part represented by Si-C3H6-(OC2H4) represents a trimethylene group (1,3-propanediyl group (-CH2CH2CH2-)).

[0078] In general formula (1), m is preferably an integer from 1 to 500, more preferably an integer from 10 to 300. n is preferably an integer from 1 to 100, more preferably an integer from 1 to 50. a is preferably an integer between 0 and 1000, more preferably an integer between 1 and 500. b is preferably an integer between 0 and 1000, more preferably an integer between 0 and 500.

[0079] The weight-average molecular weight of the polyether-modified silicone compound represented by general formula (1) is preferably 200 to 100,000, more preferably 1,000 to 80,000.

[0080] In general formula (2), p is preferably an integer between 1 and 500, more preferably an integer between 10 and 300. c and f are preferably integers between 0 and 1000, more preferably integers between 1 and 500. d and e are preferably integers between 0 and 1000, more preferably integers between 0 and 500.

[0081] The weight-average molecular weight of the polyether-modified silicone compound represented by general formula (2) is preferably 200 to 100,000, more preferably 1,000 to 80,000.

[0082] In general formula (1), the mole fraction of the silicone unit [i.e., (m+n) / (m+n+a+b)] is preferably 0.08 to 0.60. The release properties can be sufficiently maintained if the mole fraction of the silicone unit is 0.08 or higher. By keeping the mole fraction of the silicone unit below 0.60, cloudiness, opacity, etc., in the cured product can be suppressed, and transparency can be maintained. From the same viewpoint as above, the mole fraction of the silicone unit in general formula (1) is more preferably 0.10 to 0.50. In general formula (1), the mole fraction of the polyether unit [i.e., (a+b) / (a+b+m+n)] is preferably 0.40 to 0.92. By having a mole fraction of 0.40 or higher for the polyether unit, clouding, opacity, etc., in the cured product can be suppressed, and transparency can be maintained. The release properties can be sufficiently maintained if the mole fraction of the polyether unit is 0.92 or less. From the same viewpoint as above, the mole fraction of the polyether unit in general formula (1) is more preferably 0.50 to 0.90.

[0083] The mole fractions of the silicone unit and the polyether unit are measured by the following method. The mole fractions of the silicone unit and the polyether unit are: 1 The following measurements are performed using 1H-NMR. First, δ ppm Let the integral value for the chemical shift of =0.4~0.6(Si-CH2-(EO)) be 2. The above integral value represents the integral value of the methylene group at the Si-CH2-(EO) site. Using this integral value as a reference, the integral values ​​X, Y, and Z for the following chemical shifts are calculated, respectively. A is calculated using the following formula (1). A = (((Z / 3) - 3) / 2) + 3 (1) In equation (1), Z is δ ppm This represents the integral value at the chemical shift of -0.2 to 0.2 (CH3-Si). The above integral value represents the integral value of the methyl group at the CH3-Si site. B is calculated using the following formula (2). B = ((XY-2) / 4) + (Y / 3) (2) In equation (2), X is δ ppm This represents the integral value in the chemical shift of =3.2~3.9(CH2-CH2-O). The above integral value represents the integral value of the methylene group in the oxyethylene moiety. In equation (2), Y is δ ppm =1.0~1.2 This is the integral value in the chemical shift of (CH2-CH(CH3)-O). The above integral value represents the integral value of the methyl group in the oxypropylene moiety. The mole fraction of the silicone unit is measured by (A / (A+B)) × 100. The mole fraction of the polyether unit is measured by (B / (A+B)) × 100.

[0084] In general formula (2), the mole fraction of the silicone unit [i.e., p / (p+c+d+e+f)] is preferably 0.08 to 0.60. In general formula (2), the mole fraction of the silicone unit is 0.08 or higher, which ensures sufficient release properties. In general formula (2), having a mole fraction of silicone units of 0.60 or less suppresses clouding, opacity, etc., in the cured product, thereby maintaining transparency. From the same viewpoint as above, the mole fraction of the silicone unit in general formula (2) is more preferably 0.10 to 0.50. In general formula (2), the mole fraction of the polyether unit [i.e., (c+d+e+f) / (c+d+e+f+p)] is preferably 0.40 to 0.92. In general formula (2), having a mole fraction of polyether units of 0.40 or higher suppresses clouding, opacity, etc., in the cured product, thereby maintaining transparency. In general formula (2), the mole fraction of the polyether unit is 0.92 or less, which ensures sufficient release properties. From the same viewpoint as above, the mole fraction of the polyether unit in general formula (2) is more preferably 0.50 to 0.90.

[0085] The method for measuring the mole fraction of the silicone unit and the polyether unit is the same as the method described above.

[0086] In general formulas (1) and (2), the total mole fraction of silicone units [i.e., (m+n+p) / (m+n+p+a+b+c+d+e+f)] is preferably 0.08 to 0.60. In general formulas (1) and (2), sufficient release properties can be maintained if the total mole fraction of silicone units is 0.08 or higher. In general formulas (1) and (2), the total mole fraction of silicone units is 0.60 or less, which suppresses clouding, opacity, etc. in the cured product and maintains transparency. From the same viewpoint as above, the mole fraction of the total silicone units in general formula (1) and general formula (2) is more preferably 0.10 to 0.50.

[0087] In general formulas (1) and (2), the mole fraction of the total polyether units [i.e., (a+b+c+d+e+f) / (a+b+c+d+e+f+m+n+p)] is preferably 0.40 to 0.92. In general formulas (1) and (2), the total mole fraction of polyether units is 0.40 or higher, which suppresses clouding, opacity, etc., in the cured product and maintains transparency. In general formulas (1) and (2), sufficient release properties can be maintained if the total mole fraction of polyether units is 0.92 or less. From the same viewpoint as above, the mole fraction of the total polyether units in general formula (1) and general formula (2) is more preferably 0.50 to 0.90.

[0088] If polyether-modified silicone compound (d) includes both polyether-modified silicone compound (d1) and polyether-modified silicone compound (d2), The ratio (b1:b2) of the polyether-modified silicone compound (d1) and the polyether-modified silicone compound (d2) may be 5:95 to 95:5, preferably 10:90 to 90:10, and more preferably 20:80 to 80:20, from the viewpoint of the effects of the second embodiment. The polyether-modified silicone compound (d) may contain at least one polyether-modified silicone compound (d1) and at least one polyether-modified silicone compound (d2), and may contain two or more.

[0089] If the composition contains a polyether-modified silicone compound (d), its content is preferably 0.01 parts by mass or more, more preferably 0.03 parts by mass or more, and even more preferably 0.05 parts by mass or more, based on the total mass of the polymerizable compound being 100 parts by mass, from the viewpoint of the release properties of the cured product. From the viewpoint of the transparency of the cured product, the content of the polyether-modified silicone compound (d) is preferably 1.00 part by mass or less, more preferably 0.50 parts by mass or less, and even more preferably 0.30 parts by mass or less, when the total mass of the polymerizable compound is 100 parts by mass.

[0090] <UV absorber (e)> The compositions of this disclosure may include an ultraviolet absorber (e). The inclusion of an ultraviolet absorber (e) in the composition improves the weather resistance of the composition or the cured product.

[0091] As the ultraviolet absorber (e), at least one selected from the group consisting of compounds represented by the following formulas (e-1) to (e-4) is preferred.

[0092] [ka]

[0093] In formula (e-1), R1 represents a hydrogen atom or a chlorine atom, and R2 and R3 each independently represent a substituted or unsubstituted linear or branched alkyl group having 1 to 12 carbon atoms, or an aromatic group or heteroaromatic group having 4 to 12 carbon atoms. When a substituted or unsubstituted linear or branched alkyl group having 1 to 12 carbon atoms contains substituents, examples of substituents include aromatic groups or heteroaromatic groups having 6 to 12 carbon atoms. Examples of aromatic groups and heteroaromatic groups include phenyl groups, biphenyl groups, 2,3,5-trimethylphenyl groups, furyl groups, and p-methoxyphenyl groups. The compound represented by formula (e-1) may be a commercially available product, such as Tinuvin 234 (manufactured by BASF Japan Ltd.) or Tinuvin 328 (manufactured by BASF Japan Ltd.).

[0094] In equation (e-2), A1 represents the structure shown in equation (e-2a) below, and R4 and R5 each independently represent the structure shown in equation (e-2b) below.

[0095] [ka]

[0096] In formulas (e-2a) and (e-2b), Q1 to Q5 each independently represent a linear or branched alkyl group having 1 to 12 carbon atoms, a linear or branched alkoxy group having 1 to 18 carbon atoms, a halogen, or an aromatic or heteroaromatic group having 4 to 12 carbon atoms. In linear or branched alkyl groups having 1 to 12 carbon atoms, the number of carbon atoms is preferably 1 to 6, and more preferably 1 to 3. Examples of linear or branched alkoxy groups having 1 to 18 carbon atoms include methoxy, butoxy, 2-hydroxy-3-octyloxy-propyroxy, and 2-ethylhexyloxy groups. Examples of aromatic groups and heteroaromatic groups include phenyl groups, biphenyl groups, 2,3,5-trimethylphenyl groups, furyl groups, and p-methoxyphenyl groups. The compound represented by formula (e-2) may be a commercially available product, such as Tinuvin 405 (manufactured by BASF Japan Ltd.) or Tinuvin 1600 (manufactured by BASF Japan Ltd.).

[0097] In formula (e-3), R6 and R7 each independently represent a linear or branched alkyl group having 1 to 6 carbon atoms, or a linear or branched alkoxy group having 1 to 6 carbon atoms. In formula (e-3), examples of linear or branched alkyl groups having 1 to 6 carbon atoms include methyl, ethyl, butyl, propyl, pentyl, and hexyl groups. Examples of linear or branched alkoxy groups having 1 to 6 carbon atoms include methoxy, ethoxy, butoxy, and phenoxy groups. The compound represented by formula (e-3) may be a commercially available product, such as Hostavin VSU (manufactured by Clariant Chemicals Co., Ltd.).

[0098] In formula (e-4), R8 represents an aromatic group having 6 to 20 carbon atoms that may be substituted, or an alicyclic group having 5 to 20 carbon atoms that may be substituted. R9 and R 10 Each of these independently represents a linear or branched alkyl group having 1 to 6 carbon atoms. Examples of aromatic groups with 6 to 20 carbon atoms that may be substituted include phenyl groups, benzyl groups, benzoyl groups, and p-methoxybenzyl groups. Examples of alicyclic groups having 5 to 20 carbon atoms that may be substituted include cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclopentanyl, and cyclodecanyl groups. When the above aromatic group or alicyclic group contains substituents, examples of substituents include alkyl groups having 1 to 6 carbon atoms and alkoxy groups having 1 to 6 carbon atoms. The compound represented by formula (e-4) may be a commercially available product, such as Hostavin PR25 (manufactured by Clariant Chemicals Co., Ltd.).

[0099] If the composition contains an ultraviolet absorber (e), its content is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, and even more preferably 0.10 parts by mass or more, based on the total mass of the polymerizable compound, from the viewpoint of the weather resistance of the cured product. If the composition contains an ultraviolet absorber (e), its content is preferably 3.00 parts by mass or less, more preferably 2.00 parts by mass or less, and even more preferably 1.00 part by mass or less, based on the total mass of the polymerizable compound being 100 parts by mass, from the viewpoint of the curability of the composition.

[0100] (Metal catalyst) The compositions of this disclosure may include a metal catalyst. When the composition contains a metal catalyst, polymerization is further improved, and improvements in the heat resistance, strength, hardness, adhesion, and bonding properties of the cured product can be expected.

[0101] From the viewpoint of enhancing polymerizability, the metal catalyst preferably contains tin, zinc, bismuth, aluminum, or zirconium, and more preferably contains tin.

[0102] Examples of tin-containing metal catalysts include dibutyltin(IV) dilaurate, dibutyltin(IV) dichloride, and dimethyltin(IV) dichloride. Among the above, dibutyltin(IV) dichloride and dimethyltin(IV) dichloride are preferred from the viewpoint of improving polymerizability.

[0103] From the viewpoint of enhancing polymerizability, the content of the metal catalyst is preferably 0.001 parts by mass or more, more preferably 0.003 parts by mass or more, and even more preferably 0.005 parts by mass or more, when the total mass of the polymerizable compound is 100 parts by mass. From the viewpoint of extending the pot life, the content of the metal catalyst is preferably 0.5 parts by mass or less, more preferably 0.1 parts by mass or less, and even more preferably 0.05 parts by mass or less, relative to the total mass of the polymerizable compound.

[0104] (Other ingredients) If necessary, the composition may contain components other than those described above. For example, the composition may contain photosensitizers, epoxy group compounds, phenol compounds, amino group compounds, inorganic compounds containing sulfur atoms, inorganic compounds containing selenium atoms, solvents, bluing agents, IR cut agents, blue light cut agents, reactive diluents, oil-soluble dyes, pigments, fragrances, fillers, coupling agents and other adhesion enhancers, chain extenders, crosslinking agents, defoaming agents, anti-sagging agents, dispersants, plasticizers, anti-sagging agents, antifouling agents, preservatives, bactericides, antifungal agents, antifungal agents, matting agents, thickeners, pigment dispersants, anti-repellent agents, scratch-resistant enhancers, slip agents, surface modifiers, color separation preventatives, emulsifiers, anti-skinning agents, drying agents, antifouling agents, antistatic agents, conductive agents (electrostatic additives), flame retardants, thermal conductivity improvers, plasticizers, silica microparticles, zirconium oxide microparticles, titanium oxide microparticles, zinc oxide microparticles, silver oxide microparticles, polyolefin microparticles, poly(meth)acrylic microparticles, polyurethane microparticles, etc.

[0105] If the composition contains the above components, their total content may be 0.1 ppm to 70% by mass, 1 ppm to 30% by mass, 10 ppm to 10% by mass, or 0.1% to 5% by mass, based on the total mass of the composition.

[0106] [Composition Kit] The composition kit disclosed herein is The first composition, which is the composition of the present disclosure described above, The present invention comprises a second composition containing a polymerizable compound comprising at least one selected from the group consisting of polyiso(thio)cyanate compounds (b2) and polythiol compounds (c2).

[0107] The composition kit of this disclosure is used, for example, in a method for producing a cured product by mixing a first composition and a second composition that have been prepared in advance (hereinafter also referred to as a two-component manufacturing method). In the two-component manufacturing method, a cured product is produced by mixing two compositions containing the necessary components in predetermined proportions. Therefore, a cured product can be produced even without the skills or knowledge required for preparing the compositions. Accordingly, the composition kit of this disclosure is easy to handle.

[0108] The first and second compositions comprising the composition kit each contain a polymerizable compound.

[0109] If the first composition contains a polyiso(thio)cyanate compound (b1) and a polythiol compound (c1) as polymerizable compounds, the mass ratio of the polymerizable compounds contained in the first composition may be determined to satisfy either condition A or condition B below. Condition A: The mass ratio (b1 / c1) of the polyiso(thio)cyanate compound (b1) to the polythiol compound (c1) contained in the polymerizable compound of the first composition is within the range of 99 / 1 to 70 / 30, 99 / 1 to 75 / 25, or 95 / 5 to 80 / 20. Condition B: The mass ratio (b1 / c1) of the polyiso(thio)cyanate compound (b1) to the polythiol compound (c1) contained in the polymerizable compound of the first composition is within the range of 1 / 99 to 30 / 70, 1 / 99 to 25 / 75, or 5 / 95 to 20 / 80.

[0110] If the first composition contains a polyiso(thio)cyanate compound (b1) and a polythiol compound (c1) as polymerizable compounds, a thiourethane compound may be formed in the first composition by a partial reaction between the polyiso(thio)cyanate compound (b1) and the polythiol compound (c1). That is, the first composition may contain a thiourethane compound, which is a reaction product of the polyiso(thio)cyanate compound (b1) and the polythiol compound (c1).

[0111] The mass ratio (b1+b2) / (c1+c2) of the polymerizable compounds contained in the first and second compositions constituting the composition kit is preferably within the range of 40 / 60 to 60 / 40. When the mass ratio (b1+b2) / (c1+c2) of the polymerizable compounds contained in the first composition and the second composition is within the range of 40 / 60 to 60 / 40, the amount of polymerizable compounds that do not contribute to the polymerization reaction can be effectively reduced.

[0112] The second composition may contain only one of the polymerizable compounds, a polyiso(thio)cyanate compound (b2) or a polythiol compound (c2), or it may contain both the polyiso(thio)cyanate compound (b2) and the polythiol compound (c2). If the first composition does not contain a polyiso(thio)cyanate compound (b1) as a polymerizable compound, the second composition contains at least a polyiso(thio)cyanate compound (b2) as a polymerizable compound. If the first composition does not contain a polythiol compound (c1) as a polymerizable compound, the second composition contains at least a polythiol compound (c2) as a polymerizable compound.

[0113] The polyiso(thio)cyanate compound (b2) or polythiol compound (c2) contained in the second composition may be the compounds exemplified as the polyiso(thio)cyanate compound (b1) or polythiol compound (c1) contained in the first composition, respectively. The polyiso(thio)cyanate compound (b1) contained in the first composition and the polyiso(thio)cyanate compound (b2) contained in the second composition may be the same or different. The polythiol compound (c1) contained in the first composition and the polythiol compound (c2) contained in the second composition may be the same or different.

[0114] The second composition may contain components other than the polyiso(thio)cyanate compound (b2) or the polythiol compound (c2). For example, the components described above may be included as components that may be included in the first composition.

[0115] From the viewpoint of ease of handling, it is preferable that the second composition does not contain a base generating agent. Furthermore, it is preferable that the second composition contains only one of either a polyiso(thio)cyanate compound (b1) or a polythiol compound (c1) as a polymerizable compound.

[0116] The applications of the composition kits of this disclosure are not particularly limited. Because the thiourethane resins formed using the composition kits of this disclosure have a high refractive index, they are suitably used as materials for components that require transparency, such as optical components.

[0117] The composition kit of this disclosure may be used as an adhesive. For example, it may be used as an adhesive for bonding optical components to optical components or to another component. Examples of optical components to be bonded include ICT (Information and Communication Technology) components, AR (Augmented Reality) components, VR (Virtual Reality) components, etc.

[0118] The composition kit of this disclosure may be used as a coating agent. For example, it may be used as a coating agent for coating the surface of an optical component. Examples of optical components to be coated include lenses, ICT components, AR components, VR components, and the like.

[0119] [Cured product] The cured product of this disclosure is a cured product of a mixture of the first composition and the second composition contained in the composition kit described above. The cured product of this disclosure can be obtained by irradiating a mixture with light to induce a polymerization reaction of polymerizable compounds. Therefore, the cured product of this disclosure may have a shape that is difficult to achieve by heat polymerization. The refractive index of the cured product of this disclosure may be in the range of 1.50 to 1.80, or in the range of 1.55 to 1.75, or in the range of 1.60 to 1.70.

[0120] When the cured product of this disclosure is an optical component, specific examples of optical components include optical adhesives, coatings, optical waveguides, films, lenses, anti-reflective coatings, microlenses, microlens arrays, wafer-level lenses, imaging lenses for cameras (automotive cameras, digital cameras, PC cameras, mobile phone cameras, surveillance cameras, etc.), eyeglass lenses, light beam focusing lenses, light diffusion lenses, camera flash lenses, and the like.

[0121] [Laminate] The laminate of this disclosure includes the cured product of this disclosure described above and a substrate. Examples of the cured material contained in the laminate include layers placed on the surface of a substrate (e.g., a coating layer) and layers placed between multiple substrates (e.g., an adhesive layer). The laminate may include an intermediate layer placed between the substrate and the cured product. By placing an intermediate layer between the substrate and the cured product of this disclosure, for example, the adhesion between the cured product and the substrate can be improved. The material of the intermediate layer is not particularly limited and can be selected according to the purpose of providing the intermediate layer. Specific examples of intermediate layer materials include polyurethane aqueous dispersions and transparent adhesives.

[0122] The thickness of the cured material contained in the laminate is not particularly limited. From the viewpoint of photocurability, the thickness of the cured material is preferably 10 mm or less, more preferably 5 mm or less, and even more preferably 3 mm or less. From the viewpoint of ensuring the required performance, the thickness of the cured material is preferably 0.01 μm or more, more preferably 0.05 μm or more, and even more preferably 0.1 μm or more.

[0123] The types of substrates included in the laminate are not particularly limited. Examples include quartz, glass, optical films, ceramic materials, vapor-deposited films, magnetic films, reflective films, metal plates, metal foils, paper, SOG (Spin On Glass), polyester resin, polycarbonate resin, polyimide resin, polyurethane resin, polythiourethane resin, polyepisulfide resin, polyurethane urea resin, polyacrylic resin, polyallyl resin, polyvinyl resin, polyolefin resin, acetylcellulose resin, TFT array substrates, PDP electrode plates, conductive substrates such as metals (e.g., ITO), insulating substrates, semiconductor fabrication substrates such as silicone, silicone nitride, polysilicone, silicone oxide, and amorphous silicone. The laminate may contain only one type of substrate or two or more types.

[0124] If necessary, pretreatment such as etching may be performed on the substrate used for the laminate. Etching methods include alkaline etching, which involves immersion in an alkaline aqueous solution; plasma etching, which involves exposure to a gas plasma such as oxygen; and UV-ozone etching, which involves exposure to ultraviolet light and ozone.

[0125] The laminate may include a functional film. When the laminate includes a functional film, possible locations for the functional film include the interior of the cured product and the surface of the cured product. There are no particular restrictions on the type of functional film, and it can be selected according to the application of the laminate. Specific examples of functional films include polarizing films, phase difference films, gas barrier films, conductive films, insulating films, and optical guide films. If the laminate includes a functional film, the cured product and at least a portion of the functional film may be in direct contact.

[0126] [Method for manufacturing hardened products] The method for producing the cured product of this disclosure involves obtaining a mixture of the first composition and the second composition contained in the composition kit of this disclosure described above, Irradiating the mixture with ultraviolet light or visible light, Includes.

[0127] The method for obtaining a mixture of the first composition and the second composition is not particularly limited and can be carried out by known methods. For example, a mixture may be obtained using a two-component dispenser that dispenses the first composition and the second composition, respectively.

[0128] The method of irradiating a mixture of the first composition and the second composition with ultraviolet light or visible light is not particularly limited and can be carried out by known methods. The ultraviolet or visible light preferably includes light with wavelengths of 200 nm to 450 nm. An example of irradiation conditions for ultraviolet or visible light is an irradiation intensity of 0.1 mW / cm². 2 ~1,000 mW / cm 2 The cumulative light intensity is 10 mJ / cm². 2 ~30,000 mJ / cm 2 Conditions include irradiation time ranging from 0.1 seconds to 500 seconds. Ultraviolet light or visible light may be irradiated directly onto the mixture, or it may be irradiated through an object (such as a mold) that is transparent to ultraviolet light or visible light.

[0129] From the viewpoint of enhancing the polymerizability of polymerizable compounds, the above method may include heating the mixture. Heating may be performed simultaneously with irradiation of ultraviolet or visible light, before irradiation of ultraviolet or visible light, or after irradiation of ultraviolet or visible light. The heating conditions are not particularly limited. For example, the heating temperature may be selected from 20°C to 200°C, and the heating time may be selected from 0.1 hours to 80 hours.

[0130] From the viewpoint of relieving internal stress generated within the cured material during curing, the above method may include annealing the cured material. The conditions for the annealing process are not particularly limited. For example, the processing temperature may be selected from 50°C to 150°C, preferably from 70°C to 140°C, and more preferably from 80°C to 130°C.

[0131] The above method may include storing the composition kit at room temperature. In this disclosure, "room temperature" means a temperature range of "15°C to 35°C". As shown in the examples described later, the composition kit of this disclosure exhibits excellent storage stability at room temperature. [Examples]

[0132] The following are examples of the embodiments of this disclosure, but this disclosure is not limited to these embodiments. In the following examples, the viscosity of the composition was measured at 20°C using a Brookfield Type B viscometer in accordance with the method described in JIS K7117:1991. In the following examples, "room temperature" refers to a temperature range of "15°C to 35°C".

[0133] <Comparative Example 1> Tetrabutylammonium tri(1-naphthyl)butylborate (0.4 parts by mass, manufactured by Showa Denko K.K.), a base-generating agent, was dissolved in xylylene diisocyanate (50.7 parts by mass), a polyisocyanate compound. After complete dissolution, a polythiol composition (49.3 parts by mass) mainly composed of 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiandecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiandecane, and 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane was added, and the mixture was stirred for a further 10 minutes to prepare the composition. The obtained composition was stored in an oven at 20°C. The viscosity of the composition was measured at the start of storage (initial) and at 1, 3, 5, 7, or 24 hours after the start of storage. The results are shown in Table 1.

[0134] <Example 1> A base-generating agent, tetrabutylammonium tri(1-naphthyl)butylborate (0.4 parts by mass, manufactured by Showa Denko K.K.), and a stabilizer, 10-camphor sulfonic acid (0.01 parts by mass, manufactured by Tokyo Chemical Industry Co., Ltd.), were dissolved in a polyisocyanate compound, xylylene diisocyanate (50.7 parts by mass). After complete dissolution, a polythiol composition (49.3 parts by mass) mainly composed of the polythiol compounds 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiandecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiandecane, and 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane was added, and the mixture was stirred for a further 10 minutes to prepare the composition. The resulting composition was stored in an oven at 20°C. The viscosity of the composition was measured at the start of storage (initial) and 1, 3, 5, 7, or 24 hours after the start of storage. The results are shown in Table 1.

[0135] [Table 1]

[0136] As shown in Table 1, compared to the composition of Comparative Example 1, which contains a base generator and a polymerizable compound but no stabilizer, the composition of Example 1, which contains a base generator, a polymerizable compound, and a stabilizer, maintained a low viscosity even after a period of time had elapsed since the start of storage.

[0137] <Comparative Example 2> Tetrabutylammonium tri(1-naphthyl)butylborate (0.06 parts by mass, manufactured by Showa Denko K.K.), a base-generating agent, was dissolved in xylylene diisocyanate (10 parts by mass), a polyisocyanate compound. After complete dissolution, the solution was stored at 25°C for 12 hours. After storage, the solution had changed into a cloudy gel-like substance.

[0138] <Example 2> Tetrabutylammonium tri(1-naphthyl)butylborate (0.06 parts by mass, manufactured by Showa Denko K.K.), a base-generating agent, was dissolved in xylylene diisocyanate (10 parts by mass), a polyisocyanate compound, together with triphenyl phosphite (0.02 parts by mass, manufactured by Tokyo Chemical Industry Co., Ltd.), a stabilizer. After complete dissolution, the solution was stored at 25°C for 12 hours. Unlike Comparative Example 2, the solution remained a clear liquid after storage. This is thought to be because the solution in Example 2, containing triphenyl phosphite as a stabilizer, suppressed the self-polymerization of the polyisocyanate compound even in the presence of the base-generating agent.

[0139] <Example 3> Tetrabutylammonium tri(1-naphthyl)butylborate (1.77 parts by mass, manufactured by Showa Denko K.K.), a base generator; 10-camphor sulfonic acid (0.018 parts by mass, manufactured by Tokyo Chemical Industry Co., Ltd.), a stabilizer; Hostavin PR-25 (0.09 parts by mass, manufactured by Clariant), an ultraviolet absorber; and SH-3773M (0.036 parts by mass, manufactured by Dow Chemical Japan Ltd.), a polyether-modified silicone compound, were dissolved in xylylene diisocyanate (90 parts by mass), a polyisocyanate compound. After complete dissolution, a polythiol composition (9 parts by mass) mainly consisting of the polythiol compounds 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiandecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiandecane, and 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane was added, and the mixture was stirred for a further 30 to 60 minutes. The mixture was then filtered through a 3 μm PTFE filter, and degassed under vacuum while stirring for 30 to 60 minutes to obtain the first composition (MB1). The obtained first composition (MB1) was stored at 5°C for 85 days. The viscosity measured at 20°C during the initial storage period was 12.3 cP, and the viscosity after 85 days was 30 cP. Furthermore, when the first composition (MB1) was stored at room temperature, after 5 days of storage, the composition (MB1) remained a clear liquid and no polymerization precipitate was observed.

[0140] Ten parts by mass of the first composition (MB1), which had been stored at 5°C for 85 days, was added to the second composition, a polythiol composition (8.67 parts by mass) mainly composed of 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiandecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiandecane, and 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and the mixture was stirred for a further 30 minutes. The mixture was then filtered through a 3 μm PTFE filter and degassed under vacuum while stirring for 30 to 60 minutes to obtain a mixture of the first and second compositions.

[0141] The resulting mixture was poured between a pair of flat glass molds secured with tape at a 0.8 mm interval. Then, it was subjected to a 30-second (9 mW / cm²) exposure test. 2 The mixture was polymerized and cured by irradiation with light (365 nm) at 1 / s and then heating in a 120°C oven for 1 hour. The resulting cured product had a refractive index of 1.67 and possessed transparency suitable for optical components.

[0142] <Example 4> Tetrabutylammonium tri(1-naphthyl)butylborate (0.53 parts by mass, manufactured by Showa Denko K.K.), a base generator; 10-camphor sulfonic acid (0.018 parts by mass, manufactured by Tokyo Chemical Industry Co., Ltd.), a stabilizer; triphenyl phosphite (0.53 parts by mass, manufactured by Tokyo Chemical Industry Co., Ltd.), a stabilizer; Hostavin PR-25 (0.35 parts by mass, manufactured by Clariant), an ultraviolet absorber; dimethyltin(IV) dichloride (0.009 parts by mass, manufactured by Tokyo Chemical Industry Co., Ltd.), a metal catalyst; and SH-3773M (0.09 parts by mass, manufactured by Dow Chemical Japan Ltd.), a polyether-modified silicone compound, were dissolved in xylylene diisocyanate (90 parts by mass), a polyisocyanate compound. The mixture was then filtered through a 3 μm PTFE filter and degassed under vacuum while stirring for 30 to 60 minutes to obtain the first composition (MB2). The obtained first composition (MB2) was stored at 5°C for 35 days. The viscosity, measured at 20°C, remained stable at 9 cP from the beginning of storage until 35 days later. Furthermore, when the first composition (MB2) was stored at room temperature, after 5 days of storage, the composition (MB2) was a pale yellow, transparent liquid, and no precipitate due to polymerization was observed.

[0143] Ten parts by mass of the first composition (MB2), which had been stored at 5°C for 35 days, was added to the second composition, a polythiol composition (9.56 parts by mass) mainly composed of 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiandecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiandecane, and 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and the mixture was stirred for a further 30 minutes. The mixture was then filtered through a 3 μm PTFE filter and degassed under vacuum while stirring for 30 to 60 minutes to obtain a mixture of the first and second compositions.

[0144] The resulting mixture was poured between a pair of flat glass molds fixed at a distance of 0.8 mm. Then, it was subjected to a 30-second (9 mW / cm²) exposure. 2The mixture was polymerized and cured by irradiation with light (365 nm) at 1 / s and then heating in a 120°C oven for 1 hour. The resulting cured product had a refractive index of 1.67 and possessed transparency suitable for optical components.

[0145] <Example 5> Tetrabutylammonium tri(1-naphthyl)butylborate (0.546 parts by mass, manufactured by Showa Denko K.K.), a base generator; 10-camphor sulfonic acid (0.018 parts by mass, manufactured by Tokyo Chemical Industry Co., Ltd.), a stabilizer; dimethyltin(IV) dichloride (0.009 parts by mass, manufactured by Tokyo Chemical Industry Co., Ltd.), a metal catalyst; and triphenyl phosphite (0.546 parts by mass, manufactured by Tokyo Chemical Industry Co., Ltd.), a stabilizer, were dissolved in xylylene diisocyanate (9 parts by mass), a polyisocyanate compound. After complete dissolution, a polythiol composition (90 parts by mass) mainly consisting of the polythiol compounds 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiandecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiandecane, and 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane was added, and the mixture was stirred for a further 30 minutes. The mixture was then filtered through a 3 μm PTFE filter, and degassed under vacuum while stirring for 30 to 60 minutes to obtain the first composition (MB3). The viscosity of the first composition (MB3) measured at 20°C after being stored at room temperature for 6 weeks was 3600 cP, indicating that it was in good condition. Furthermore, the yellow index (measured in a 10 mm thick cell) measured after 6 weeks of storage was also stable and below 0.5.

[0146] The first composition (MB3) (40 parts by mass), which had been stored at 5°C for 40 days, was mixed with the second composition, which contained xylylene diisocyanate (36.96 parts by mass), SH-3773M (0.04 parts by mass, manufactured by Dow Chemical Japan Ltd.), a polyether-modified silicone compound, and Hostavin PR-25 (0.144 parts by mass, manufactured by Clariant), an ultraviolet absorber, and stirred for 30 minutes. The viscosity measured at 20°C at this time was 39 cP. Subsequently, the mixture was filtered through a 3 μm PTFE filter and degassed under vacuum while stirring for 30 to 60 minutes to obtain a mixture of the first and second compositions. The resulting mixture was poured between a pair of flat glass molds fixed at a distance of 0.8 mm. Then, it was subjected to a 60-second (9 mW / cm²) exposure. 2 The mixture was polymerized and cured by irradiation with light (365 nm) at 1 / s and then heating in a 120°C oven for 1 hour. The resulting cured product had a refractive index of 1.67 and possessed transparency suitable for optical components. The cured product obtained in the same manner as above, except that the first composition (MB3) stored at room temperature for 40 days was used instead of the first composition (MB3) stored at 5°C for 40 days, also had a refractive index of 1.67 and possessed transparency suitable for optical components.

[0147] <Example 6> Tetrabutylammonium tri(1-naphthyl)butylborate (0.784 parts by mass, manufactured by Showa Denko K.K.), a base-generating agent, was dissolved in a mixture of the polyisocyanate compounds 2,5-bis(isocyanatomethyl)bicyclo[2.2.1]heptane and 2,6-bis(isocyanatomethyl)bicyclo[2.2.1]heptane (9 parts by mass, containing 2000 ppm triphenyl phosphite as a stabilizer). After complete dissolution, a polythiol composition mainly composed of the polythiol compound 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (90 parts by mass) was added and stirred for 30 minutes. The mixture was then filtered through a 3 μm PTFE filter and degassed under vacuum while stirring for 30 to 60 minutes to obtain the first composition (MB4). The viscosity of the first composition (MB3) measured at 20°C after being stored at room temperature for 6 weeks was 247 cP, indicating that it was in good condition. Furthermore, the yellow index (measured in a 10 mm thick cell) measured after 6 weeks of storage was also stable and below 0.5.

[0148] 40 parts by mass of the first composition (MB4), which had been stored at 5°C for 40 days, was mixed with a second composition containing a mixture of the polyisocyanate compounds 2,5-bis(isocyanatomethyl)bicyclo[2.2.1]heptane and 2,6-bis(isocyanatomethyl)bicyclo[2.2.1]heptane (42.96 parts by mass), the polyether-modified silicone compound KF-351A (0.08 parts by mass, manufactured by Shin-Etsu Chemical Co., Ltd.), and the ultraviolet absorber Hostavin PR-25 (0.16 parts by mass, manufactured by Clariant), and stirred for 30 minutes. The viscosity measured at 20°C was 32 cP. Subsequently, the mixture was filtered through a 3 μm PTFE filter and degassed under vacuum while stirring for 30 minutes to obtain a mixture of the first and second compositions.

[0149] The resulting mixture was poured between a pair of flat glass molds fixed at an interval of 9 mW / cm². Then, it was subjected to a 30-second burst (9 mW / cm²). 2 The mixture was polymerized and cured by irradiation with light (365 nm) at 1 / s and then heating in a 120°C oven for 1 hour. The resulting cured product had a refractive index of 1.62 and possessed transparency suitable for optical components. The cured product obtained in the same manner as above, except that the first composition (MB4) stored at room temperature for 40 days was used instead of the first composition (MB4) stored at 5°C for 40 days, also had a refractive index of 1.62 and possessed transparency suitable for optical components.

[0150] <Example 7> A layer of polyurethane aqueous dispersion (SF-470, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was formed on one side of a glass wafer (soda glass, 100 mm in diameter, 0.5 mm thick) by spin coating. This layer was dried at 80°C for 30 seconds and cured at 100°C for 2 hours to form a thin film. The mixture obtained in Example 5 was placed on top of this thin film, and a flat glass mold was placed on top of that. The distance between the glass wafer and the glass mold was adjusted to approximately 0.45 mm. Then, a saturation test was performed for 60 seconds (1.5 mW / cm²). 2 After irradiation with light (365 nm) at 1 / s, the mixture was heated in a 120°C oven for 1 hour to polymerize and cure. Subsequently, the laminate, in which layers consisting of a glass wafer, a thin film made of SF-470, and a cured mixture were arranged in this order, was peeled from the glass mold and subjected to annealing at 120°C for 1 hour. The thickness of the layer consisting of the cured mixture was 0.4 mm and it had transparency suitable for optical components. The laminate shown in Example 7 can be suitably used in products such as head-mounted displays and microlenses used in AR / VR technology.

[0151] <Example 8> The mixture obtained in Example 6 was placed on a curved glass mold having a microlens pattern. Next, the surface of the curved lens substrate (MR-10 resin) was subjected to alkali treatment or plasma treatment, and the treated surface was pressed onto the mixture on the glass mold to spread the mixture between the glass mold and the lens substrate. Then, for 60 seconds (9.5 mW / cm²), 2 After irradiation with light (365 nm) at 1 / s, the mixture was heated in a 90°C oven for 30 minutes to polymerize and cure. Subsequently, the laminate, consisting of the lens substrate and the cured layer of the composition, was peeled from the glass mold and annealed at 120°C for 1 hour. A microlens pattern was transferred to the cured layer of the resulting laminate. The transferability of the pattern was analyzed by laser microscopy and interferometer spectroscopy. The thickness of the cured layer was approximately 10 μm, and it possessed transparency suitable for optical components. A laminate having a microlens pattern as shown in Example 8 can be suitably used in products such as eyeglasses with microlenses for myopia correction.

[0152] <Example 9> Tetrabutylammonium tri(1-naphthyl)butylborate (2.5 parts by mass, manufactured by Showa Denko K.K.), a base generator; 10-camphor sulfonic acid (0.06 parts by mass, manufactured by Tokyo Chemical Industry Co., Ltd.), a stabilizer; dimethyltin(IV) dichloride (0.03 parts by mass, manufactured by Tokyo Chemical Industry Co., Ltd.), a metal catalyst; and triphenyl phosphite (1.88 parts by mass, manufactured by Tokyo Chemical Industry Co., Ltd.), a stabilizer, were dissolved in xylylene diisocyanate (30 parts by mass), a polyisocyanate compound. After complete dissolution, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (300 parts by mass), a polythiol compound, was added, and the mixture was stirred for a further 2 hours to obtain the first composition (MB5). The first composition (MB5) was then stored in a glass container at room temperature. Meanwhile, KF-640 (1.9 parts by mass, manufactured by Shin-Etsu Chemical Co., Ltd.), a polyether-modified silicone compound, and Hostavin PR-25 (1.27 parts by mass, manufactured by Clariant), an ultraviolet absorber, were dissolved in xylylene diisocyanate (300 parts by mass), a polyisocyanate compound, and stirred for 2 hours to obtain a second composition. The second composition was then placed in a glass container and stored at room temperature.

[0153] The first and second compositions were filtered through a 3 μm PTFE filter, degassed under vacuum while stirring for 30 minutes, and then filled into the tanks of a dispenser (Dual Mixer MRP-150, manufactured by Nippon Sosei Kogyo Co., Ltd.) equipped with a function to mix the two liquids. The filled first and second compositions were mixed in the dispenser, and immediately thereafter the mixture was poured between a pair of glass molds placed 2 mm apart. The mixture was then subjected to aeration for 30 seconds (9 mW / cm²). 2After irradiation with light (365 nm) at 1 / s, the mixture was polymerized and cured by heating in a 120°C oven for 1 hour. The resulting cured product had a refractive index of 1.67 and possessed transparency suitable for optical components. From these results, it was found that the composition kit containing the first composition and the second composition can be suitably used for the production of cured products using a two-component dispenser.

[0154] The disclosure of Japanese Patent Application No. 2023-041165 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 as being incorporated by reference.

Claims

1. Base generator (a), A polymerizable compound comprising at least one selected from the group consisting of polyiso(thio)cyanate compounds (b1) and polythiol compounds (c1), It contains a stabilizer (S), A composition wherein the stabilizer (S) comprises at least one selected from the group consisting of sulfonic acid and phosphite ester compounds having a pKa of 0.2 or more and less than 2.

0.

2. The composition according to claim 1, wherein the polymerizable compound comprises a polyiso(thio)cyanate compound (b1) and a polythiol compound (c1).

3. The composition according to claim 2, wherein the mass ratio (b1 / c1) of the polyiso(thio)cyanate compound (b1) to the polythiol compound (c1) contained in the polymerizable compound is 99 / 1 to 1 / 99.

4. The composition according to claim 2, comprising a thiourethane compound which is a reaction product of the polyiso(thio)cyanate compound (b1) and the polythiol compound (c1).

5. The composition according to claim 1, wherein the polyiso(thio)cyanate compound (b1) comprises at least one selected from the group consisting of pentamethylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, bis(isocyanatomethyl)cyclohexane, bis(isocyanatocyclohexyl)methane, 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and phenylene diisocyanate.

6. The polythiol compound (c1) is 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(2-mercaptoacetate), 2,5-bis(mercapto The composition according to claim 1, comprising at least one selected from the group consisting of (ptomethyl)-1,4-dithiane, bis(2-mercaptoethyl) sulfide, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 4,6-bis(mercaptomethylthio)-1,3-dithiane, 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithiethane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 3-mercaptomethyl-1,5-dimercapto-2,4-dithiapentane, and tris(mercaptomethylthio)methane.

7. The composition according to claim 1, wherein the base generating agent (a) comprises at least one selected from the group consisting of compounds represented by the following formulas (1) to (4). 【Chemistry 1】 In formula (1), R １ ~R ４ Each of these independently represents an alkyl group having 1 to 8 carbon atoms, R ５ ~R ８ Each of these independently represents an alkyl group having 1 to 8 carbon atoms, a phenyl group, a naphthyl group, an anthracenyl group, or a phenanthyl group. In formula (2), R １ ~R ７ Each of these independently represents an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 3 to 8 carbon atoms, R ８ ~R １１ Each of these independently represents an alkyl group having 1 to 8 carbon atoms, a phenyl group, a naphthyl group, an anthracenyl group, or a phenanthyl group. In formula (3), n represents an integer of 1 to 3, and R １ ~R ４ each independently represents an alkyl group having 1 to 8 carbon atoms, a phenyl group, a naphthyl group, an anthracenyl group or a phenanthryl group, In formula (4), R １ ~R ４ Each of these independently represents an alkyl group having 1 to 8 carbon atoms, a phenyl group, a naphthyl group, an anthracenyl group, or a phenanthyl group. In formulas (1) to (4), the phenyl group, the naphthyl group, the anthracenyl group, and the phenanthrill group may be substituted with a halogen atom, an alkyl group, an aryl group, an alkenyl group, a cycloalkyl group, or a heterocyclic group.

8. The composition according to claim 1, further comprising a tin-containing metal catalyst, wherein the content of the tin-containing metal catalyst is 0.001 parts by mass to 0.05 parts by mass when the total mass of the polymerizable compound is 100 parts by mass.

9. The composition according to claim 1, further comprising an ultraviolet absorber (e).

10. The composition according to claim 1, further comprising a polyether-modified silicone compound (d).

11. A first composition which is the composition described in any one of claims 1 to 10, It consists of a polyiso(thio)cyanate compound (b2) and a polythiol compound (c2). A second composition comprising a polymerizable compound containing at least one selected from the group, A composition kit containing the following:

12. The composition kit according to claim 11, wherein the second composition comprises only one of a polyiso(thio)cyanate compound (b2) or a polythiol compound (c2).

13. A cured product of a mixture of the first composition and the second composition contained in the composition kit according to claim 11.

14. The cured product according to claim 13, wherein the refractive index is 1.50 to 1.

80.

15. A laminate comprising the cured product described in claim 13 and a substrate.

16. The laminate according to claim 15, further comprising a functional film.

17. The laminate according to claim 16, wherein the functional film includes at least one selected from the group consisting of a polarizing film, a phase difference film, a gas barrier film, a conductive film, an insulating film, and an optical guide film.

18. The laminate according to claim 16, wherein the cured product and at least a portion of the functional film are in direct contact.

19. To obtain a mixture of the first composition and the second composition contained in the composition kit described in claim 11, Irradiating the mixture with ultraviolet light or visible light, A method for producing a cured product containing [the specified ingredient].

20. The method for producing a cured product according to claim 19, wherein the mixture is obtained using a two-component dispenser.

21. A method for producing a cured product according to claim 19, comprising storing the composition kit at room temperature.

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