Polymerizable composition and method for selecting same

Abstract

This method for selecting a polymerizable composition containing a polymerizable compound involves selecting, on the basis of proton dissociation energy of a proton-dissociable group in a carboxylic acid and an inflection point temperature in a temperature-dependent curve of the density of the carboxylic acid, a polymerizable composition containing a borate anion and at least one selected from the group consisting of the carboxylic acid, a salt of the carboxylic acid, and a hydrate of the carboxylic acid.

Description

Polymerizable composition and method for selecting same

[0001] The present disclosure relates to a polymerizable composition, a selection method thereof, and the like.

[0002] In recent years, polymerizable compositions have been used to bond various components in the manufacture of various devices. For example, Patent Document 1 listed below describes a thermosetting composition containing a polymerizable compound.

[0003] JP 2014-156522 A

[0004] With the recent trend toward miniaturization and high performance of various devices, there are cases where a polymerizable composition is thermally cured near a component that should be avoided from being exposed to high heat, where a polymerizable composition is thermally cured in contact with a component that should be avoided from being exposed to high heat, etc. In these cases, from the viewpoint of avoiding deterioration of the component by performing thermal curing at a low temperature, a method is required for lowering the reaction initiation temperature of the polymerizable composition in the initial preparation stage.

[0005] Furthermore, according to the findings of the present inventors, when a polymerizable composition is thermally cured after a certain time has elapsed since the polymerizable composition was prepared by mixing the components, the reaction initiation temperature may change compared to the temperature immediately after the preparation of the polymerizable composition. Therefore, a method for suppressing the change over time in the reaction initiation temperature of a polymerizable composition after preparation is required.

[0006] For such polymerizable compositions, a new method is required for adjusting the reaction initiation temperature at the initial stage of preparation of the polymerizable composition and the change over time in the reaction initiation temperature after preparation of the polymerizable composition.

[0007] An object of one aspect of the present disclosure is to provide a method for selecting a polymerizable composition that is capable of adjusting the reaction initiation temperature at an early stage of preparation of the polymerizable composition and the change over time in the reaction initiation temperature after preparation of the polymerizable composition.An object of another aspect of the present disclosure is to provide a polymerizable composition that is capable of lowering the reaction initiation temperature at an early stage of preparation of the polymerizable composition and suppressing the change over time in the reaction initiation temperature after preparation of the polymerizable composition.

[0008] The present disclosure relates to the following items [1] to

[12] , etc. [1] A method for selecting a polymerizable composition containing a polymerizable compound, comprising selecting a polymerizable composition containing a borate anion and at least one selected from the group consisting of a carboxylic acid, a salt of the carboxylic acid, and a hydrate of the carboxylic acid, based on the proton dissociation energy of a proton dissociative group of the carboxylic acid and the inflection point temperature in a temperature dependence curve of the density of the carboxylic acid. [2] The method for selecting a polymerizable composition according to [1], wherein the borate anion comprises a borate anion having a naphthalene ring. [3] The method for selecting a polymerizable composition according to [1] or [2], wherein the borate anion comprises an alkyltriarylborate anion. [4] The method for selecting a polymerizable composition according to any one of [1] to [3], wherein the carboxylic acid comprises an aromatic carboxylic acid. [5] The method for selecting a polymerizable composition according to any one of [1] to [4], wherein the carboxylic acid has two hydroxy groups. [6] The method for selecting a polymerizable composition according to any one of [1] to [5], wherein the polymerizable compound comprises a (meth)acrylate compound. [7] A polymerizable composition containing a polymerizable compound, the polymerizable composition comprising a borate anion and at least one selected from the group consisting of a carboxylic acid, a salt of the carboxylic acid, and a hydrate of the carboxylic acid, wherein the proton dissociation energy of a proton dissociative group of the carboxylic acid is 295.5 kJ / mol or more, and the inflection point temperature in a temperature dependence curve of density of the carboxylic acid is 135.0°C or less. [8] The polymerizable composition according to [7], wherein the borate anion comprises a borate anion having a naphthalene ring. [9] The polymerizable composition according to [7] or [8], wherein the borate anion comprises an alkyltriarylborate anion.

[10] The polymerizable composition according to any one of [7] to [9], wherein the carboxylic acid comprises an aromatic carboxylic acid.

[11] The polymerizable composition according to any one of [7] to

[10] , wherein the number of hydroxy groups in the carboxylic acid is two.

[12] The polymerizable composition according to any one of [7] to

[11] , wherein the polymerizable compound includes a (meth)acrylate compound.

[0009] According to one aspect of the present disclosure, it is possible to provide a method for selecting a polymerizable composition that is capable of adjusting the reaction initiation temperature at the initial stage of preparation of the polymerizable composition and the change over time in the reaction initiation temperature after preparation of the polymerizable composition. According to another aspect of the present disclosure, it is possible to provide a polymerizable composition that is capable of lowering the reaction initiation temperature at the initial stage of preparation of the polymerizable composition and suppressing the change over time in the reaction initiation temperature after preparation of the polymerizable composition.

[0010] Hereinafter, embodiments of the present disclosure will be described in detail, but the present disclosure is not limited to the following embodiments.

[0011] In this specification, numerical ranges indicated using "to" indicate a range that includes the numerical values ​​before and after "to" as the minimum and maximum values, respectively. A numerical range "A or greater" means a range exceeding A and A. A numerical range "A or less" means a range less than A and A. In numerical ranges described in stages in this specification, the upper or lower limit of a numerical range in a certain stage can be arbitrarily combined with the upper or lower limit of a numerical range in another stage. In numerical ranges described in this specification, the upper or lower limit of the numerical range may be replaced with a value shown in the examples. "A or B" may include either A or B, or may include both. Unless otherwise specified, the materials exemplified in this specification can be used alone or in combination of two or more. When multiple substances corresponding to each component are present in the composition, the content of each component in the composition refers to the total amount of the multiple substances present in the composition, unless otherwise specified. "(Meth)acrylate" means at least one of acrylate and the corresponding methacrylate. The same applies to other similar expressions such as "(meth)acrylic." The content of (meth)acrylate compounds refers to the total amount of acrylate compounds and methacrylate compounds. Unless otherwise specified, "alkyl groups" may be linear, branched, or cyclic. "Hydroxy groups" do not include OH groups contained in carboxy groups. "Total mass of polymerizable composition" refers to the total mass of the solid content of the polymerizable composition. The solid content of the polymerizable composition refers to the non-volatile content excluding volatile components that can volatilize (water, organic solvents, etc.). In other words, the solid content refers to components that remain without volatilizing when the polymerizable composition is dried, and includes components that are liquid, syrup-like, waxy, etc. at 25°C.

[0012] In this specification, the "weight average molecular weight" can be measured by gel permeation chromatography (GPC) under the following measurement conditions, by conversion from a calibration curve using standard polystyrene. (Measurement conditions) Apparatus: GPC-8020, manufactured by Tosoh Corporation Detector: RI-8020, manufactured by Tosoh Corporation Column: Gelpack GL-A-160-S + GL-A150, manufactured by Resonaq Corporation Sample concentration: 120 mg / 3 mL Solvent: tetrahydrofuran Injection volume: 60 μL Pressure: 294 × 10 ６ Pa (30kgf / cm ２ ) Flow rate: 1.00mL / min

[0013] The polymerizable composition according to this embodiment is a polymerizable composition containing a polymerizable compound, and includes (A) a borate anion (hereinafter sometimes referred to as "component (A)") and (B) at least one carboxylic acid component (hereinafter sometimes referred to as "component (B)") selected from the group consisting of carboxylic acids, salts of the carboxylic acids, and hydrates of the carboxylic acids. The proton dissociation energy of the proton dissociative group of the carboxylic acid (hereinafter sometimes referred to as "proton dissociation energy E") is 295.5 kJ / mol or more, and the inflection point temperature in the temperature dependence curve of the density of the carboxylic acid (hereinafter sometimes referred to as "density inflection point temperature T") is 135.0°C or less. Hereinafter, a carboxylic acid having the above-mentioned specific proton dissociation energy E and density inflection point temperature T will be referred to as "carboxylic acid b." Component (B) is at least one carboxylic acid component selected from the group consisting of carboxylic acid b, salts of carboxylic acid b, and hydrates of carboxylic acid b.

[0014] The polymerizable composition according to this embodiment contains at least one polymerizable compound, and may contain, as the polymerizable compound, at least one selected from the group consisting of a compound containing component (A) and a component (B), or may contain a polymerizable compound other than the compound containing component (A) and the at least one selected from the group consisting of component (B). When at least one selected from the group consisting of a compound containing component (A) and a component (B) is a polymerizable compound, the polymerizable composition according to this embodiment may contain a compound containing component (A) and a polymerizable compound other than the compound containing component (B).

[0015] The polymerizable composition according to this embodiment can be used as a thermosetting polymerizable composition. The polymerizable composition according to this embodiment can reduce the reaction initiation temperature at the initial stage of preparation of the polymerizable composition. The polymerizable composition according to this embodiment can achieve a reaction initiation temperature T1 of, for example, 85.00°C or lower (preferably, 80.00°C or lower, 75.00°C or lower, 70.00°C or lower, 65.00°C or lower, etc.) in the evaluation method described in the Examples below. The cured product according to this embodiment is obtained by curing the polymerizable composition according to this embodiment, and is a cured product of the polymerizable composition according to this embodiment.

[0016] The polymerizable composition according to this embodiment can suppress the change in reaction initiation temperature over time after preparation of the polymerizable composition (obtaining excellent storage stability with respect to the reaction initiation temperature), and can suppress the change in reaction initiation temperature over time after obtaining a film-shaped polymerizable composition using a polymerizable composition prepared by mixing the respective components. The polymerizable composition according to this embodiment can obtain, in the evaluation method described in the Examples below, an absolute value |T2-T1| of the temperature difference between the reaction initiation temperature T1 and the reaction initiation temperature T2 of, for example, 50.00°C or less (preferably 30.00°C or less, 10.00°C or less, 5.00°C or less, 3.00°C or less, etc.).

[0017] The use of the polymerizable composition according to this embodiment is not particularly limited, and examples thereof include display devices, semiconductor devices, and electronic device components. The polymerizable composition according to this embodiment may be used in micro LEDs (light emitting diodes), micro OLEDs (organic light emitting diodes), and the like. The cured product according to this embodiment is a cured product of the polymerizable composition according to this embodiment.

[0018] The polymerizable composition according to this embodiment contains a borate anion as component (A). The polymerizable composition according to this embodiment may contain a boron salt containing a borate anion (a salt of component (A) and a counter cation of component (A); hereinafter referred to as "component (a1)"). In the polymerizable composition according to this embodiment, component (A) may be bonded to a counter cation, or may be free and not bonded to a counter cation.

[0019] In the component (A), the number of boron atoms (number per molecule) may be 1 to 4, 1 to 3, or 1 to 2, from the viewpoint of easily lowering the reaction initiation temperature in the initial stage of preparation of the polymerizable composition.

[0020] From the viewpoint of easily lowering the reaction initiation temperature in the initial stage of preparation of the polymerizable composition, the component (A) may include a borate anion having a naphthalene ring (a substituted or unsubstituted naphthyl group), may include a borate anion having a naphthalene ring (a substituted or unsubstituted naphthyl group) bonded to a boron atom, may include at least one anion selected from the group consisting of an alkyltriarylborate anion and a tetraarylborate anion, may include an alkyltriarylborate anion, may include an alkyltrinaphthylborate anion, may include a butyltrinaphthylborate anion, or may include an n-butyltrinaphthylborate anion.

[0021] In the component (A), the number of naphthalene rings (the number per molecule) or the number of naphthalene rings bonded to boron atoms (the number per molecule) may be 1 to 4, 1 to 3, 2 to 4, 2 to 3, or 3 to 4, or may be 3, from the viewpoint of making it easier to lower the reaction initiation temperature in the initial stage of preparation of the polymerizable composition.

[0022] Component (A) may have an unsubstituted naphthalene ring or a naphthalene ring having a substituent, such as a halogen atom, an alkyl group, an aryl group, or an alkoxy group.

[0023] From the viewpoint of easily lowering the reaction initiation temperature in the early stages of preparation of the polymerizable composition, the component (A) may have an alkyl group bonded to a boron atom. From the viewpoint of easily lowering the reaction initiation temperature in the early stages of preparation of the polymerizable composition, the number of alkyl groups bonded to boron atoms in the component (A) (the number per molecule) may be 1 to 3, or 1 to 2.

[0024] The number of carbon atoms in the alkyl group bonded to the boron atom may be within the following ranges, from the viewpoint of easily lowering the reaction initiation temperature in the initial stage of preparation of the polymerizable composition. The number of carbon atoms in the alkyl group may be 1 or more, 2 or more, 3 or more, or 4 or more. The number of carbon atoms in the alkyl group may be 12 or less, 10 or less, 8 or less, 6 or less, 5 or less, or 4 or less. From these viewpoints, the number of carbon atoms in the alkyl group may be 1 to 12, 1 to 8, 1 to 4, 2 to 12, 2 to 8, 2 to 4, 3 to 12, 3 to 8, 3 to 4, 4 to 12, or 4 to 8.

[0025] Component (A) may have a functional group bonded to the boron atom other than a naphthalene ring (naphthyl group) or an alkyl group, such as an aryl group other than a naphthyl group (e.g., a phenyl group).

[0026] Examples of the counter cation in the component (a1) include a quaternary ammonium ion, a tertiary ammonium ion, a secondary ammonium ion, a primary ammonium ion, an ammonium ion, an imidazolium ion, an imidazolinium ion, a pyridinium ion, an alkali metal ion (such as a sodium ion or a potassium ion), a phosphonium cation, a sulfonium cation, and an iodonium cation. The component (a1) may or may not contain a metal ion. Examples of the metal ion include an alkali metal ion (such as a sodium ion or a potassium ion). The component (a1) may contain a quaternary ammonium ion as a counter cation, from the viewpoint of easily lowering the reaction initiation temperature in the initial stage of preparation of the polymerizable composition.

[0027] In the quaternary ammonium ion, examples of the substituent bonded to the nitrogen atom include an alkyl group, an aryl group (e.g., a phenyl group), etc. From the viewpoint of easily lowering the reaction initiation temperature in the initial stage of preparation of the polymerizable composition, the component (a1) may contain, as a counter cation, a quaternary ammonium ion having an alkyl group bonded to the nitrogen atom, or may contain a quaternary ammonium ion having at least one alkyl group selected from the group consisting of a linear alkyl group bonded to the nitrogen atom and a branched alkyl group bonded to the nitrogen atom.

[0028] The number of carbon atoms in the alkyl group bonded to the nitrogen atom may be within the following ranges, from the viewpoint of easily lowering the reaction initiation temperature in the initial stage of preparation of the polymerizable composition. The number of carbon atoms in the alkyl group may be 1 or more, 2 or more, 3 or more, or 4 or more. The number of carbon atoms in the alkyl group may be 18 or less, 16 or less, 14 or less, 12 or less, 10 or less, 8 or less, 6 or less, 5 or less, or 4 or less. From these viewpoints, the number of carbon atoms in the alkyl group may be 1 to 18, 1 to 8, 1 to 4, 2 to 6, 4 to 18, or 4 to 8.

[0029] Examples of quaternary ammonium ions include tetraalkylammonium ions, trialkylammonium ions, dialkylammonium ions, monoalkylammonium ions, tetraarylammonium ions, triarylammonium ions, diarylammonium ions, monoarylammonium ions, etc. From the viewpoint of easily lowering the reaction initiation temperature in the initial stage of preparation of the polymerizable composition, the component (a1) may contain a tetraalkylammonium ion as a counter cation.

[0030] Examples of the tetraalkylammonium ion include a tetramethylammonium ion, a tetraethylammonium ion, a tetrapropylammonium ion, a tetrabutylammonium ion, a tetrahexylammonium ion, a triethylmethylammonium ion, a tributylethylammonium ion, a trimethyldecylammonium ion, etc. From the viewpoint of easily lowering the reaction initiation temperature in the initial stage of preparation of the polymerizable composition, the component (a1) may contain a tetrabutylammonium ion as a counter cation.

[0031] From the viewpoint of easily lowering the reaction initiation temperature in the initial stage of preparation of the polymerizable composition, the content of the component (a1) may be in the following ranges based on the total mass of the polymerizable composition: The content of the component (a1) may be 0.01 mass% or more, 0.05 mass% or more, 0.10 mass% or more, 0.20 mass% or more, 0.30 mass% or more, 0.40 mass% or more, 0.50 mass% or more, 0.60 mass% or more, 0.70 mass% or more, 0.80 mass% or more, 0.90 mass% or more, 1.00 mass% or more, 1.10 mass% or more, or 1.15 mass% or more. The content of the (a1) component may be 20.00% by mass or less, 15.00% by mass or less, 10.00% by mass or less, 8.00% by mass or less, 7.00% by mass or less, 6.00% by mass or less, 5.00% by mass or less, 4.00% by mass or less, 3.00% by mass or less, 2.00% by mass or less, 1.50% by mass or less, or 1.20% by mass or less. From these viewpoints, the content of the (a1) component may be 0.01 to 20.00% by mass, 0.30 to 20.00% by mass, 0.70 to 20.00% by mass, 0.01 to 5.00% by mass, 0.30 to 5.00% by mass, 0.70 to 5.00% by mass, 0.01 to 2.00% by mass, 0.30 to 2.00% by mass, or 0.70 to 2.00% by mass.

[0032] The polymerizable composition according to this embodiment contains, as component (B), at least one selected from the group consisting of carboxylic acid b, a salt of carboxylic acid b, and a hydrate of carboxylic acid b (excluding compounds corresponding to component (a1)). Examples of the salt of carboxylic acid b include alkali metal salts such as sodium salts and potassium salts.

[0033] In the carboxylic acid b, the number of carboxy groups (the number in one molecule) may be 1, from the viewpoint of easily lowering the reaction initiation temperature in the initial stage of preparation of the polymerizable composition and easily obtaining excellent storage stability with respect to the reaction initiation temperature.

[0034] The carboxylic acid b may have a functional group other than a carboxy group. Examples of the substituent include a hydroxy group, an alkyl group (e.g., a methyl group), an alkoxy group (e.g., a methoxy group), an ester group, an amino group (excluding alkylamino groups), an alkylamino group (e.g., a methylamino group), a nitro group, an anilino group, a sulfo group, and an alkylsulfonyl group (e.g., a methylsulfonyl group).

[0035] From the viewpoint of easily lowering the reaction initiation temperature in the initial stage of preparation of the polymerizable composition and easily obtaining excellent storage stability with respect to the reaction initiation temperature, the carboxylic acid b may have at least one selected from the group consisting of a hydroxy group, an alkyl group, an alkoxy group, an ester group, an amino group, an alkylamino group, a nitro group, an anilino group, a sulfo group, and an alkylsulfonyl group, and may have a hydroxy group. In the carboxylic acid b, from the viewpoint of easily lowering the reaction initiation temperature in the initial stage of preparation of the polymerizable composition and easily obtaining excellent storage stability with respect to the reaction initiation temperature, the number of hydroxy groups, alkyl groups, alkoxy groups, ester groups, amino groups, alkylamino groups, nitro groups, anilino groups, sulfo groups, or alkylsulfonyl groups (number per molecule) may be 1 to 4, 1 to 3, 1 to 2, 2 to 4, 2 to 3, or 3 to 4, or may be 2.

[0036] From the viewpoint of easily lowering the reaction initiation temperature in the initial stage of preparation of the polymerizable composition and easily achieving excellent storage stability with respect to the reaction initiation temperature, the carboxylic acid b may include at least one selected from the group consisting of aromatic carboxylic acids and aliphatic carboxylic acids, and may include an aromatic carboxylic acid. Hereinafter, a carboxylic acid having the above-mentioned specific proton dissociation energy E and density inflection point temperature T will be referred to as "aromatic carboxylic acid b."

[0037] The aromatic carboxylic acid b has at least one aromatic ring. The number of aromatic rings (the number in one molecule) may be 1 or 2, or may be 1, from the viewpoint of easily lowering the reaction initiation temperature in the early stage of preparation of the polymerizable composition and easily achieving excellent storage stability with respect to the reaction initiation temperature. Examples of the aromatic ring include a benzene ring and a naphthalene ring. The aromatic carboxylic acid b may include at least one selected from the group consisting of aromatic carboxylic acids having a benzene ring and aromatic carboxylic acids having a naphthalene ring, and may include an aromatic carboxylic acid having a benzene ring, from the viewpoint of easily lowering the reaction initiation temperature in the early stage of preparation of the polymerizable composition and easily achieving excellent storage stability with respect to the reaction initiation temperature.

[0038] The aromatic carboxylic acid b has a carboxy group bonded to an aromatic ring. From the viewpoint of easily lowering the reaction initiation temperature in the initial stage of preparation of the polymerizable composition and easily achieving excellent storage stability with respect to the reaction initiation temperature, the aromatic carboxylic acid b may include an aromatic carboxylic acid having a hydroxy group (phenolic hydroxy group) bonded to an aromatic ring.

[0039] In the aromatic carboxylic acid b, the number of carboxy groups bonded to the aromatic ring (the number per molecule) may be 1, from the viewpoint of easily lowering the reaction initiation temperature in the initial stage of preparation of the polymerizable composition and easily obtaining excellent storage stability with respect to the reaction initiation temperature. In the aromatic carboxylic acid b, the number of hydroxy groups (the number per molecule) or the number of hydroxy groups bonded to the aromatic ring (the number per molecule) may be 1 to 4, 1 to 3, 1 to 2, 2 to 4, or 2 to 3, or may be 2, from the viewpoint of easily lowering the reaction initiation temperature in the initial stage of preparation of the polymerizable composition and easily obtaining excellent storage stability with respect to the reaction initiation temperature.

[0040] From the viewpoint of easily lowering the reaction initiation temperature in the initial preparation of the polymerizable composition and easily achieving excellent storage stability with respect to the reaction initiation temperature, the aromatic carboxylic acid b may have a functional group bonded to the para-position relative to the carboxy group bonded to the benzene ring, one or two functional groups bonded to the meta-position relative to the carboxy group bonded to the benzene ring, or one or two functional groups bonded to the ortho-position relative to the carboxy group bonded to the benzene ring. Examples of these functional groups include a hydroxy group, an alkyl group, an alkoxy group, an ester group, an amino group, an alkylamino group, a nitro group, an anilino group, a sulfo group, and an alkylsulfonyl group.

[0041] Examples of aromatic carboxylic acids b include 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, 5-amino-2-hydroxybenzoic acid (also known as 5-aminosalicylic acid), 2-amino-3-hydroxybenzoic acid, 4-amino-3-hydroxybenzoic acid, 2-amino-5-hydroxybenzoic acid, 2-hydroxy-4-methoxybenzoic acid (also known as 4-methoxysalicylic acid), monomethyl phthalate, 4-nitrobenzoic acid, 2,4-dinitrobenzoic acid, 3-hydroxy-4-nitrobenzoic acid, 3-methyl-2-nitrobenzoic acid, and 5-nitroisophthalic acid monoethyl ester. Examples of the benzoic acid include benzoic acid, 4-methylsulfonyl-2-nitrobenzoic acid, N-methyl-2-aminobenzoic acid, 2-anilinobenzoic acid, 3,4-dihydroxybenzoic acid (also known as protocatechuic acid), 3,5-dihydroxybenzoic acid (also known as α-resorcylic acid), 2,3-dihydroxybenzoic acid (also known as 2-pyrocatechuic acid), 2,5-dihydroxybenzoic acid (also known as gentisic acid), 2,4-dihydroxy-6-methylbenzoic acid (also known as orsellinic acid), 3,4,5-trihydroxybenzoic acid (also known as gallic acid), and 1-hydroxy-2-naphthoic acid. From the viewpoint of easily achieving both a low reaction initiation temperature at the initial stage of preparation of the polymerizable composition and excellent storage stability with respect to the reaction initiation temperature, the aromatic carboxylic acid b is preferably 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, 5-amino-2-hydroxybenzoic acid, 2-amino-3-hydroxybenzoic acid, 4-amino-3-hydroxybenzoic acid, 2-amino-5-hydroxybenzoic acid, 2-hydroxy-4-methoxybenzoic acid, monomethyl phthalate, 4-nitrobenzoic acid, 2,4-dinitrobenzoic acid, 3-hydroxy-4-nitrobenzoic acid, 3-methyl The hydroxybenzoic acid may contain at least one selected from the group consisting of 1-hydroxy-2-naphthoic acid, 2-aminobenzoic acid, 2-anilinobenzoic acid, 3,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 2,3-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,4-dihydroxy-6-methylbenzoic acid, 3,4,5-trihydroxybenzoic acid, and 1-hydroxy-2-naphthoic acid, and may contain 3,4-dihydroxybenzoic acid.

[0042] The proton dissociation energy E of the proton dissociative group of carboxylic acid b is 295.5 kJ / mol or more from the viewpoint of lowering the reaction initiation temperature at the initial stage of preparation of the polymerizable composition. Carboxylic acid b has a carboxy group as a proton dissociative group and may further have a proton dissociative group other than a carboxy group. Examples of proton dissociative groups other than a carboxy group include a carboxy group, a hydroxy group, and a sulfo group. When carboxylic acid b has multiple carboxy groups or when carboxylic acid b has a proton dissociative group other than a carboxy group, the proton dissociation energy E refers to the minimum value of the proton dissociation energies E of the multiple proton dissociative groups of carboxylic acid b. The proton dissociation energy E can be calculated by the method described in the Examples below, and can be calculated by quantum chemical calculations based on density functional theory using the program Gaussian 16 (manufactured by Gaussian Corporation), the functional B3LYP, and the basis set 6-31G(d).

[0043] The proton dissociation energy E is 295.5 kJ / mol or more as described above, and may be in the following range (for convenience, the unit "kJ / mol" is omitted) from the viewpoint of easily achieving both the reaction initiation temperature at the initial stage of preparation of the polymerizable composition and excellent storage stability with respect to the reaction initiation temperature. The proton dissociation energy E may be 300.0 or more, 305.0 or more, 308.0 or more, 310.0 or more, 315.0 or more, 316.0 or more, 320.0 or more, 325.0 or more, 330.0 or more, 340.0 or more, 345.0 or more, 350.0 or more, 360.0 or more, 365.0 or more, 370.0 or more, 373.0 or more, 375.0 or more, 377.0 or more, 380.0 or more, 400.0 or more, 450.0 or more, 452.0 or more, 454.0 or more, 455.0 or more, or 456.0 or more. The proton dissociation energy E may be 500.0 or less, 480.0 or less, 460.0 or less, 456.0 or less, 455.0 or less, 454.0 or less, 452.0 or less, 450.0 or less, 400.0 or less, 380.0 or less, 377.0 or less, 375.0 or less, 373.0 or less, 370.0 or less, 365.0 or less, 360.0 or less, 350.0 or less, 345.0 or less, 340.0 or less, 330.0 or less, 325.0 or less, 320.0 or less, 316.0 or less, 315.0 or less, 310.0 or less, 308.0 or less, or 305.0 or less. From these viewpoints, the proton dissociation energy E may be 295.5 to 500.0, 310.0 to 500.0, 320.0 to 500.0, 295.5 to 400.0, 310.0 to 400.0, 320.0 to 400.0, 295.5 to 350.0, 310.0 to 350.0, or 320.0 to 350.0.

[0044] The density inflection temperature T in the temperature dependence curve of the density of carboxylic acid b (curve showing the temperature dependence of density: curve showing the relationship between density and temperature) is 135.0°C or lower from the viewpoint of obtaining excellent storage stability with respect to the reaction initiation temperature. The density inflection temperature T is the temperature at which the approximation lines of the low-temperature region and the high-temperature region in the temperature dependence curve of the density of carboxylic acid b intersect when extended, and is the temperature at which the approximation lines of the low-temperature region (five measurement points from the terminal 280 K) and the high-temperature region (five measurement points from the terminal 500 K) in the temperature dependence curve in 10 K increments in the temperature range of 280 to 500 K intersect when extended. The temperature dependence curve can be obtained by the method described in the Examples below, and can be obtained by acquiring the density every 10 K in the temperature range of 280 to 500 K based on molecular dynamics calculations (program: GROMACS 2020, force field: GAFF2, charge: RESP (calculated using the program Gaussian16 (manufactured by Gaussian), B3LYP / 6-31G(d) / / HF / 6-31G(d))).

[0045] The density inflection point temperature T is 135.0°C or lower as described above, and from the viewpoint of easily achieving both the reaction initiation temperature at the initial stage of preparation of the polymerizable composition and excellent storage stability related to the reaction initiation temperature, it may be in the following range: The density inflection point temperature T may be 130.0°C or lower, 125.0°C or lower, 120.0°C or lower, 115.0°C or lower, 110.0°C or lower, 105.0°C or lower, 100.0°C or lower, 95.0°C or lower, 90.0°C or lower, 85.0°C or lower, 80.0°C or lower, 75.0°C or lower, 70.0°C or lower, 65.0°C or lower, 60.0°C or lower, or 55.0°C or lower. The density inflection point temperature T may be 30.0°C or higher, 35.0°C or higher, 40.0°C or higher, 45.0°C or higher, 50.0°C or higher, 55.0°C or higher, 60.0°C or higher, 65.0°C or higher, 70.0°C or higher, 75.0°C or higher, 80.0°C or higher, 85.0°C or higher, 90.0°C or higher, 95.0°C or higher, 100.0°C or higher, 105.0°C or higher, 110.0°C or higher, 115.0°C or higher, or 120.0°C or higher. From these viewpoints, the density inflection point temperature T may be 30.0 to 135.0 ° C., 70.0 to 135.0 ° C., 100.0 to 135.0 ° C., 30.0 to 125.0 ° C., 70.0 to 125.0 ° C., 100.0 to 125.0 ° C., 30.0 to 120.0 ° C., 70.0 to 120.0 ° C., or 100.0 to 120.0 ° C.

[0046] From the viewpoint of easily lowering the reaction initiation temperature in the initial preparation of the polymerizable composition and easily obtaining excellent storage stability with respect to the reaction initiation temperature, the content of the component (B) may be 50.00 mass% or more, more than 50.00 mass%, 70.00 mass% or more, 80.00 mass% or more, 90.00 mass% or more, 92.00 mass% or more, 95.00 mass% or more, 97.00 mass% or more, 98.00 mass% or more, 99.00 mass% or more, or substantially 100.00 mass% based on the total amount of carboxylic acids (the same applies to carboxylic acids b and carboxylic acids other than carboxylic acids b: salts and hydrates) contained in the polymerizable composition.

[0047] From the viewpoint of easily lowering the reaction initiation temperature in the initial preparation of the polymerizable composition and easily achieving excellent storage stability with respect to the reaction initiation temperature, the content of the component (B) may be in the following ranges based on the total mass of the polymerizable composition: The content of the component (B) may be 0.01 mass% or more, 0.05 mass% or more, 0.10 mass% or more, 0.30 mass% or more, 0.50 mass% or more, 0.80 mass% or more, 1.00 mass% or more, 1.05 mass% or more, 1.10 mass% or more, 1.15 mass% or more, 1.20 mass% or more, or 1.25 mass% or more. The content of component (B) is 10.00% by mass or less, 8.00% by mass or less, 6.00% by mass or less, 5.00% by mass or less, 4.00% by mass or less, 3.00% by mass or less, 2.50% by mass or less. The content may be 2.00% by mass or less, 1.90% by mass or less, 1.80% by mass or less, 1.60% by mass or less, 1.50% by mass or less, 1.40% by mass or less, or 1.30% by mass or less. From these viewpoints, the content of component (B) may be 0.01 to 10.00 mass%, 0.01 to 2.50 mass%, 0.01 to 1.50 mass%, 0.50 to 10.00 mass%, 0.50 to 2.50 mass%, 0.50 to 1.50 mass%, 1.00 to 10.00 mass%, 1.00 to 2.50 mass%, or 1.00 to 1.50 mass%.

[0048] The mass ratio R1 of the content of the component (B) to the content of the component (a1) (component (B) / component (a1)) may be within the following range, from the viewpoint of easily lowering the reaction initiation temperature in the initial preparation of the polymerizable composition and easily achieving excellent storage stability with respect to the reaction initiation temperature. The mass ratio R1 may be 0.01 or more, 0.05 or more, 0.10 or more, 0.20 or more, 0.30 or more, 0.40 or more, 0.50 or more, 0.60 or more, 0.70 or more, 0.80 or more, 0.90 or more, or 1.00 or more. The mass ratio R1 may be 10.00 or less, 8.00 or less, 6.00 or less, 5.00 or less, 4.50 or less, 4.00 or less, 3.50 or less, 3.00 or less, 2.50 or less, 2.00 or less, 1.80 or less, 1.50 or less, or 1.20 or less. From these viewpoints, the mass ratio R1 may be 0.01 to 10.00, 0.01 to 6.00, 0.01 to 3.00, 0.30 to 10.00, 0.30 to 6.00, 0.30 to 3.00, 0.50 to 10.00, 0.50 to 6.00, or 0.50 to 3.00.

[0049] The polymerizable composition according to this embodiment may contain, as component (C), a phosphorus compound having a P═O(OH) structure (excluding compounds corresponding to component (a1) or component (B); hereinafter, sometimes referred to as "component (C)"). The polymerizable composition according to this embodiment may contain, as a polymerizable compound, component (C), or may contain a polymerizable compound that does not correspond to component (C). In a phosphorus compound having a P═O(OH) structure, as shown in the following general formula (c1), an oxygen atom is bonded to a phosphorus atom via a double bond, and a hydroxy group is bonded to the phosphorus atom via a single bond. In component (C), the number of P═O(OH) structures (the number per molecule) may be 1, from the viewpoint of easily lowering the reaction initiation temperature in the initial stage of preparation of the polymerizable composition.

[0050] [In the formula, c11 represents an integer of 1 to 3, c12 represents an integer of 0 to 2, c11+c12 is 3, and R ｃ１ represents a monovalent group.

[0051] c11 may be 1 to 2, or 2 to 3, from the viewpoint of easily lowering the reaction initiation temperature in the initial stage of preparation of the polymerizable composition.

[0052] The component (C) has a monovalent group other than a hydroxy group (R in general formula (c1)) as a functional group bonded to a phosphorus atom. ｃ１ ) Examples of the monovalent group include a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group (e.g., a phenyl group), and a (meth)acryloyl group-containing group. The (meth)acryloyl group-containing group is a group having at least one group selected from the group consisting of an acryloyl group and a methacryloyl group.

[0053] From the viewpoint of easily lowering the reaction initiation temperature in the initial stage of preparation of the polymerizable composition, the component (C) may include at least one selected from the group consisting of a (meth)acrylate compound having a P═O(OH) structure, phosphoric acid, and phenylphosphonic acid, may include a (meth)acrylate compound having a P═O(OH) structure, and may include a compound represented by the following general formula (c2):

[0054] [In the formula, c21 represents an integer of 1 or 2, c22 represents an integer of 1 or 2, c21 + c22 is 3, c23 and c24 each independently represent an integer of 1 or more, and R ｃ２ represents a hydrogen atom or a methyl group.

[0055] From the viewpoint of easily lowering the reaction initiation temperature in the initial stage of preparation of the polymerizable composition, c23 may be 1 to 8, 1 to 6, 1 to 5, 3 to 8, 3 to 6, 3 to 5, 5 to 8, or 5 to 6. From the viewpoint of easily lowering the reaction initiation temperature in the initial stage of preparation of the polymerizable composition, c24 may be 1 to 4, 2 to 4, 1 to 3, or 1 to 2.

[0056] From the viewpoint of easily lowering the reaction initiation temperature in the initial stage of preparation of the polymerizable composition, the content of the component (C) may be 50.00 mass% or more, more than 50.00 mass%, 70.00 mass% or more, 80.00 mass% or more, 90.00 mass% or more, 92.00 mass% or more, 95.00 mass% or more, 97.00 mass% or more, 98.00 mass% or more, 99.00 mass% or more, or substantially 100.00 mass% based on the total mass of the phosphorus-containing compounds (compounds containing a phosphorus atom) contained in the polymerizable composition.

[0057] From the viewpoint of easily lowering the reaction initiation temperature at the initial stage of preparation of the polymerizable composition, the content of the component (C) may be within the following ranges based on the total mass of the polymerizable composition. The content of the component (C) may be 0.01 mass% or more, 0.05 mass% or more, 0.10 mass% or more, 0.20 mass% or more, 0.30 mass% or more, 0.40 mass% or more, 0.50 mass% or more, 0.60 mass% or more, 0.70 mass% or more, 0.80 mass% or more, or 0.90 mass% or more. The content of the component (C) may be 10.00 mass% or less, 8.00 mass% or less, 6.00 mass% or less, 5.00 mass% or less, 4.00 mass% or less, 3.00 mass% or less, 2.00 mass% or less, 1.80 mass% or less, 1.50 mass% or less, 1.20 mass% or less, or 1.00 mass% or less. From these viewpoints, the content of the component (C) may be 0.01 to 10.00 mass%, 0.01 to 2.00 mass%, 0.01 to 1.00 mass%, 0.20 to 10.00 mass%, 0.20 to 2.00 mass%, 0.20 to 1.00 mass%, 0.50 to 10.00 mass%, 0.50 to 2.00 mass%, or 0.50 to 1.00 mass%.

[0058] The mass ratio R21 of the content of the component (C) to the content of the component (a1) (component (C) / component (a1)) may be within the following range, from the viewpoint of easily lowering the reaction initiation temperature at the initial stage of preparation of the polymerizable composition. The mass ratio R21 may be 0.01 or more, 0.05 or more, 0.08 or more, 0.10 or more, 0.20 or more, 0.30 or more, 0.40 or more, 0.50 or more, 0.60 or more, or 0.70 or more. The mass ratio R21 may be 10.00 or less, 8.00 or less, 6.00 or less, 5.00 or less, 4.00 or less, 3.00 or less, 2.50 or less, 2.00 or less, 1.80 or less, 1.50 or less, 1.30 or less, 1.20 or less, 1.10 or less, 1.00 or less, 0.90 or less, or 0.80 or less. From these viewpoints, the mass ratio R21 may be 0.01 to 10.00, 0.01 to 5.00, 0.01 to 1.00, 0.10 to 10.00, 0.10 to 5.00, 0.10 to 1.00, 0.50 to 10.00, 0.50 to 5.00, or 0.50 to 1.00.

[0059] The mass ratio R22 of the content of the component (C) to the content of the component (B) (component (C) / component (B)) may be within the following range, from the viewpoint of easily lowering the reaction initiation temperature in the initial preparation of the polymerizable composition and easily achieving excellent storage stability with respect to the reaction initiation temperature. The mass ratio R22 may be 0.01 or more, 0.05 or more, 0.10 or more, 0.15 or more, 0.20 or more, 0.25 or more, 0.30 or more, 0.35 or more, 0.40 or more, 0.45 or more, 0.50 or more, 0.55 or more, 0.60 or more, 0.65 or more, or 0.70 or more. The mass ratio R22 may be 5.00 or less, 4.00 or less, 3.00 or less, 2.00 or less, 1.50 or less, 1.00 or less, 0.90 or less, 0.85 or less, 0.80 or less, or 0.75 or less. From these viewpoints, the mass ratio R22 may be 0.01 to 5.00, 0.01 to 1.50, 0.01 to 0.80, 0.20 to 5.00, 0.20 to 1.50, 0.20 to 0.80, 0.40 to 5.00, 0.40 to 1.50, or 0.40 to 0.80.

[0060] The polymerizable composition according to this embodiment may contain a polymerizable compound (excluding compounds corresponding to the component (a1), the component (B), or the component (C)) as the component (D).

[0061] Examples of the component (D) include a radically polymerizable compound, a cationically polymerizable compound, an anionically polymerizable compound, etc. The component (D) may contain a radically polymerizable compound from the viewpoint of easily lowering the reaction initiation temperature in the initial stage of preparation of the polymerizable composition.

[0062] Examples of the component (D) include (meth)acrylate compounds, maleimide compounds, vinyl ether compounds, allyl compounds, styrene compounds, (meth)acrylamide compounds, nadimide compounds, natural rubber, isoprene rubber, butyl rubber, nitrile rubber, butadiene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, carboxylated nitrile rubber, epoxy compounds, oxetane compounds, lactone compounds, etc. From the viewpoint of easily lowering the reaction initiation temperature in the initial stage of preparation of the polymerizable composition, the component (D) may include a compound having an ethylenically unsaturated bond and may include a (meth)acrylate compound.

[0063] Examples of the (meth)acrylate compound include (poly)urethane (meth)acrylate, epoxy (meth)acrylate, methyl (meth)acrylate, polyether (meth)acrylate, polyester (meth)acrylate, polybutadiene (meth)acrylate, silicone (meth)acrylate, ethyl (meth)acrylate, 2-cyanoethyl (meth)acrylate, 2-(2-ethoxyethoxy)ethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and n-hexyl (meth)acrylate. acrylate, 2-hydroxyethyl (meth)acrylate, isopropyl (meth)acrylate, hydroxypropyl (meth)acrylate, isobutyl (meth)acrylate, isobornyl (meth)acrylate, isodecyl (meth)acrylate, isooctyl (meth)acrylate, n-lauryl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, polyethylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol (meth)acrylate

[0033] Examples of the alkylene oxide-modified isocyanuric acid tri(meth)acrylate include 2-hydroxy-1,3-di(meth)acryloxypropane, 2,2-bis[4-((meth)acryloxymethoxy)phenyl]propane, and 2,2-bis[4-((meth)acryloxypolyethoxy)phenyl]propane.“Polyurethane (meth)acrylate” and “urethane (meth)acrylate” are collectively referred to as “(poly)urethane (meth)acrylate.” Component (D) may contain a difunctional (meth)acrylate compound.

[0064] From the viewpoint of easily lowering the reaction initiation temperature in the initial stage of preparation of the polymerizable composition, the component (D) may include a urethane (meth)acrylate compound having a polycarbonate skeleton (hereinafter referred to as “component (d1)”), may include a urethane (meth)acrylate compound having a structure derived from a polycarbonate polyol, or may include a compound represented by the following general formula (d1):

[0065] [In the formula, R １ represents a hydrogen atom or a methyl group, j represents an integer of 1 to 3, k represents an integer of 2 to 7, m represents an integer of 1 to 8, and n represents an integer of 5 to 7.

[0066] In general formula (d1), j may be 1 to 2 or 2 to 3, k may be 2 to 3 or 3 to 5, m may be 1 to 6, 1 to 4, or 1 to 2, and n may be 5 to 6 or 6 to 7, from the viewpoint of making it easy to decrease the reaction initiation temperature in the initial stage of preparation of the polymerizable composition.

[0067] From the viewpoint of easily lowering the reaction initiation temperature in the initial stage of preparation of the polymerizable composition, the weight average molecular weight of the component (d1) may be 1,000 or more, 3,000 or more, 5,000 or more, 8,000 or more, 10,000 or more, 12,000 or more, 13,000 or more, 14,000 or more, or 15,000 or more. From the viewpoint of easily lowering the reaction initiation temperature in the initial stage of preparation of the polymerizable composition, the weight average molecular weight of the component (d1) may be 100,000 or less, 50,000 or less, 30,000 or less, 25,000 or less, 20,000 or less, 18,000 or less, or 15,000 or less. From these viewpoints, the weight average molecular weight of the component (d1) may be 1,000 to 100,000, 5,000 to 50,000, or 10,000 to 30,000.

[0068] From the viewpoint of easily lowering the reaction initiation temperature at the initial stage of preparation of the polymerizable composition, the content of component (d1) may be within the following ranges based on the total mass of component (D). The content of component (d1) may be 10.00 mass% or more, 15.00 mass% or more, 20.00 mass% or more, 25.00 mass% or more, 30.00 mass% or more, 35.00 mass% or more, 40.00 mass% or more, 45.00 mass% or more, 50.00 mass% or more, or 55.00 mass% or more. The content of component (d1) may be 90.00 mass% or less, 85.00 mass% or less, 80.00 mass% or less, 75.00 mass% or less, 70.00 mass% or less, 65.00 mass% or less, or 60.00 mass% or less. From these viewpoints, the content of the (d1) component may be 10.00 to 90.00 mass%, 10.00 to 80.00 mass%, 10.00 to 70.00 mass%, 20.00 to 90.00 mass%, 20.00 to 80.00 mass%, 20.00 to 70.00 mass%, 40.00 to 90.00 mass%, 40.00 to 80.00 mass%, or 40.00 to 70.00 mass%.

[0069] From the viewpoint of easily lowering the reaction initiation temperature at the initial stage of preparation of the polymerizable composition, the content of the component (d1) may be within the following ranges based on the total mass of the polymerizable composition. The content of the component (d1) may be 5.00 mass% or more, 10.00 mass% or more, 15.00 mass% or more, or 20.00 mass% or more. The content of the component (d1) may be 50.00 mass% or less, 45.00 mass% or less, 40.00 mass% or less, 35.00 mass% or less, 30.00 mass% or less, or 25.00 mass% or less. From these viewpoints, the content of the (d1) component may be 5.00 to 50.00 mass%, 5.00 to 40.00 mass%, 5.00 to 30.00 mass%, 10.00 to 50.00 mass%, 10.00 to 40.00 mass%, 10.00 to 30.00 mass%, 20.00 to 50.00 mass%, 20.00 to 40.00 mass%, or 20.00 to 30.00 mass%.

[0070] From the viewpoint of easily lowering the reaction initiation temperature in the initial stage of preparation of the polymerizable composition, the component (D) may contain an isocyanuric acid alkylene oxide-modified di(meth)acrylate (excluding compounds corresponding to the component (d1); hereinafter referred to as “component (d2)”) or an isocyanuric acid ethylene oxide-modified di(meth)acrylate.

[0071] From the viewpoint of easily lowering the reaction initiation temperature at the initial stage of preparation of the polymerizable composition, the content of the component (d2) may be within the following ranges based on the total mass of the component (D): The content of the component (d2) may be 1.00 mass% or more, 5.00 mass% or more, 10.00 mass% or more, 15.00 mass% or more, or 20.00 mass% or more; The content of the component (d2) may be 50.00 mass% or less, 45.00 mass% or less, 40.00 mass% or less, 35.00 mass% or less, 30.00 mass% or less, or 25.00 mass% or less. From these viewpoints, the content of the (d2) component may be 1.00 to 50.00 mass%, 1.00 to 40.00 mass%, 1.00 to 30.00 mass%, 10.00 to 50.00 mass%, 10.00 to 40.00 mass%, 10.00 to 30.00 mass%, 20.00 to 50.00 mass%, 20.00 to 40.00 mass%, or 20.00 to 30.00 mass%.

[0072] From the viewpoint of easily lowering the reaction initiation temperature at the initial stage of preparation of the polymerizable composition, the content of the component (d2) may be within the following ranges based on the total mass of the polymerizable composition. The content of the component (d2) may be 1.00 mass% or more, 3.00 mass% or more, 5.00 mass% or more, 8.00 mass% or more, or 9.00 mass% or more. The content of the component (d2) may be 30.00 mass% or less, 25.00 mass% or less, 20.00 mass% or less, 15.00 mass% or less, or 10.00 mass% or less. From these viewpoints, the content of the (d2) component may be 1.00 to 30.00 mass%, 1.00 to 20.00 mass%, 1.00 to 10.00 mass%, 5.00 to 30.00 mass%, 5.00 to 20.00 mass%, 5.00 to 10.00 mass%, 7.00 to 30.00 mass%, 7.00 to 20.00 mass%, or 7.00 to 10.00 mass%.

[0073] From the viewpoint of making it easier to lower the reaction initiation temperature in the initial stage of preparation of the polymerizable composition, the component (D) may include a di(meth)acrylate compound having at least one selected from the group consisting of a dicyclopentanyl structure and a dicyclopentenyl structure (excluding compounds corresponding to the component (d1) or the component (d2); hereinafter referred to as “component (d3)”), and may include at least one selected from the group consisting of dimethyloltricyclodecanedi(meth)acrylate and tricyclodecanedioldi(meth)acrylate.

[0074] From the viewpoint of easily lowering the reaction initiation temperature at the initial stage of preparation of the polymerizable composition, the content of the component (d3) may be within the following ranges based on the total mass of the component (D): The content of the component (d3) may be 1.00 mass% or more, 5.00 mass% or more, 10.00 mass% or more, 15.00 mass% or more, or 20.00 mass% or more. The content of the component (d3) may be 50.00 mass% or less, 45.00 mass% or less, 40.00 mass% or less, 35.00 mass% or less, 30.00 mass% or less, or 25.00 mass% or less. From these viewpoints, the content of the (d3) component may be 1.00 to 50.00 mass%, 1.00 to 40.00 mass%, 1.00 to 30.00 mass%, 10.00 to 50.00 mass%, 10.00 to 40.00 mass%, 10.00 to 30.00 mass%, 20.00 to 50.00 mass%, 20.00 to 40.00 mass%, or 20.00 to 30.00 mass%.

[0075] From the viewpoint of easily lowering the reaction initiation temperature at the initial stage of preparation of the polymerizable composition, the content of the component (d3) may be within the following ranges based on the total mass of the polymerizable composition. The content of the component (d3) may be 1.00 mass% or more, 3.00 mass% or more, 5.00 mass% or more, 8.00 mass% or more, or 9.00 mass% or more. The content of the component (d3) may be 30.00 mass% or less, 25.00 mass% or less, 20.00 mass% or less, 15.00 mass% or less, or 10.00 mass% or less. From these viewpoints, the content of the (d3) component may be 1.00 to 30.00 mass%, 1.00 to 20.00 mass%, 1.00 to 10.00 mass%, 5.00 to 30.00 mass%, 5.00 to 20.00 mass%, 5.00 to 10.00 mass%, 7.00 to 30.00 mass%, 7.00 to 20.00 mass%, or 7.00 to 10.00 mass%.

[0076] From the viewpoint of easily lowering the reaction initiation temperature at the initial stage of preparation of the polymerizable composition, the content of the component (D) may be within the following ranges based on the total mass of the polymerizable composition. The content of the component (D) may be 10.00 mass% or more, 15.00 mass% or more, 20.00 mass% or more, 25.00 mass% or more, 30.00 mass% or more, 35.00 mass% or more, or 40.00 mass% or more. The content of the component (D) may be 80.00 mass% or less, 75.00 mass% or less, 70.00 mass% or less, 65.00 mass% or less, 60.00 mass% or less, 55.00 mass% or less, 50.00 mass% or less, or 45.00 mass% or less. From these viewpoints, the content of the (D) component may be 10.00 to 80.00 mass%, 10.00 to 60.00 mass%, 10.00 to 50.00 mass%, 30.00 to 80.00 mass%, 30.00 to 60.00 mass%, 30.00 to 50.00 mass%, 35.00 to 80.00 mass%, 35.00 to 60.00 mass%, or 35.00 to 50.00 mass%.

[0077] The mass ratio R31 of the content of the component (D) to the content of the component (a1) (component (D) / component (a1)) may be within the following ranges, from the viewpoint of easily lowering the reaction initiation temperature at the initial stage of preparation of the polymerizable composition. The mass ratio R31 may be 1.00 or more, 5.00 or more, 10.00 or more, 15.00 or more, 20.00 or more, 25.00 or more, or 30.00 or more. The mass ratio R31 may be 300.00 or less, 250.00 or less, 200.00 or less, 150.00 or less, 120.00 or less, 100.00 or less, 80.00 or less, 60.00 or less, 50.00 or less, or 40.00 or less. From these viewpoints, the mass ratio R31 may be 1.00 to 300.00, 1.00 to 120.00, 1.00 to 60.00, 20.00 to 300.00, 20.00 to 120.00, 20.00 to 60.00, 30.00 to 300.00, 30.00 to 120.00, or 30.00 to 60.00.

[0078] The mass ratio R32 of the content of the component (D) to the content of the component (B) (component (D) / component (B)) may be within the following range, from the viewpoint of easily lowering the reaction initiation temperature in the initial preparation of the polymerizable composition and easily achieving excellent storage stability with respect to the reaction initiation temperature. The mass ratio R32 may be 1.00 or more, 5.00 or more, 10.00 or more, 15.00 or more, 20.00 or more, 25.00 or more, or 30.00 or more. The mass ratio R32 may be 300.00 or less, 200.00 or less, 100.00 or less, 80.00 or less, 50.00 or less, 45.00 or less, 40.00 or less, or 35.00 or less. From these viewpoints, the mass ratio R32 may be 1.00 to 300.00, 1.00 to 100.00, 1.00 to 50.00, 10.00 to 300.00, 10.00 to 100.00, 10.00 to 50.00, 20.00 to 300.00, 20.00 to 100.00, or 20.00 to 50.00.

[0079] The mass ratio R33 of the content of the component (D) to the content of the component (C) (component (D) / component (C)) may be within the following ranges, from the viewpoint of easily lowering the reaction initiation temperature at the initial stage of preparation of the polymerizable composition. The mass ratio R33 may be 1.00 or more, 5.00 or more, 10.00 or more, 15.00 or more, 20.00 or more, 25.00 or more, 30.00 or more, 35.00 or more, 40.00 or more, or 45.00 or more. The mass ratio R33 may be 300.00 or less, 250.00 or less, 200.00 or less, 150.00 or less, 140.00 or less, 100.00 or less, 80.00 or less, 70.00 or less, 60.00 or less, 50.00 or less, or 45.00 or less. From these viewpoints, the mass ratio R33 may be 1.00 to 300.00, 1.00 to 100.00, 1.00 to 60.00, 20.00 to 300.00, 20.00 to 100.00, 20.00 to 60.00, 30.00 to 300.00, 30.00 to 100.00, or 30.00 to 60.00.

[0080] The polymerizable composition according to this embodiment may contain a polymerization initiator (excluding compounds corresponding to the components (a1), (B), (C), or (D)) as the component (E). The component (E) may contain a thermal polymerization initiator. Examples of the component (E) include a radical polymerization initiator, a cationic polymerization initiator, and an anionic polymerization initiator. The component (E) may contain a radical polymerization initiator from the viewpoint of easily lowering the reaction initiation temperature in the initial stage of preparation of the polymerizable composition.

[0081] Examples of the component (E) include ketone peroxides such as methyl ethyl ketone peroxide, cyclohexanone peroxide, and methylcyclohexanone peroxide; peroxyketals such as 1,1-bis(tert-butylperoxy)cyclohexane, 1,1-bis(tert-butylperoxy)-2-methylcyclohexane, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-hexylperoxy)cyclohexane, and 1,1-bis(tert-hexylperoxy)-3,3,5-trimethylcyclohexane; and hydroperoxides such as p-menthane hydroperoxide. peroxides such as α,α'-bis(tert-butylperoxy)diisopropylbenzene, dicumyl peroxide, tert-butylcumyl peroxide, and di-tert-butyl peroxide; diacyl peroxides such as dioctanoyl peroxide, dilauroyl peroxide, distearyl peroxide, and dibenzoyl peroxide; peroxycarbonates such as bis(4-tert-butylcyclohexyl)peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, and di-3-methoxybutyl peroxycarbonate;tert-Butyl peroxypivalate, tert-hexyl peroxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane, tert-hexylperoxy-2-ethylhexanoate, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxyisobutyrate, tert-hexylperoxyisopropyl monocarbonate, tert- Peroxyesters such as butylperoxy-3,5,5-trimethylhexanoate, tert-butylperoxylaurate, tert-butylperoxyisopropyl monocarbonate, tert-butylperoxy-2-ethylhexyl monocarbonate, tert-butylperoxybenzoate, tert-hexylperoxybenzoate, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane, and tert-butylperoxyacetate; phthalic anhydride, maleic anhydride Acid, trimellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylnadic anhydride, nadic anhydride, glutaric anhydride, dimethylglutaric anhydride, diethylglutaric anhydride, succinic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 4,4'-biphthalic anhydride, 4,4'-carbonyldiphthalic anhydride, 4,4'-sulfonyldiphthalic anhydride, 4,4'-(hexafluoroisopropyl) acid anhydrides such as 4,4'-hydroxydiphthalic anhydride, 4,4'-oxydiphthalic anhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, and 2,3,6,7-naphthalenetetracarboxylic dianhydride; azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), and 2,2'-azobis(4-methoxy-2'-dimethylvaleronitrile); iodonium salts; sulfonium salts; phosphonium salts; and imidazole compounds.

[0082] The component (E) may contain a peroxide, an organic peroxide, or a diacyl peroxide, from the viewpoint of easily lowering the reaction initiation temperature in the initial stage of preparation of the polymerizable composition.

[0083] From the viewpoint of easily lowering the reaction initiation temperature at the initial stage of preparation of the polymerizable composition, the content of the component (E) may be within the following ranges based on the total mass of the polymerizable composition. The content of the component (E) may be 0.10 mass% or more, 0.50 mass% or more, 1.00 mass% or more, 1.50 mass% or more, 2.00 mass% or more, 2.50 mass% or more, 3.00 mass% or more, 3.50 mass% or more, 4.00 mass% or more, or 4.50 mass% or more. The content of the component (E) may be 20.00 mass% or less, 15.00 mass% or less, 10.00 mass% or less, 9.00 mass% or less, 8.00 mass% or less, 7.00 mass% or less, 6.00 mass% or less, or 5.00 mass% or less. From these viewpoints, the content of the component (E) may be 0.10 to 20.00 mass%, 0.10 to 10.00 mass%, 0.10 to 5.00 mass%, 1.00 to 20.00 mass%, 1.00 to 10.00 mass%, 1.00 to 5.00 mass%, 3.00 to 20.00 mass%, 3.00 to 10.00 mass%, or 3.00 to 5.00 mass%.

[0084] The mass ratio R41 of the content of the component (E) to the content of the component (a1) (component (E) / component (a1)) may be within the following range, from the viewpoint of easily lowering the reaction initiation temperature in the initial stage of preparation of the polymerizable composition. The mass ratio R41 may be 0.10 or more, 0.50 or more, 1.00 or more, 2.00 or more, 3.00 or more, or 3.50 or more. The mass ratio R41 may be 50.00 or less, 30.00 or less, 20.00 or less, 15.00 or less, 10.00 or less, 8.00 or less, 6.00 or less, 5.00 or less, or 4.00 or less. From these viewpoints, the mass ratio R41 may be 0.10 to 50.00, 0.10 to 15.00, 0.10 to 6.00, 1.00 to 50.00, 1.00 to 15.00, 1.00 to 6.00, 3.00 to 50.00, 3.00 to 15.00, or 3.00 to 6.00.

[0085] The mass ratio R42 of the content of the component (E) to the content of the component (B) (component (E) / component (B)) may be within the following range, from the viewpoint of easily lowering the reaction initiation temperature in the initial stage of preparation of the polymerizable composition and easily achieving excellent storage stability with respect to the reaction initiation temperature. The mass ratio R42 may be 0.10 or more, 0.50 or more, 1.00 or more, 1.50 or more, 2.00 or more, 2.50 or more, 3.00 or more, or 3.50 or more. The mass ratio R42 may be 50.00 or less, 30.00 or less, 20.00 or less, 15.00 or less, 10.00 or less, 8.00 or less, 5.00 or less, 4.50 or less, or 4.00 or less. From these viewpoints, the mass ratio R42 may be 0.10 to 50.00, 0.10 to 20.00, 0.10 to 5.00, 1.00 to 50.00, 1.00 to 20.00, 1.00 to 5.00, 2.00 to 50.00, 2.00 to 20.00, or 2.00 to 5.00.

[0086] The mass ratio R43 of the content of the component (E) to the content of the component (C) (component (E) / component (C)) may be within the following range, from the viewpoint of easily lowering the reaction initiation temperature at the initial stage of preparation of the polymerizable composition. The mass ratio R43 may be 0.10 or more, 0.50 or more, 1.00 or more, 1.50 or more, 2.00 or more, 2.50 or more, 3.00 or more, 3.50 or more, 4.00 or more, 4.50 or more, or 5.00 or more. The mass ratio R43 may be 50.00 or less, 30.00 or less, 20.00 or less, 15.00 or less, 12.00 or less, 10.00 or less, 9.00 or less, 8.00 or less, 7.00 or less, 6.50 or less, 6.00 or less, 5.50 or less, or 5.00 or less. From these viewpoints, the mass ratio R43 may be 0.10 to 50.00, 0.10 to 10.00, 0.10 to 6.00, 1.00 to 50.00, 1.00 to 10.00, 1.00 to 6.00, 3.00 to 50.00, 3.00 to 10.00, or 3.00 to 6.00.

[0087] The mass ratio R44 of the content of the component (E) to the content of the component (D) (component (E) / component (D)) may be within the following range, from the viewpoint of easily lowering the reaction initiation temperature in the initial stage of preparation of the polymerizable composition. The mass ratio R44 may be 0.01 or more, 0.03 or more, 0.05 or more, 0.08 or more, or 0.10 or more. The mass ratio R44 may be 5.00 or less, 3.00 or less, 1.00 or less, 0.50 or less, 0.30 or less, 0.20 or less, or 0.15 or less. From these viewpoints, the mass ratio R44 may be 0.01 to 5.00, 0.01 to 1.00, 0.01 to 0.50, 0.05 to 5.00, 0.05 to 1.00, 0.05 to 0.50, 0.10 to 5.00, 0.10 to 1.00, or 0.10 to 0.50.

[0088] The polymerizable composition according to this embodiment may contain a thermoplastic resin as the component (F).

[0089] Examples of the component (F) include phenoxy resins, polyesters, polyurethanes (excluding polyesterurethanes), polyesterurethanes, ethylene-vinyl acetate copolymers, butyral resins, etc. The component (F) may contain at least one selected from the group consisting of polyesterurethanes and ethylene-vinyl acetate copolymers, from the viewpoint of easily lowering the reaction initiation temperature in the initial stage of preparation of the polymerizable composition.

[0090] From the viewpoint of easily lowering the reaction initiation temperature at the initial stage of preparation of the polymerizable composition, the content of the component (F) may be within the following ranges based on the total mass of the polymerizable composition. The content of the component (F) may be 10.00 mass% or more, 15.00 mass% or more, 20.00 mass% or more, 25.00 mass% or more, 30.00 mass% or more, 35.00 mass% or more, 40.00 mass% or more, 45.00 mass% or more, or 50.00 mass% or more. The content of the component (F) may be 90.00 mass% or less, 85.00 mass% or less, 80.00 mass% or less, 75.00 mass% or less, 70.00 mass% or less, 65.00 mass% or less, 60.00 mass% or less, or 55.00 mass% or less. From these viewpoints, the content of the (F) component may be 10.00 to 90.00 mass%, 10.00 to 70.00 mass%, 10.00 to 60.00 mass%, 30.00 to 90.00 mass%, 30.00 to 70.00 mass%, 30.00 to 60.00 mass%, 40.00 to 90.00 mass%, 40.00 to 70.00 mass%, or 40.00 to 60.00 mass%.

[0091] The polymerizable composition according to this embodiment may contain components other than those described above. Examples of such components include water, organic solvents, coupling agents, fillers, softeners, accelerators, anti-degradants, colorants, flame retardants, and thixotropic agents. The polymerizable composition according to this embodiment may contain at least one of these components, or may not contain at least one of these components.

[0092] The polymerizable composition according to this embodiment may be in the form of a film. The thickness of the film-like polymerizable composition or the thickness of the cured product according to this embodiment may be in the following ranges. The thickness may be 1 μm or more, 3 μm or more, 5 μm or more, 8 μm or more, 10 μm or more, 12 μm or more, 15 μm or more, 18 μm or more, or 20 μm or more. The thickness may be 500 μm or less, 300 μm or less, 200 μm or less, 100 μm or less, 80 μm or less, 50 μm or less, 30 μm or less, or 20 μm or less. From these viewpoints, the thickness may be 1 to 500 μm, 1 to 100 μm, 1 to 50 μm, 5 to 500 μm, 5 to 100 μm, 5 to 50 μm, 10 to 500 μm, 10 to 100 μm, or 10 to 50 μm.

[0093] The method for selecting a polymerizable composition (screening method) according to the present embodiment is a method for selecting a polymerizable composition containing a polymerizable compound. The method involves selecting a polymerizable composition containing a borate anion and at least one carboxylic acid component selected from the group consisting of a carboxylic acid, a salt of the carboxylic acid, and a hydrate of the carboxylic acid, based on the proton dissociation energy (proton dissociation energy E) of the proton dissociation group of the carboxylic acid and the inflection point temperature (density inflection point temperature T) in the temperature dependence curve of the density of the carboxylic acid. According to the method for selecting a polymerizable composition according to the present embodiment, a carboxylic acid is selected based on the proton dissociation energy E and the density inflection point temperature T, and a polymerizable composition containing a borate anion and at least one carboxylic acid component selected from the group consisting of the carboxylic acid, a salt of the carboxylic acid, and a hydrate of the carboxylic acid is selected. This makes it possible to adjust the reaction initiation temperature at the initial stage of preparation of the polymerizable composition and the change in the reaction initiation temperature over time after preparation of the polymerizable composition, thereby enabling the production of a polymerizable composition with a desired reaction initiation temperature and its change over time. The method for selecting a polymerizable composition according to the present embodiment allows the selection of a polymerizable composition according to the present embodiment. In the method for selecting a polymerizable composition according to this embodiment, a polymerizable composition containing a borate anion and at least one carboxylic acid component selected from the group consisting of carboxylic acid b, a salt of carboxylic acid b, and a hydrate of carboxylic acid b, each of which has a proton dissociation energy E of 295.5 kJ / mol or more and a density inflection point temperature T of 135.0°C or less, may be selected.

[0094] The method for producing a polymerizable composition according to this embodiment includes a mixing step of mixing borate anions with at least one carboxylic acid component selected from the group consisting of carboxylic acid b, a salt of carboxylic acid b, and a hydrate of carboxylic acid b. The method for producing a polymerizable composition according to this embodiment can provide the polymerizable composition according to this embodiment. The method for producing a polymerizable composition according to this embodiment may include a step of selecting carboxylic acid b based on the proton dissociation energy (proton dissociation energy E) of a proton dissociative group of the carboxylic acid and the inflection point temperature (density inflection point temperature T) in a temperature dependence curve of the density of the carboxylic acid, prior to the mixing step.

[0095] In the method for selecting a polymerizable composition and the method for producing a polymerizable composition according to this embodiment, the same borate anion as that of the component (A) of the polymerizable composition according to this embodiment can be used as the borate anion. The borate anion in the method for selecting a polymerizable composition and the method for producing a polymerizable composition according to this embodiment may satisfy the characteristics described above for the component (A) of the polymerizable composition according to this embodiment.

[0096] In the method for selecting a polymerizable composition and the method for producing a polymerizable composition according to this embodiment, a component similar to the component (B) of the polymerizable composition according to this embodiment can be used as the carboxylic acid component. The carboxylic acid component in the method for selecting a polymerizable composition and the method for producing a polymerizable composition according to this embodiment may satisfy the characteristics described above for the component (B) of the polymerizable composition according to this embodiment.

[0097] The present disclosure will be further described below using examples and comparative examples, but the present disclosure is not limited to the following examples.

[0098] <Synthesis of urethane acrylate (UA1)> 2,500 parts by mass (2.50 mol) of poly(1,6-hexanediol carbonate) (trade name: Duranol T5652, manufactured by Asahi Kasei Chemicals Corporation) and 666 parts by mass (3.00 mol) of isophorone diisocyanate (manufactured by Sigma-Aldrich Co.) were uniformly added dropwise over 3 hours to a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser with a calcium chloride drying tube, and a nitrogen gas inlet tube. Next, nitrogen gas was sufficiently introduced into the reaction vessel, and the reaction vessel was then heated to 70 to 75°C to allow the mixture to react. Next, 0.53 parts by mass (4.3 mmol) of hydroquinone monomethyl ether (Sigma-Aldrich) and 5.53 parts by mass (8.8 mmol) of dibutyltin dilaurate (Sigma-Aldrich) were added to the reaction vessel, followed by the addition of 238 parts by mass (2.05 mol) of 2-hydroxyethyl acrylate (Sigma-Aldrich), and the mixture was allowed to react at 70°C for 6 hours in an air atmosphere. This yielded a urethane acrylate (UA1) having a polycarbonate skeleton. The weight-average molecular weight of the urethane acrylate (UA1) was 15,000.

[0099] <Synthesis of Polyester Urethane (EU1)> 48 parts by mass of isophthalic acid and 37 parts by mass of neopentyl glycol were added to a heated stainless steel autoclave equipped with a stirrer, thermometer, condenser, vacuum generator, and nitrogen gas inlet tube, followed by 0.02 parts by mass of tetrabutoxy titanate as a catalyst. The mixture was then heated to 220°C under a nitrogen stream and stirred for 8 hours. The pressure was then reduced to atmospheric pressure (760 mmHg) and cooled to room temperature. This resulted in the deposition of a white precipitate, which was then removed. The precipitate was washed with water and vacuum-dried to obtain a polyester polyol. After thoroughly drying the polyester polyol, it was dissolved in MEK (methyl ethyl ketone) and added to a four-neck flask equipped with a stirrer, a dropping funnel, a reflux condenser, and a nitrogen gas inlet tube. Furthermore, 0.05 parts by mass of dibutyltin dilaurate (catalyst) was added relative to 100 parts by mass of the polyester polyol, and 50 parts by mass of 4,4'-diphenylmethane diisocyanate was dissolved in MEK relative to 100 parts by mass of the polyester polyol and added using a dropping funnel. The mixture was then stirred at 80°C for 4 hours to obtain a polyester urethane (EU1).

[0100] <Preparation of Polymerizable Composition> A polymerizable composition was prepared by mixing a methyl ethyl ketone solution (solids content: 20% by mass) of a boron salt (tetrabutylammonium = butyltrinaphthyl borate, manufactured by Resonac Corporation, trade name: Karenz N3B), the types of acid components shown in Table 1, a urethane acrylate (UA1), an isocyanuric acid ethylene oxide-modified diacrylate (manufactured by Toagosei Co., Ltd., trade name: M-215), dimethylol tricyclodecane diacrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name: Light Acrylate DCP-A), a toluene solution (solids content: 20% by mass) of a polymerization initiator (diacyl peroxide, manufactured by NOF Corporation, trade name: Perloyl L), a methyl ethyl ketone / toluene mixed solution (mass ratio: 1 / 1, solids content: 40% by mass) of a polyester urethane (EU1), and a toluene solution (solids content: 30% by mass) of an ethylene vinyl acetate copolymer (manufactured by DuPont Co., Ltd., trade name: EV40W). The amount of boron salt used (solid content) was 1.29 parts by mass, the amount of acid component used (solid content) was 1.41 parts by mass, the amount of urethane acrylate (UA1) used was 25.00 parts by mass, the amount of isocyanuric acid ethylene oxide-modified diacrylate used was 10.00 parts by mass, the amount of dimethyloltricyclodecane diacrylate used was 10.00 parts by mass, the amount of polymerization initiator used (solid content) was 5.00 parts by mass, the amount of polyester urethane (EU1) used (solid content) was 47.50 parts by mass, and the amount of ethylene vinyl acetate copolymer used (solid content) was 7.50 parts by mass. Acid components manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd. were used as each acid component in the examples and comparative examples.

[0101] <Calculation of Proton Dissociation Energy E and Density Inflection Point Temperature T> The proton dissociation energy E and density inflection point temperature T of each acid component in the Examples and Comparative Examples were calculated by the following procedure.

[0102] (Proton Dissociation Energy E) The structure of the target acid component was optimized by quantum chemical calculation, and the "energy E1 of the entire molecule of the acid component," "energy E2 of the entire molecule when the proton to be dissociated dissociates from the proton dissociative group of the acid component," and "energy E3 of the dissociated proton alone" were calculated. The quantum chemical calculation was performed based on density functional theory using the program Gaussian 16 (manufactured by Gaussian Corporation), functional B3LYP, and basis function 6-31G(d). The proton dissociation energy E was then calculated based on "proton dissociation energy E = (E2 + E3) - E1." The proton dissociation energy E was calculated for all proton dissociative groups contained in the acid component. Table 1 shows the minimum value of the proton dissociation energy E of the proton dissociative group in each acid component of the Examples and Comparative Examples.

[0103] (Density inflection point temperature T) Using the Packmol program, an initial structure was obtained by packing the target acid component molecules to approximately 10,000 atoms. Using this initial structure, molecular dynamics calculations for the temperature range of 280 to 500 K (program: GROMACS 2020, force field: GAFF2, charge: RESP (calculated using the program Gaussian16 (Gaussian), B3LYP / 6-31G(d) / / HF / 6-31G(d))) were performed in the following procedure to obtain the density for each temperature. First, a relaxation calculation was performed at a temperature of 500 K to allow equilibration. After equilibration, sampling was performed for 10 ns to obtain the density. The temperature was lowered by 10 K, a relaxation calculation was performed to allow equilibration, and then sampling was performed for 10 ns to obtain the density. This operation was repeated up to a temperature of 280 K.

[0104] Next, the density obtained at each temperature was plotted against the temperature to obtain a temperature dependence curve of density. Approximate lines were obtained for the five end points of the low-temperature region (five measurement points from the end at 280 K) and the five end points of the high-temperature region (five measurement points from the end at 500 K), and then the density inflection temperature T (unit: °C) was obtained by subtracting 273.15 from the temperature (unit: K) at the intersection point where the two approximate lines were extended. The density inflection temperatures T for each acid component in the Examples and Comparative Examples are shown in Table 1.

[0105] <Evaluation> The above-described polymerizable composition was applied to a PET film (with release treatment, thickness: 50 μm) using a bar coater (manufactured by Yasui Seiki Co., Ltd., product name "KNIFE COATER SNC-300"), and then dried in an oven at 60°C for 3 minutes to prepare a laminated film including a 20 μm-thick film of the polymerizable composition disposed on the PET film.

[0106] After peeling the PET film from the laminate film immediately after preparation, the exothermic behavior of the film-like polymerizable composition during curing was measured by differential scanning calorimetry (DSC), and the onset temperature of the exothermic peak was obtained as an index of the polymerization reaction initiation temperature. DSC measurements were performed under the following conditions to obtain the reaction initiation temperature T1. Furthermore, the laminate film immediately after preparation in the examples was placed in a nylon plastic bag (manufactured by Fukusuke Kogyo Co., Ltd., product name "Nylon Poly S Type"), and the bag was then sealed using a vacuum degassing sealer to enclose the laminate film. This bag was then placed in an aluminum light-shielding bag. After leaving the laminate film in this state at 25°C for 24 hours, the laminate film was removed from the light-shielding bag, and the reaction initiation temperature T2 was obtained using the same procedure as described above. The difference in reaction initiation temperature, "T2 - T1," was then calculated. The results are shown in Table 1. (DSC measurement conditions) Measurement device: PerkinElmer Japan Co., Ltd., product name "DSC8500" Sample amount: 10.0±0.2 mg Measurement temperature range: 30 to 200°C Heating rate: 30°C / min Measurement atmosphere: nitrogen

[0107]

Claims

1. A method for selecting a polymerizable composition containing a polymerizable compound, comprising selecting a polymerizable composition containing a borate anion and at least one selected from the group consisting of a carboxylic acid, a salt of the carboxylic acid, and a hydrate of the carboxylic acid, based on the proton dissociation energy of a proton dissociative group of the carboxylic acid and the inflection point temperature in a temperature dependence curve of the density of the carboxylic acid.

2. The method for selecting a polymerizable composition according to claim 1, wherein the borate anion includes a borate anion having a naphthalene ring.

3. The method for selecting a polymerizable composition according to claim 1, wherein the borate anion comprises an alkyltriarylborate anion.

4. The method for selecting a polymerizable composition according to any one of claims 1 to 3, wherein the carboxylic acid comprises an aromatic carboxylic acid.

5. The method for selecting a polymerizable composition according to any one of claims 1 to 3, wherein the number of hydroxy groups in the carboxylic acid is two.

6. The method for selecting a polymerizable composition according to any one of claims 1 to 3, wherein the polymerizable compound includes a (meth)acrylate compound.

7. A polymerizable composition containing a polymerizable compound, comprising a borate anion and at least one selected from the group consisting of a carboxylic acid, a salt of the carboxylic acid, and a hydrate of the carboxylic acid, wherein the proton dissociation energy of a proton dissociative group of the carboxylic acid is 295.5 kJ / mol or more, and the inflection point temperature in a temperature dependence curve of the density of the carboxylic acid is 135.0°C or less.

8. The polymerizable composition of claim 7, wherein the borate anion comprises a borate anion having a naphthalene ring.

9. The polymerizable composition of claim 7, wherein the borate anion comprises an alkyltriarylborate anion.

10. The polymerizable composition of any one of claims 7 to 9, wherein the carboxylic acid comprises an aromatic carboxylic acid.

11. The polymerizable composition according to any one of claims 7 to 9, wherein the number of hydroxy groups in the carboxylic acid is two.

12. The polymerizable composition according to any one of claims 7 to 9, wherein the polymerizable compound comprises a (meth)acrylate compound.

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