Composition, cured product, method for producing cured product, compound, and base generator

Abstract

Provided is a composition which contains a base generator and a polymerizable compound. The base generator contains a salt of a cation and an anion. The cation contains a carbonyl group and a partial structure comprising: a carbon atom; a nitrogen atom N1 bonded via a single bond to the carbon atom; and a nitrogen atom N2 bonded via a double bond to the carbon atom. The polymerizable compound contains a polyiso(thio)cyanate compound and a polythiol compound.

Description

Composition, cured product, method for producing cured product, compound, and base generator

[0001] The present disclosure relates to a composition, a cured product, a method for producing the cured product, a compound, and a base generator.

[0002] High-refractive-index plastic materials are increasingly being used as optical components such as eyeglass lenses because they are lighter and less likely to break than inorganic materials such as glass, can be dyed, etc. Examples of plastic materials for optical components include acrylic resins, polycarbonates, and thiourethane resins, and among these, thiourethane resins are known as plastic materials that can achieve a high refractive index (see, for example, Patent Document 1).

[0003] Products made from thiourethane resins are generally produced by a cast polymerization method, in which a composition containing raw materials for the thiourethane resin is poured between a pair of molds spaced a predetermined distance apart, and the composition is cured by heating to obtain a cured product.

[0004] Japanese Patent Application Laid-Open No. 2019-15922

[0005] In conventional methods for producing thiourethane resins, a composition containing raw materials for the thiourethane resin is cured solely by heating. As a result, it takes a long time to produce a cured product. One possible method for shortening the time required to produce a cured product is to add a component that imparts photocurability to the composition and combine a curing process by light irradiation with a curing process by heating. However, adding a component that imparts photocurability to the composition may make it more likely for a polymerization reaction to occur before the composition is cured, potentially reducing pot life. It is an object of one aspect of the present disclosure to provide a composition that exhibits photocurability and has an excellent pot life, a cured product of this composition, and a method for producing a cured product using this composition. It is an object of another aspect of the present disclosure to provide a novel compound and base generator.

[0006] The means for solving the above problems include the following aspects: <1> A polymerizable compound including a base generator and a polymerizable compound, wherein the base generator includes a salt of a cation and an anion, and the cation is a carbon atom and a nitrogen atom N bonded to the carbon atom by a single bond.１ and a nitrogen atom N bonded to the carbon atom by a double bond. ２ and a carbonyl group, wherein the polymerizable compound comprises a polyiso(thio)cyanate compound and a polythiol compound. １ The composition according to <1>, wherein the cation has a structure represented by the following formula (1), n ​​is an integer of 1 to 3, and R is a monovalent organic group containing a carbonyl group: <5> The composition according to any one of <1> to <4>, wherein the anion is a borate anion. <6> The composition according to <5>, wherein the borate anion has a structure in which three aromatic hydrocarbon groups and one aliphatic hydrocarbon group are bonded to a boron atom. <7> The composition according to any one of <1> to <6>, wherein the content of the base generator is 0.1 parts by mass to 2.0 parts by mass, relative to 100 parts by mass of the total mass of the polymerizable compounds. <8> The composition according to any one of <1> to <7>, further comprising a stabilizer. <9> The composition according to <8>, wherein the stabilizer comprises at least one of a phosphite ester compound and an acid having a pKa of -1.0 or more and less than 2.0. <10> The composition according to <8>, wherein the stabilizer comprises a phosphite ester compound and an acid having a pKa of less than 2.0. <11> The composition according to any one of <1> to <10>, further comprising a tin-containing metal catalyst, wherein the content of the tin-containing metal catalyst is 0.001 to 0.05 parts by mass relative to 100 parts by mass of the total mass of the polymerizable compounds. <12> The composition according to any one of <1> to <11>, wherein a ratio (A / B) of the mass A of the polyiso(thio)cyanate compound to the mass B of the polythiol compound is 99 / 1 to 1 / 99. <13> The composition according to any one of <1> to <12>, wherein the polyiso(thio)cyanate compound includes 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.<14> The polythiol compound 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(mercaptomethyl 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithiane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 3-mercaptomethyl-1,5-dimercapto-2,4-dithiapentane, and tris(mercaptomethylthio)methane. <15> The composition according to any one of <1> to <14>, which is used in a method for producing a cured product, the method including irradiating the product with light having a wavelength of 340 nm to 500 nm. <16> A cured product of the composition according to any one of <1> to <14>. <17> A method for producing a cured product, comprising a curing step of curing the composition according to any one of <1> to <14>, wherein the curing step comprises irradiating the composition with light having a wavelength of 340 nm to 500 nm. <18> A method for producing a cured product according to <17>, wherein the irradiation with light having a wavelength of 340 nm to 500 nm is performed using an LED. <19> A method for producing a cured product according to <17> or <18>, wherein the curing step further comprises heating the composition. <20> A method for producing a cured product according to any one of <17> to <19>, further comprising a viscosity adjusting step of adjusting the viscosity of the composition before the curing step. <21> A compound which is a salt of a cation and an anion, wherein the cation has a structure represented by the following formula (1), wherein n is an integer of 1 to 3, and R is a monovalent organic group containing a carbonyl group. <22> A base generator containing the compound according to <21>.

[0007] According to one aspect of the present disclosure, there are provided a composition that exhibits photocurability and has an excellent pot life, a cured product of the composition, and a method for producing a cured product using the composition. According to another aspect of the present disclosure, there are provided a novel compound and a base generator.

[0008] In the present disclosure, a numerical range expressed using "to" means a range that includes the numerical values ​​written before and after "to" as the lower and upper limits. In the present disclosure, when a composition contains multiple substances corresponding to each component, the amount of each component refers to the total amount of the multiple substances present in the composition, unless otherwise specified. In the numerical ranges described in stages in the present disclosure, the upper or lower limit described in one numerical range may be replaced with the upper or lower limit of another numerical range described in stages. Furthermore, in the numerical ranges described in the present disclosure, the upper or lower limit of that numerical range may be replaced with a value shown in the examples.

[0009] [Composition] The composition of the present disclosure includes a base generator and a polymerizable compound, wherein the base generator includes a salt of a cation and an anion, and the cation has a carbon atom and a nitrogen atom N bonded to the carbon atom by a single bond. １ and a nitrogen atom N bonded to the carbon atom by a double bond. ２ and a carbonyl group, and the polymerizable compound includes a polyiso(thio)cyanate compound and a polythiol compound.

[0010] The composition of the present disclosure contains a polyiso(thio)cyanate compound and a polythiol compound as polymerizable compounds. That is, the composition of the present disclosure is used to form a cured product (i.e., a thiourethane resin) obtained by a polymerization reaction between the polyiso(thio)cyanate compound and the polythiol compound. The thiourethane resin is suitable for use in applications requiring a high refractive index, such as optical components.

[0011] Furthermore, the composition of the present disclosure contains a base generator. Conventional thiourethane resins are produced by heating to cause a polymerization reaction between a polyiso(thio)cyanate compound and a polythiol compound. The composition of the present disclosure exhibits photocurability due to the inclusion of a base generator. Therefore, at least a portion of the polymerization reaction between the polyiso(thio)cyanate compound and the polythiol compound can be caused by light irradiation. In other words, the composition of the present disclosure can shorten the time required for curing compared to conventional compositions that are cured only by heating.

[0012] Furthermore, the composition of the present disclosure contains a salt of a cation and an anion as a base generator, and the cation has a carbon atom and a nitrogen atom N bonded to the carbon atom by a single bond. １ and a nitrogen atom N bonded to the carbon atom by a double bond. ２ The composition of the present disclosure includes a partial structure (hereinafter also referred to as a specific partial structure) consisting of the following: and a carbonyl group. As shown in the examples described below, a composition containing a salt of a cation containing the specific partial structure and a carbonyl group and an anion as a base generator exhibits photocurability and has an excellent pot life. The components contained in the composition of the present disclosure will be described below.

[0013] <Base Generator> The composition of the present disclosure contains a base generator. In the present disclosure, the term "base generator" refers to a compound that liberates a base by at least one of light energy such as electromagnetic waves and thermal energy. The composition of the present disclosure contains, as a base generator, a salt of an anion and a cation having a specific partial structure and a carbonyl group (hereinafter also referred to as a specific base generator).

[0014] The specific base generator is a so-called photobase generator that has the property of liberating a base upon irradiation with light. The mechanism by which the specific base generator liberates a base upon irradiation with light is thought to be, for example, as follows: When the specific base generator is irradiated with light, a radical is generated at the carbonyl group of the cation. Next, a radical containing a specific partial structure is generated by radical cleavage. Next, one electron is donated from the anion to the radical containing the specific partial structure, converting it into a base containing the specific partial structure. This base acts on a polymerizable compound to initiate a polymerization reaction.

[0015] The structure of the cation of the specific base generator is not particularly limited as long as it contains a specific partial structure and a carbonyl group. １ ) ｎ -C=N ２ In formula (2), n represents a nitrogen atom N bonded to a carbon atom by a single bond. １ represents the number of nitrogen atoms bonded by a single bond, and is 1 or 2. １ When the number of is 1, the specific base generator has an aminidium ion as a cation and liberates amidine as a base. １ When the number of is 2, the specific base generator has a guanidinium ion as a cation and liberates guanidine as a base.

[0016] The positional relationship between the specific partial structure in the cation and the carbonyl group is not particularly limited. １ (Nitrogen atom N １ When the number of nitrogen atoms is two, at least one of the nitrogen atoms N １ ) and this monovalent organic group preferably contains a carbonyl group. １ The number of carbon atoms in the monovalent organic group bonded to is not particularly limited, but may be 3 or more, 5 or more, or 8 or more. １ The number of carbon atoms in the monovalent organic group bonded to is not particularly limited, but may be 30 or less, 20 or less, or 15 or less.

[0017] Nitrogen atom N １ When the monovalent organic group bonded to the carbonyl group (C═O) contains a carbonyl group, the carbon atom in the carbonyl group (C═O) is １ is preferably bonded to via an alkylene group having 1 to 5 carbon atoms, more preferably via an alkylene group having 1 to 3 carbon atoms, and even more preferably via a methylene group.

[0018] Nitrogen atom N １When the monovalent organic group bonded to the carbonyl group contains a carbonyl group, it is preferable that the monovalent organic group further contains an aromatic ring. The aromatic ring is preferably bonded to a carbon atom in the carbonyl group via a single bond or an alkylene group having 1 to 5 carbon atoms, more preferably bonded to a carbon atom in the carbonyl group via a single bond or an alkylene group having 1 to 3 carbon atoms, and even more preferably bonded to a carbon atom in the carbonyl group via a single bond. Specific examples of the aromatic ring contained in the monovalent organic group include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring, with a benzene ring or a naphthalene ring being preferred.

[0019] Nitrogen atom N １ When the monovalent organic group bonded to contains an aromatic ring, the aromatic ring may or may not have a substituent. Examples of the substituent include an alkyl group having 1 to 18 carbon atoms, an aryl group, an alkenyl group having 3 to 18 carbon atoms, an alkynyl group having 3 to 18 carbon atoms, a haloalkyl group having 1 to 18 carbon atoms, -NO ２ , -OH, -CN, a halogen atom, -OR, -SR, -C(=O)R, -C(=O)OR, and combinations of these substituents. R in the above-mentioned substituents is an alkyl group or an aryl group having 1 to 18 carbon atoms. Examples of the aryl group include a phenyl group, a naphthyl group, an anthracenyl group, and a phenanthryl group.

[0020] Nitrogen atom N １ The monovalent organic group bonded to the above and containing a carbonyl group may be a monovalent organic group represented by the following formula (3-1) or (3-2):

[0021]

[0022] In formula (3-1) and formula (3-2), X represents a substituent, and n is a number from 0 to 5. * represents a nitrogen atom N １represents a bonding site with. The substituent represented by X can be selected from the examples of substituents that the aromatic ring may have described above. The substituent represented by X is preferably an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or an aryl group, and more preferably a methyl group, a methoxy group, or a phenyl group. When the number of X is 2 or more, the two or more Xs may be the same or different. n is preferably 0 to 2, and more preferably 0 or 1.

[0023] The cation of the specific base generator may have a cyclic structure or may have a structure represented by the following formula (1).

[0024]

[0025] In formula (1), R is a monovalent organic group containing a carbonyl group. Details of the monovalent organic group containing a carbonyl group represented by R are as follows: １ The details of the monovalent organic group bonded to formula (1) are the same as those of the monovalent organic group bonded to formula (1). In formula (1), n ​​is an integer of 1 to 3, and is preferably 1 or 3. A cation in which n is 1 in formula (1) is shown in formula (1-1) below, and a cation in which n is 3 in formula (1) is shown in formula (1-2) below.

[0026]

[0027] The specific base generator containing the cation represented by formula (1-1) liberates diazabicyclononene (DBN) as a base. The specific base generator containing the cation represented by formula (1-2) liberates diazabicycloundecene (DBU) as a base.

[0028] The type of anion of the specific base generator is not particularly limited. From the viewpoint of imparting hydrophobicity to the specific base generator, the anion may be a borate anion, a hexafluorophosphate anion (PF ６ － ), tetrafluoroborate anion (BF ４ － ) and other hydrophobic anions are preferred.

[0029] The anion of the specific base generator may be a borate anion having a structure represented by the following formula (4).

[0030] In formula (4), R １ ~R ４ each independently represents a monovalent organic group. Specific examples of the monovalent organic group include alkyl groups or aryl groups having 1 to 8 carbon atoms. Specific examples of the aryl group include a phenyl group, a naphthyl group, an anthracenyl group, and a phenanthryl group. The aryl group may or may not have a substituent. Specific examples of the substituent include a halogen atom, an alkyl group, an aryl group, an alkenyl group, a cycloalkyl group, and a heterocyclic group.

[0031] The anion of the specific base generator may be a borate anion having a structure in which three aromatic hydrocarbon groups and one aliphatic hydrocarbon group are bonded to a boron atom. For example, the ... represented by the formula (4) １ ~R ３ is an aryl group, and R ４ may be a borate anion in which R is an alkyl group. １ ~R ３ The aryl group represented by R is 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, and even more preferably a phenyl group. １ ~R ３ The aryl groups represented by R may be the same or different, and are preferably the same. ４ 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. That is, the anion of the specific base generator is preferably a triphenylalkylborate anion, and more preferably a triphenyl(n-butyl)borate anion.

[0032] The composition of the present disclosure may contain only a specific base generator as a base generator, or may contain the specific base generator and a base generator other than the specific base generator as a base generator. When the composition of the present disclosure contains the specific base generator and a base generator other than the specific base generator as a base generator, the proportion of the specific base generator in the base generators is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more. The type of base generator other than the specific base generator is not particularly limited and can be selected from known base generators.

[0033] From the viewpoint of promoting the polymerization reaction of the polymerizable compounds, the content of the base generator contained in the composition is preferably 0.1 parts by mass or more, more preferably 0.15 parts by mass or more, and even more preferably 0.2 parts by mass or more, relative to 100 parts by mass of the total mass of the polymerizable compounds. From the viewpoint of the pot life of the composition, the content of the base generator contained in the composition is preferably 2.0 parts by mass or less, more preferably 1.5 parts by mass or less, and even more preferably 1.0 part by mass or less, relative to 100 parts by mass of the total mass of the polymerizable compounds.

[0034] The specific base generator preferably exhibits reactivity to ultraviolet light, more preferably exhibits reactivity to light with a wavelength of 340 nm to 500 nm, further preferably exhibits reactivity to light with a wavelength of 365 nm to 450 nm, and particularly preferably exhibits reactivity to light with a wavelength of 365 nm to 410 nm.

[0035] <Polymerizable Compound> The composition of the present disclosure contains a polymerizable compound. The polymerizable compound contains at least a polyiso(thio)cyanate compound and a polythiol compound, and may contain other polymerizable compounds as needed.

[0036] (Polyiso(thio)cyanate Compound) In the present disclosure, a polyiso(thio)cyanate compound refers to a compound having two or more isocyanate groups or isothiocyanate groups in one molecule. The type of polyiso(thio)cyanate compound contained in the composition is not particularly limited and can be selected depending on the application of the cured product of the composition, etc. The polyiso(thio)cyanate compound contained in the composition may be one type or two or more types.

[0037] The polyiso(thio)cyanate compound may be either a non-aromatic polyiso(thio)cyanate compound or an aromatic polyiso(thio)cyanate compound. In the present disclosure, an aromatic polyiso(thio)cyanate compound refers to a polyiso(thio)cyanate compound containing an aromatic ring, and a non-aromatic polyiso(thio)cyanate compound refers to a polyiso(thio)cyanate compound not containing an aromatic ring. The aromatic ring may be an aromatic ring consisting only of carbon atoms and hydrogen atoms, or a heterocyclic ring consisting of carbon atoms, hydrogen atoms, and heteroatoms.

[0038] The polyiso(thio)cyanate compound (b) is preferably a compound having 2 to 4 isocyanate groups or isothiocyanate groups, more preferably 2 or 3 isocyanate groups or isothiocyanate groups, and even more preferably 2 isocyanate groups or isothiocyanate groups.

[0039] From the viewpoint of excellent adhesiveness and refractive index of the cured product, and excellent photocurability, the polyiso(thio)cyanate compound preferably includes 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 that the compound contains 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, and it is even more preferable that the compound contains 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.

[0040] The polyiso(thio)cyanate compound may include a dimer, a trimer, or a prepolymer. Examples of these polyiso(thio)cyanate compounds include the compounds exemplified in WO 2011 / 055540.

[0041] (Polythiol Compound) In the present disclosure, a polythiol compound refers to a compound having two or more thiol groups in one molecule. The type of polythiol compound contained in the composition is not particularly limited and can be selected depending on the application of the cured product of the composition. The polythiol compound contained in the composition may be one type or two or more types.

[0042] The polythiol compound is preferably a compound having 2 to 8 thiol groups, more preferably a compound having 2 to 6 thiol groups, and even more preferably a compound having 2 to 4 thiol groups.

[0043] Specific examples of the polythiol compound include the compounds exemplified in WO 2016 / 125736.

[0044] From the viewpoint of excellent photocurability, the polythiol compound may be 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(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-dithietane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 3-mercaptomethyl-1,5-dimercapto-2,4-dithiapentane, and tris(mercaptomethylthio)methane, more preferably, the mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane is 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 tetrakis(3-mercaptopropionate), and pentaerythritol tetrakis(2-mercaptoacetate); It is more preferable that the mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane be 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.

[0045] From the viewpoint of the refractive index of the cured product to be obtained, the polythiol compound preferably has a refractive index at 20° C. of 1.60 to 1.80 for sodium D lines (that is, light with a wavelength of 589.3 nm).

[0046] (Other Polymerizable Compounds) If necessary, the composition of the present disclosure may contain a polymerizable compound other than a polyiso(thio)cyanate compound and a polythiol compound. For example, the composition may contain a polyepisulfide compound as a polymerizable compound. In the present disclosure, a polyepisulfide compound means a compound having two or more episulfide groups in one molecule.

[0047] The polyepisulfide compound includes a compound represented by the following formula (5).

[0048]

[0049] In formula (5), Y represents a divalent organic group, m represents an integer of 0 to 2, and n represents an integer of 0 to 3. Examples of the divalent organic group represented by Y include a linear 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, and an aralkylene group. Y may contain a substituent or may be unsubstituted.

[0050] The divalent organic group represented by Y is preferably 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 is preferably 0 or 1, and more preferably 0. n is preferably 0 or 1, and more preferably 1.

[0051] The polyepisulfide 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.

[0052] From the viewpoint of the refractive index of the cured product to be obtained, the polyepisulfide compound preferably has a refractive index at 20° C. of 1.60 to 1.80 for sodium D lines (that is, light with a wavelength of 589.3 nm).

[0053] When the composition contains polymerizable compounds other than a polyiso(thio)cyanate compound and a polythiol compound, the total content of the polyiso(thio)cyanate compound and the polythiol compound is preferably 50 mass% or more, more preferably 70 mass% or more, and even more preferably 80 mass% or more of the total polymerizable compounds.

[0054] The ratio (A / B) of the mass A of the polyiso(thio)cyanate compound to the mass B of the polythiol compound contained in the composition is not particularly limited and can be selected from the range of 99 / 1 to 1 / 99. The range may be 80 / 20 to 20 / 80, 70 / 30 to 30 / 70, or 60 / 40 to 40 / 60.

[0055] When the composition contains a polyiso(thio)cyanate compound and a polythiol compound as polymerizable compounds, the polyiso(thio)cyanate compound and the polythiol compound may partially react in the composition to produce a thiourethane compound. That is, the composition may contain a thiourethane compound that is a reaction product of the polyiso(thio)cyanate compound and the polythiol compound.

[0056] From the viewpoints of photocurability and the adhesion and bonding properties of the cured product, the total content of the polymerizable compounds contained 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, relative to the total mass of the composition. The total content of the polymerizable compounds contained in the composition may be 99.9% by mass or less, or may be 99.8% by mass or less, relative to the total mass of the composition.

[0057] <Stabilizer> The composition of the present disclosure may contain a stabilizer. When the composition of the present disclosure contains a stabilizer, the polymerization reaction of the polymerizable compound during storage can be more effectively suppressed.

[0058] Preferred examples of the stabilizer include an acid having a pKa of less than 2.0, an anhydride of an acid having a pKa of less than 2.0, and a phosphite ester. The stabilizer contained in the composition may be one type or two or more types.

[0059] Specific examples of acids having 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 having a pKa of less than 2.0. From the viewpoint of the pot life of the composition, sulfonic acids having a pKa of less than 2.0 are preferred. Specific examples of sulfonic acids having a pKa of less than 2.0 include 10-camphorsulfonic acid (pKa: 1.2), methanesulfonic acid (pKa: -2.6), paratoluenesulfonic acid (pKa: -2.8), vinylsulfonic acid (pKa: -2.7), and benzenesulfonic acid (pKa: 0.7). Acids having a pKa of less than 2.0 may form hydrates. The pKa of an acid having a pKa of less than 2.0 may be 1.8 or less, 1.5 or less, or 1.2 or less. Acids having a pKa of less than 2.0 may have a pKa of -1.0 or greater, 0.0 or greater, 0.2 or greater, 0.5 or greater, or 1.0 or greater.

[0060] Examples of the anhydride of an acid having a pKa of less than 2.0 include the anhydrides of the acids described above. From the viewpoint of the pot life of the composition, anhydrides of sulfonic acids having a pKa of less than 2.0 are preferred.

[0061] Specific examples of phosphite esters include triphenyl phosphite, tris(4-methoxyphenyl)phosphite, and tris(4-methylphenyl)phosphite. Triphenyl phosphite is preferred from the viewpoint of suppressing self-polymerization of the polyiso(thio)cyanate compound in the presence of a base generator. The composition may contain at least one of a phosphite ester compound and an acid having a pKa of -1.0 or more and less than 2.0 as a stabilizer. The composition may contain a phosphite ester compound and an acid having a pKa of less than 2.0 as stabilizers.

[0062] From the viewpoint of pot life of the composition, the content of the stabilizer is preferably 0.001 part by mass or more, more preferably 0.005 part by mass or more, and even more preferably 0.01 part by mass or more, when the total mass of the polymerizable compounds is 100 parts by mass. From the viewpoint of polymerizability of the polymerizable compounds, the content of the stabilizer is preferably 1.0 part by mass or less, more preferably 0.5 part by mass or less, and even more preferably 0.3 part by mass or less, when the total mass of the polymerizable compounds is 100 parts by mass.

[0063] <Ultraviolet Absorber> The composition of the present disclosure may contain an ultraviolet absorber. When the composition contains an ultraviolet absorber, the weather resistance of the composition or the cured product is improved.

[0064] The ultraviolet absorber is preferably at least one selected from the group consisting of compounds represented by the following formulas (e-1) to (e-4).

[0065]

[0066] In formula (e-1), R １ represents a hydrogen atom or a chlorine atom, R ２ and R ３ each independently represents a substituted or unsubstituted linear or branched alkyl group having 1 to 12 carbon atoms, or an aromatic or heteroaromatic group having 4 to 12 carbon atoms. When the substituted or unsubstituted linear or branched alkyl group having 1 to 12 carbon atoms contains a substituent, the substituent may be an aromatic or heteroaromatic group having 6 to 12 carbon atoms. Examples of the aromatic group and heteroaromatic group include a phenyl group, a biphenyl group, a 2,3,5-trimethylphenyl group, a furyl group, and a p-methoxyphenyl group. The compound represented by formula (e-1) may be a commercially available product, and examples thereof include Tinuvin 234 (manufactured by BASF Japan Ltd.) and Tinuvin 328 (manufactured by BASF Japan Ltd.).

[0067] In formula (e-2), A １ represents a structure represented by the following formula (e-2a), and R ４ and R ５each independently represents a structure represented by the following formula (e-2b):

[0068]

[0069] In formula (e-2a) and formula (e-2b), Q １ ~Q ５ each independently represents 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 atom, or an aromatic or heteroaromatic group having 4 to 12 carbon atoms. The linear or branched alkyl group having 1 to 12 carbon atoms preferably has 1 to 6 carbon atoms, and more preferably 1 to 3 carbon atoms. Examples of linear or branched alkoxy groups having 1 to 18 carbon atoms include a methoxy group, a butoxy group, a 2-hydroxy-3-octyloxypropyloxy group, and a 2-ethylhexyloxy group. Examples of aromatic and heteroaromatic groups include a phenyl group, a biphenyl group, a 2,3,5-trimethylphenyl group, a furyl group, and a p-methoxyphenyl group. 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.).

[0070] In formula (e-3), R ６ and R ７ each independently represents 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 the linear or branched alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a butyl group, a propyl group, a pentyl group, and a hexyl group. Examples of the linear or branched alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, a butoxy group, and a phenoxy group. The compound represented by formula (e-3) may be a commercially available product, and an example thereof is Hostavin VSU (manufactured by Clariant Chemicals K.K.).

[0071] In formula (e-4), R ８represents an optionally substituted aromatic group having 6 to 20 carbon atoms or an optionally substituted alicyclic group having 5 to 20 carbon atoms. ９ and R １０ each independently represent a linear or branched alkyl group having 1 to 6 carbon atoms. Examples of optionally substituted aromatic groups having 6 to 20 carbon atoms include a phenyl group, a benzyl group, a benzoyl group, and a p-methoxybenzyl group. Examples of optionally substituted alicyclic groups having 5 to 20 carbon atoms include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclopentanyl group, and a cyclodecanyl group. When the aromatic group or alicyclic group contains a substituent, examples of the substituent include an alkyl group having 1 to 6 carbon atoms and an alkoxy group 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).

[0072] When the composition contains an ultraviolet absorber, the content thereof 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, when the total mass of the polymerizable compounds is 100 parts by mass, from the viewpoint of weather resistance of the cured product. When the composition contains an ultraviolet absorber, the content thereof is preferably 3.00 parts by mass or less, more preferably 2.00 parts by mass or less, and even more preferably 1.00 parts by mass or less, when the total mass of the polymerizable compounds is 100 parts by mass, from the viewpoint of curability of the composition.

[0073] (Metal Catalyst) The composition of the present disclosure may contain a metal catalyst. When the composition contains a metal catalyst, the polymerization of the polymerizable compound is further improved, and improvements in heat resistance, strength, hardness, adhesion, adhesiveness, etc. of the cured product can be expected.

[0074] From the viewpoint of enhancing the polymerizability, the metal catalyst preferably contains tin, zinc, bismuth, aluminum or zirconium, and more preferably contains tin.

[0075] Examples of the tin-containing metal catalyst include dibutyltin(IV) dilaurate, dibutyltin(IV) dichloride, dimethyltin(IV) dichloride, etc. Among these, dibutyltin(IV) dichloride and dimethyltin(IV) dichloride are preferred from the viewpoint of enhancing polymerization properties.

[0076] 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, relative to the total mass of the polymerizable compounds, taken as 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 compounds.

[0077] <Polyether-modified silicone compound> The composition of the present disclosure may contain a polyether-modified silicone compound. When the composition contains a polyether-modified silicone compound, the mold releasability of the cured product is improved.

[0078] From the viewpoint of releasability, the polyether-modified silicone compound preferably contains at least one selected from the group consisting of polyether-modified silicone compounds represented by the following general formula (1) and polyether-modified silicone compounds represented by the following general formula (2):

[0079]

[0080] In general formula (1), m and n each independently represent an integer of 1 or more, a and b each independently represent an integer of 0 or more (excluding the case where both a and b are 0). １ 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 (excluding the case where c, d, e, and f are all 0). R ２ and R ３each independently 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.

[0081] In the general formulas (1) and (2), (OC ３ H ６ The unit represented by the formula (O—CH(CH)) is an oxypropylene group (O—CH(CH) ３ )-CH ２ ) and Si—C ３ H ６ - (OC ２ H ４ ) C at the site represented by ３ H ６ is a trimethylene group (1,3-propanediyl group (-CH ２ CH ２ CH ２ -)).

[0082] In general formula (1), m is preferably an integer of 1 to 500, more preferably an integer of 10 to 300. n is preferably an integer of 1 to 100, more preferably an integer of 1 to 50. a is preferably an integer of 0 to 1000, more preferably an integer of 1 to 500. b is preferably an integer of 0 to 1000, more preferably an integer of 0 to 500.

[0083] The weight average molecular weight of the polyether-modified silicone compound represented by general formula (1) is preferably 200 to 100,000, and more preferably 1,000 to 80,000.

[0084] In general formula (2), p is preferably an integer of 1 to 500, more preferably an integer of 10 to 300. c and f are preferably integers of 0 to 1000, more preferably an integer of 1 to 500. d and e are preferably integers of 0 to 1000, more preferably an integer of 0 to 500.

[0085] The weight average molecular weight of the polyether-modified silicone compound represented by general formula (2) is preferably 200 to 100,000, and more preferably 1,000 to 80,000.

[0086] When the polyether-modified silicone compound contains both a polyether-modified silicone compound (d1) represented by general formula (1) and a polyether-modified silicone compound (d2) represented by general formula (2), the ratio (b1:b2) of the polyether-modified silicone compound (d1) to 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. The polyether-modified silicone compound may contain at least one type of polyether-modified silicone compound (d1) and at least one type of polyether-modified silicone compound (d2), or may contain two or more types.

[0087] When the composition contains a polyether-modified silicone compound, the content thereof 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 compounds is 100 parts by mass, from the viewpoint of the releasability of the cured product. The content of the polyether-modified silicone compound is preferably 1.00 parts 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 compounds is 100 parts by mass, from the viewpoint of the transparency of the cured product.

[0088] (Other Components) If necessary, the composition may contain components other than the above-mentioned components. For example, the composition may contain photosensitizers, compounds having epoxy groups, phenolic compounds, compounds having amino groups, inorganic compounds having sulfur atoms, inorganic compounds having selenium atoms, solvents, bluing agents, IR-cutting agents, blue light-cutting agents, reactive diluents, oil-soluble dyes, pigments, fragrances, fillers, adhesion improvers such as coupling agents, chain extenders, crosslinking agents, antifoaming agents, suspending agents, dispersants, plasticizers, anti-sagging agents, antifouling agents, preservatives, disinfectants, antibacterial agents, antifungal agents, matting agents, thickeners, pigment dispersants, anti-cising agents, scratch resistance improvers, slip agents, surface modifiers, color separation inhibitors, emulsifiers, anti-skinning agents, desiccants, antifouling agents, antistatic agents, conductive agents (electrostatic assistants), flame retardants, thermal conductivity improvers, plasticizers, silica fine particles, zirconium oxide fine particles, titanium oxide fine particles, zinc oxide fine particles, silver oxide fine particles, polyolefin fine particles, poly(meth)acrylic fine particles, polyurethane fine particles, and the like.

[0089] When the composition contains the above components, the total content thereof may be 0.1 ppm by mass to 70% by mass, 1 ppm by mass to 30% by mass, 10 ppm by mass to 10% by mass, or 0.1% by mass to 5% by mass, relative to the total mass of the composition.

[0090] [Cured Product] The cured product of the present disclosure is a cured product of the above-described composition. The cured product of the present disclosure can be obtained by irradiating the mixture with light to cause a polymerization reaction of the polymerizable compound. Therefore, the cured product of the present disclosure may have a shape that is difficult to achieve by thermal polymerization methods. The refractive index of the cured product of the present 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.

[0091] When the cured product of the present disclosure is an optical component, specific examples of the optical component include optical adhesives, coatings, optical waveguides, films, lenses, anti-reflection films, microlenses, microlens arrays, wafer-level lenses, imaging lenses for cameras (such as in-vehicle cameras, digital cameras, PC cameras, mobile phone cameras, and surveillance cameras), eyeglass lenses, light beam focusing lenses, light diffusing lenses, and camera flash lenses.

[0092] One embodiment of the cured product of the present disclosure is a laminate including the cured product of the present disclosure and a substrate. Examples of the cured product included in the laminate include a layer disposed on the surface of the substrate (e.g., a coating layer) and a layer disposed between multiple substrates (e.g., an adhesive layer). The laminate may also include an intermediate layer disposed between the substrate and the cured product. By disposing an intermediate layer between the substrate and the cured product of the present disclosure, it is possible to enhance the adhesion between the cured product and the substrate, for example. The material for the intermediate layer is not particularly limited and can be selected depending on the purpose for providing the intermediate layer. Specific examples of materials for the intermediate layer include polyurethane water dispersions and transparent adhesives.

[0093] The thickness of the cured product contained in the laminate is not particularly limited. From the viewpoint of photocurability, the thickness of the cured product 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 product is preferably 0.01 μm or more, more preferably 0.05 μm or more, and even more preferably 0.1 μm or more.

[0094] The type of substrate contained in the laminate is not particularly limited. For example, quartz, glass, optical film, ceramic material, vapor deposition film, magnetic film, reflective film, metal plate, metal foil, 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, acetyl cellulose resin, TFT array substrate, PDP electrode plate, conductive substrate such as metal (e.g., ITO), insulating substrate, silicon, silicon nitride, polysilicone, silicon oxide, semiconductor production substrate such as amorphous silicon, etc. The substrate contained in the laminate may be one type or two or more types.

[0095] If necessary, the substrate to be used for the laminate may be subjected to a pretreatment such as etching, etc. Examples of the etching method include alkaline etching in which the substrate is immersed in an alkaline aqueous solution, plasma etching in which the substrate is exposed to gas plasma such as oxygen, and UV ozone etching in which the substrate is exposed to ultraviolet light and ozone.

[0096] The laminate may include a functional film. When the laminate includes a functional film, the functional film may be disposed inside the cured product or on the surface of the cured product. The type of functional film is not particularly limited and can be selected depending on the application of the laminate. Specific examples of functional films include polarizing films and retardation films. When the laminate includes a functional film, the cured product and at least a part of the functional film may be in direct contact with each other.

[0097] [Method for Producing a Cured Product] A method for producing a cured product of the present disclosure includes a curing step of curing the composition of the present disclosure, and the curing step includes irradiating the composition with light having a wavelength of 340 nm to 500 nm.

[0098] The method for irradiating the composition with light having a wavelength of 340 nm to 500 nm is not particularly limited, and can be performed by a known method. Examples of devices for irradiating light having a wavelength of 340 nm to 500 nm include devices that use an LED (light-emitting diode), a high-pressure mercury lamp, a metal halide lamp, or the like as a light source. Among these, LEDs are preferred from the viewpoints of low energy consumption, low heat generation, resistance to resin deterioration, long life, and excellent affinity with the human body and the environment because they do not use mercury.

[0099] An example of the light irradiation conditions is an irradiation intensity of 0.1 mW / cm ２ ~1,000mW / cm ２ , the cumulative light amount is 10 mJ / cm ２ ~30,000mJ / cm ２ and the irradiation time is 0.1 to 500 seconds. The composition may be irradiated directly with light, or may be irradiated through an object (such as a mold) that is transparent to light with a wavelength of 340 to 500 nm.

[0100] From the viewpoint of enhancing the polymerizability of the polymerizable compound, the curing step may include heating the composition. Heating may be carried out simultaneously with, before, or after light irradiation. From the viewpoint of workability, heating is preferably carried out after light irradiation.

[0101] The heating conditions are not particularly limited and can be selected depending on the shape or size of the cured product, the components of the composition, etc. 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.

[0102] The method of the present disclosure may further include a viscosity adjustment step of adjusting the viscosity of the composition before the curing step. Including the viscosity adjustment step before the curing step can improve workability in the production, storage, and distribution of the composition, as well as the production of a cured product. An example of a method for adjusting the viscosity of the composition is a method in which the remaining components are added to a mixture (masterbatch) containing some of the components contained in the composition. The viscosity of the composition after the viscosity adjustment in the viscosity adjustment step is not particularly limited. For example, the viscosity at 25°C of the composition after the viscosity adjustment may be selected from the range of 100 cP to 1000 cP.

[0103] The above method may include annealing the cured product to relieve internal stress generated in the curing process. The conditions for the annealing are not particularly limited. For example, the treatment temperature may be selected from the range of 50°C to 150°C, preferably 70°C to 140°C, and more preferably 80°C to 130°C.

[0104] <Compound and Base Generator> The compound of the present disclosure is a salt of a cation having a structure represented by the following formula (1) and an anion: The base generator of the present disclosure includes the compound of the present disclosure described above.

[0105]

[0106] In formula (1), n ​​is an integer of 1 to 3, and R is a monovalent organic group containing a carbonyl group. Details and preferred embodiments of the monovalent organic group containing a carbonyl group represented by R are described in detail below with reference to the nitrogen atom N １The details and preferred embodiments of the monovalent organic group bonded to the compound of the present disclosure are the same as those of the anion of the specific base generator described above. The details and preferred embodiments of the anion in the compound of the present disclosure are the same as those of the anion of the specific base generator described above. The compound of the present disclosure can be synthesized, for example, by the synthesis method described in the examples below.

[0107] The compound of the present disclosure is useful as a base generator. The base generator is used, for example, as a raw material for a composition containing a polymerizable compound. The type of polymerizable compound is not particularly limited. For example, it may be selected from the polymerizable compounds contained in the composition of the present disclosure described above. The compound of the present disclosure has the property of liberating a base upon irradiation with light. Therefore, a composition containing the compound of the present disclosure and a polymerizable compound exhibits photocurability.

[0108] Examples of the present disclosure are shown below, but the present disclosure is not limited to the following examples. In the following examples, the viscosity of the composition is a value measured at 20°C using a Brookfield B-type 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."

[0109] <Synthesis of Base Generator> Base Generators 1 to 4 of the Examples were synthesized according to the synthesis method shown below. A solution obtained by dissolving a base compound (1 mmol) in toluene (3 mL) was stirred, and a solution obtained by dissolving a 2-halogenacetyl derivative (1 mmol) in toluene (5 mL) was added dropwise to obtain a mixed solution. This mixed solution was stirred at room temperature for 3 hours, filtered through a 3 μm PTFE filter, and the recovered material was washed with diethyl ether. The recovered material was dried under vacuum and immediately dissolved in distilled water (10 mL) to obtain an aqueous solution. Lithium triphenyl(n-butyl)borate (1 mmol, 20% by weight aqueous solution, Hokko Chemical Industry Co., Ltd.) was added to this aqueous solution with stirring to obtain a mixed solution. This mixed solution was stirred at room temperature for 1 hour, and the precipitate was filtered through a paper filter. The recovered material was washed with water. The recovered material was re-dispersed in ethanol (20 mL) at 70°C with stirring and cooled to room temperature. The dispersion was filtered through a paper filter under vacuum, and the recovered material was washed with ethanol and dried under vacuum.

[0110] Example 1 Synthesis of Base Generator 1 In the above synthesis method, 1,5-diazabicyclo(4.3.0)non-5-ene (0.124 mg, 1 mmol, Tokyo Chemical Industry Co., Ltd.) was used as the base, and 2-chloro-4′-methoxyacetophenone (0.184 mg, 1 mmol, Tokyo Chemical Industry Co., Ltd.) was used as the 2-halogenacetyl derivative, to obtain powdery base generator 1 (structure shown below) (yield 61%, 0.352 mg).

[0111] 1 H NMR (400 MHz, CDCl3): δ 0.81 (t, J = 7.3Hz, 3H), 1.01 (m, 4H), 1.26 (m, 2H), 1.77 (m, 6H), 2.66 (t, J = 6.0Hz, 2H), 2.96 (t, J = 5.5Hz, 2H), 3.32 (t, J = 7.3Hz, 2H), 3.79 (s, 2H), 3.91 (s, 3H), 6.82 (m, 3H), 6.97 (m, 8H), 7.45 (d, J = 6.9Hz, 6H), 7.72 (d, J = 8.7Hz, 2H). 13 C NMR (100 MHz, CDCl3): δ 14.6, 17.8, 18.8, 28.2, 29.5, 30.5, 42.1, 46.0, 54.3, 55.7, 58.0, 114.3, 121.6, 125.6, 126.1, 130.9, 135.1, 164.9, 165.5, 189.9.

[0112]

[0113] Example 2 Synthesis of Base Generator 2 In the above synthesis method, 1,5-diazabicyclo(4.3.0)non-5-ene (0.124 mg, 1 mmol, Tokyo Chemical Industry Co., Ltd.) was used as the base, and 2-chloro-4′-phenylacetophenone (0.230 mg, 1 mmol, Tokyo Chemical Industry Co., Ltd.) was used as the 2-halogenacetyl derivative, to obtain powdery base generator 2 (structure shown below) (yield 69%, 0.428 mg).

[0114] 1 ​​H NMR (400 MHz, CDCl3): δ 0.80 (t, J = 7.3Hz, 3H), 1.02 (m, 4H), 1.27 (m, 2H), 1.74 (m, 4H), 1.87 (m, 2H), 2.66 (t, J = 6.0Hz, 2H), 2.92 (t, J = 5.5Hz, 2H), 3.29 (t, J = 7.3Hz, 2H), 3.89 (s, 2H), 6.83 (m, 3H), 6.97 (m, 6H), 7.46 (m, 9H), 7.66 (m, 2H), 7.74, (m, 2H), 7.82, (m, 2H). 13 C NMR (100 MHz, CDCl3): δ 14.6, 17.8, 18.8, 28.1, 29.5, 30.5, 42.1, 46.0, 54.3, 58.3, 121.6, 125.6, 127.3, 127.6, 128.7, 129.0, 129.1, 131.8, 135.1, 139.3, 147.5, 165.5, 191.3.

[0115]

[0116] Example 3 Synthesis of Base Generator 3 In the above synthesis method, 1,5-diazabicyclo(4.3.0)non-5-ene (0.124 mg, 1 mmol, Tokyo Chemical Industry Co., Ltd.) was used as the base, and 2-bromoacetylnaphthalene (0.249 mg, 1 mmol, Tokyo Chemical Industry Co., Ltd.) was used as the 2-halogenacetyl derivative, to obtain powdery base generator 3 (structure shown below) (yield 65%, 0.386 mg).

[0117] 1 ​H NMR (400 MHz, DMSO-d6): δ 0.75 (t, J = 7.3Hz, 3H), 0.85 (m, 4H), 1.18 (m, 2H), 2.05 (m, 4H), 2.89 (t, J = 7.8Hz, 2H), 3.44 (m, 4H), 3.74 (t, J = 7.3Hz, 2H), 5.36 (s, 2H), 6.72 (m, 3H), 6.89 (t, J = 7.3Hz, 6H), 7.19 (d, J = 6.8Hz, 6H), 7.7 (m, 2H), 8.07 (m, 4H), 8.71 (s, 1H). 13 C NMR (100 MHz, CDCl3): δ 14.6, 17.7, 18.7, 27.5, 30.0, 30.3, 42.1, 46.1, 54.2, 58.6, 121.0, 123.3, 125.2, 127.3, 127.8, 128.5, 129.2, 129.5, 130.5, 131.4, 131.9, 134.3, 135.4, 165.6, 193.0.

[0118]

[0119] Example 4 Synthesis of Base Generator 4 In the above synthesis method, 1,5-diazabicyclo(4.3.0)non-5-ene (0.124 mg, 1 mmol, Tokyo Chemical Industry Co., Ltd.) was used as the base, and 2-(bromoacetyl)-6-methoxynaphthalene (0.279 mg, 1 mmol, Tokyo Chemical Industry Co., Ltd.) was used as the 2-halogenacetyl derivative, to obtain powdery base generator 4 (structure shown below) (yield 56%, 0.353 mg).

[0120] 1 ​H NMR (400 MHz, CDCl3): δ 0.78 (t, J = 7.3Hz, 3H), 1.04 (broad s, 4H), 1.25 (m, 2H), 1.77 (m, 4H), 1.89 (m, 2H), 2.70 (t, J = 5.5Hz, 2H), 2.95 (t, J = 5.5Hz, 2H), 3.30 (t, J = 7.3Hz, 2H), 3.93 (s, 2H), 3.96 (s, 3H), 6.80 (m, 3H), 6.95 (t, J = 7.3Hz, 6H), 7.17 (m, 1H), 7.26 (m, 1H), 7.48 (m, 6H), 7.79 (s, 2H), 7.95 (d, J = 9.2Hz, 1H), 8.18 (s, 1H). 13 C NMR (100 MHz, CDCl3): δ 14.6, 17.8, 18.7, 28.1, 29.5, 30.5, 42.1, 46.0, 54.3, 55.5, 58.1, 105.6, 120.3, 121.5, 123.8, 125.6, 127.6, 127.7, 128.3, 128.4, 130.8, 131.7, 135.1, 138.2, 160.6, 165.5, 191.1.

[0121]

[0122] <Measurement of molar absorption coefficient> The molar absorption coefficients (0.5 mg / mL, in acetonitrile) of the base generators synthesized in Examples 1 to 4 were measured. The results are shown in Table 1. As shown in Table 1, the chromophores of Base Generators 1 to 4 exhibited sufficiently high absorption coefficients for light with a wavelength of 365 nm or 395 nm.

[0123]

[0124] <Preparation of Cured Product 1> The base generator (0.02 g) synthesized in Examples 1 to 4 was dissolved in norbornane diisocyanate (5.43 g, Mitsui Chemicals, Inc.), a polyisocyanate compound. To the resulting solution, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (4.57 g, Mitsui Chemicals, Inc.), a polythiol compound, was added and vigorously stirred for 30 minutes. Next, the mixture was degassed under vacuum while stirring for 30 minutes, yielding a composition containing a polymerizable compound and a base generator. The resulting composition was left at room temperature for 8 hours. As a result, the viscosity of the composition did not increase too much and it remained in a usable state.

[0125] The composition was applied to a glass plate using a bar coater to form a thin film. This thin film was irradiated with light having a wavelength of 365 nm for 60 seconds (3 mW / cm ２ The resulting cured product had a refractive index of 1.67 and transparency suitable for use as an optical member.

[0126] <Preparation of Cured Product 2> Base generator 4 (0.57 g) synthesized in Example 4, 10-camphorsulfonic acid (0.019 g, Tokyo Chemical Industry Co., Ltd.) as a stabilizer, dimethyltin(IV) dichloride (0.009 g, Tokyo Chemical Industry Co., Ltd.) as a metal catalyst, and triphenyl phosphite (0.38 g, Tokyo Chemical Industry Co., Ltd.) as a stabilizer were dissolved in xylylene diisocyanate (13.5 g, Mitsui Chemicals, Inc.), a polyisocyanate compound. To this solution, 4-mercaptomethyl-8-dimercapto-3,6-dithiaoctane (90 g, Mitsui Chemicals, Inc.), a polythiol compound, was added and stirred vigorously for 30 minutes. The solution was then filtered through a 3 μm PTFE filter and degassed under vacuum while stirring for 30 minutes to obtain a masterbatch. The viscosity of the masterbatch at 25°C measured after stabilization was 640 cP. This masterbatch was stored at room temperature for 20 days.

[0127] A mixture containing xylylene diisocyanate (8.27 g), a polyisocyanate compound; KF-640 (0.055 g, Shin-Etsu Chemical Co., Ltd.), a polyether-modified silicone compound; and Hostavin PR-25 (0.036 g, Clariant), an ultraviolet absorber, was prepared. The stored masterbatch (10 g) was added to this mixture, and the mixture was vigorously stirred for 30 minutes to obtain a composition. The viscosity of the composition at 25°C was less than 40 cP. The composition was filtered through a 3 μm PTFE filter and degassed under vacuum while stirring for 30 minutes. The resulting composition was then poured into a glass mold capable of producing a 2 mm thick, flat-plate-shaped cured product, and irradiated with 365 nm light for 60 seconds (3 mW / cm). ２ The glass mold was then placed in an oven and heated at 120°C for 1 hour to completely cure the composition. The resulting cured product had a refractive index of 1.67 and transparency suitable for optical components.

[0128] As shown by the above results, the compositions of Examples 1 to 4 containing Base Generators 1 to 4 exhibited photocurability and an excellent pot life.

[0129] Comparative Example 1: Synthesis of Base Generator 5 Thioanisole (0.497 g, 4 mmol, Tokyo Chemical Industry Co., Ltd.) and aluminum chloride (AlCl ３ , 1.067 g, 8 mmol, Fujifilm Wako Pure Chemical Industries, Ltd.) was dissolved in anhydrous CH ２ Cl ２ The dispersion was cooled to 0°C, and ethyl chloroglyoxylate (0.437 mg, Tokyo Chemical Industry Co., Ltd.) was added to anhydrous CH4. ２ Cl ２ (10 mL, Kanto Chemical Co., Inc.) over 30 minutes to obtain a reaction solution. This reaction solution was stirred at 25°C for 4 hours, and distilled water (50 mL) was added. The aqueous phase was separated and ２ Cl ２ (10 mL) three times. The concentrated organic phase was washed with brine and ２ SO ４The resulting material (0.668 mg) was dissolved in aqueous NaOH (10 mL, 1 M) and stirred at room temperature for 3 hours. The aqueous phase was extracted with CH ２ Cl ２ (10 mL) twice, and the aqueous phase after extraction was cooled to 0° C. in an ice bath and adjusted to pH 3 with 1 M hydrochloric acid. ２ Cl ２ (10 mL) three times, and the concentrated organic phase was washed with brine and ２ SO ４ The extract was dried at rt, filtered and concentrated under vacuum to give 0.448 mg of 4-(methylthio)phenylglyoxylic acid (71% yield).

[0130] 1 H NMR (400 MHz, CDCl3): δ 2.55 (s, 3H), 7.30 (d, J = 9.2 Hz, 2H), 8.29 (d, J= 9.2 Hz, 2H), 9.15 (broad s, 1H). 13 C NMR (100 MHz, CDCl3): δ 14.5, 124.8, 127.7, 131.7, 150.5, 161.6, 182.7.

[0131] 4-(Methylthio)phenylglyoxylic acid (100 mg) and 1,8-diazabicyclo(5.4.0)undec-7-ene (77 mg, Tokyo Chemical Industry Co., Ltd.) were dissolved in CH ２ Cl ２ (5 mL) to obtain a solution. The solution was stirred at room temperature for 3 hours, the volatile components were removed under vacuum, and the oil was dispersed in diethyl ether (5 mL) with stirring. The oil phase was separated with diethyl ether and dried under vacuum to obtain Base Generator 5 (structure shown below).

[0132] 1 ​​H NMR (400 MHz, CDCl3): δ 1.65 (m, 2H), 1.72 (m, 4H), 1.99 (m, 2H), 2.50 (s, 3H), 2.82 (m, 2H), 3.43 (m, 6H), 5.52 (brs, 1H), 7.24 (d, J = 8.2Hz, 2H), 7.97 (d, J = 8.2Hz, 2H). 13 C NMR (100 MHz, CDCl3): δ 14.7, 19.5, 23.9, 26.7, 28.9, 32.2, 38.1, 48.5, 54.1, 124.7, 130.1, 130.6, 145.4, 165.9, 171.5, 195.1.

[0133]

[0134] A composition was prepared in the same manner as in <Preparation of cured product 1> except for using base generator 5. As a result, the viscosity increased within a short time (about 10 minutes) after preparation, and the composition became unusable for preparing a cured product.

[0135] The disclosure of Japanese Patent Application No. 2024-042780 is incorporated herein by reference in its entirety. All publications, patent applications, and technical standards mentioned herein are incorporated by reference to the same extent as if each individual publication, patent application, and technical standard was specifically and individually indicated to be incorporated by reference.

Claims

1. A polymerizable compound comprising a base generator and a polymerizable compound, wherein the base generator comprises a salt of a cation and an anion, and the cation comprises a carbon atom and a nitrogen atom N bonded to the carbon atom by a single bond. １ and a nitrogen atom N bonded to the carbon atom by a double bond. ２ and a carbonyl group, wherein the polymerizable compound comprises a polyiso(thio)cyanate compound and a polythiol compound.

2. The cation is a nitrogen atom N １ 2. The composition of claim 1, comprising a monovalent organic group bonded to said carbonyl group.

3. The composition of claim 2, wherein the monovalent organic group further comprises an aromatic ring.

4. The composition according to claim 1, wherein the cation has a structure represented by the following formula (1), where n is an integer of 1 to 3, and R is a monovalent organic group containing a carbonyl group:

5. The composition of claim 1, wherein said anion is a borate anion.

6. The composition according to claim 5, wherein the borate anion has a structure in which three aromatic hydrocarbon groups and one aliphatic hydrocarbon group are bonded to a boron atom.

7. The composition according to claim 1, wherein the content of the base generator is 0.1 to 2.0 parts by mass, relative to 100 parts by mass of the total mass of the polymerizable compounds.

8. The composition of claim 1, further comprising a stabilizer.

9. The composition according to claim 8, wherein the stabilizer comprises at least one of a phosphite compound and an acid having a pKa of -1.0 or more and less than 2.

0.

10. The composition of claim 8, wherein the stabilizer comprises a phosphite compound and an acid having a pKa of less than 2.

0.

11. 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 to 0.05 parts by mass, relative to 100 parts by mass of the total mass of the polymerizable compounds.

12. The composition according to claim 1, wherein the ratio (A / B) of the mass A of the polyiso(thio)cyanate compound to the mass B of the polythiol compound is 99 / 1 to 1 / 99.

13. The composition of claim 1, wherein the polyiso(thio)cyanate compound 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.

14. The polythiol compound 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 2,2-bis(mercaptomethylthio)ethyl)-1,3-dithiane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 3-mercaptomethyl-1,5-dimercapto-2,4-dithiapentane, and tris(mercaptomethylthio)methane.

15. The composition according to any one of claims 1 to 14, for use in a method for producing a cured product, which method comprises irradiating the composition with light having a wavelength of 340 nm to 500 nm.

16. A cured product of the composition according to any one of claims 1 to 14.

17. A method for producing a cured product, comprising a curing step of curing the composition according to any one of claims 1 to 14, wherein the curing step comprises irradiating the composition with light having a wavelength of 340 nm to 500 nm.

18. The method for producing a cured product according to claim 17, wherein the irradiation with light having a wavelength of 340 nm to 500 nm is carried out using an LED.

19. The method for producing a cured product according to claim 17, wherein the curing step further comprises heating the composition.

20. The method for producing a cured product according to claim 17, further comprising a viscosity adjusting step of adjusting the viscosity of the composition before the curing step.

21. A compound which is a salt of a cation and an anion, wherein the cation has a structure represented by the following formula (1), n ​​is an integer of 1 to 3, and R is a monovalent organic group containing a carbonyl group:

22. A base generator comprising the compound of claim 21.

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