Polymerizable composition

Abstract

Provided is a polymerizable composition containing a polymerizable compound, the polymerizable composition containing (A) a borate anion and (B) at least one substance selected from the group consisting of an aromatic carboxylic acid having two or more hydroxyl groups, a salt of the aromatic carboxylic acid, and a hydrate of the aromatic carboxylic acid.

Description

Technical Field

[0001] The present invention relates to a polymerizable composition, etc. Background Art

[0002] In recent years, polymerizable compositions have been used for bonding various parts when manufacturing various devices. For example, Patent Document 1 below describes a thermosetting composition containing a polymerizable compound.

[0003] Previous technical literature

[0004] Patent Literature

[0005] Patent Document 1: Japanese Patent Application Publication No. 2014-156522 Summary of the invention

[0006] Technical issues to be solved by the invention

[0007] In recent years, with the miniaturization and high performance of various devices, when a polymerizable composition is thermally cured near a part that should be avoided from being exposed to high heat, there are cases where a polymerizable composition is thermally cured in contact with a part that should be avoided from being exposed to high heat, etc. In these cases, from the viewpoint of avoiding degradation of the part by thermal curing at a low temperature, it is required to lower the reaction starting temperature of the polymerizable composition.

[0008] An object of one aspect of the present invention is to provide a polymerizable composition capable of lowering the reaction initiation temperature.

[0009] Means for solving technical problems

[0010] The present invention relates to the following [1] to

[11] and the like in several aspects.

[0011] [1] A polymerizable composition comprising a polymerizable compound, wherein the polymerizable composition comprises (A) a borate anion and (B) at least one selected from the group consisting of an aromatic carboxylic acid having two or more hydroxyl groups, a salt of the aromatic carboxylic acid, and a hydrate of the aromatic carboxylic acid.

[0012] [2] The polymerizable composition according to [1], wherein the component (A) contains a borate anion having a naphthalene ring.

[0013] [3] The polymerizable composition according to [1] or [2], wherein the component (A) contains an alkyltriarylborate anion.

[0014] [4] The polymerizable composition according to any one of [1] to [3], wherein the number of naphthalene rings in the component (A) is 3.

[0015] [5] The polymerizable composition according to any one of [1] to [4], wherein the content of the boron salt contained in the component (A) is 0.01 to 20.00% by mass.

[0016] [6] The polymerizable composition according to any one of [1] to [5], wherein the number of hydroxyl groups in the aromatic carboxylic acid is 2.

[0017] [7] The polymerizable composition according to any one of [1] to [5], wherein the number of hydroxyl groups in the aromatic carboxylic acid is 3.

[0018] [8] The polymerizable composition according to any one of [1] to [7], wherein the content of the component (B) is 0.01 to 10.00% by mass.

[0019] [9] The polymerizable composition according to any one of [1] to [8], wherein the mass ratio of the content of the component (B) to the content of the boron salt contained in the component (A) is 0.01 to 10.00.

[0020]

[10] The polymerizable composition according to any one of [1] to [9], wherein the polymerizable compound contains a (meth)acrylate compound.

[0021]

[11] The polymerizable composition according to any one of [1] to

[10] , further comprising a polymerization initiator.

[0022] Effects of the Invention

[0023] According to one aspect of the present invention, a polymerizable composition capable of lowering a reaction initiation temperature can be provided. DETAILED DESCRIPTION

[0024] Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited to the following embodiments.

[0025] In this specification, the numerical range indicated by "~" indicates a range including the numerical values ​​recorded before and after "~" as the minimum and maximum values, respectively. "Above A" in the numerical range refers to A and the range exceeding A. "Below A" in the numerical range refers to A and the range less than A. In the numerical range described in stages in this specification, the upper limit or lower limit of the numerical range of a certain stage can be arbitrarily combined with the upper limit or lower limit of the numerical range of other stages. In the numerical range described in this specification, the upper limit or lower limit of the numerical range can be replaced by the value shown in the embodiment. "A or B" can include either A and B, or both. The materials exemplified in this specification are not particularly limited and can be used alone or in combination of two or more. Regarding the content of each component in the composition, when there are multiple substances corresponding to each component in the composition, unless otherwise specified, it refers to the total amount of the multiple substances present in the composition. "(Meth)acrylate" refers to at least one of acrylate and its corresponding methacrylate. The same is true in other similar expressions such as "(meth)acrylic acid". The content of (meth)acrylate compounds refers to the total amount of acrylate compounds and methacrylate compounds. Unless otherwise specified, "alkyl" can be any of linear, branched or cyclic. "Hydroxyl" does not include the OH group contained in the carboxyl group. "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 component from which the volatile components (water, organic solvents, etc.) that can volatilize are removed. That is, the solid component refers to the component that does not volatilize and remains during the drying of the polymerizable composition, and also includes components that are liquid, maltose, waxy, etc. at 25°C.

[0026] In this specification, the "weight average molecular weight" can be measured by gel permeation chromatography (GPC) under the following measurement conditions and converted from a calibration curve using standard polystyrene.

[0027] (Measurement conditions)

[0028] Device: Made by TOSOH CORPORATION, GPC-8020

[0029] Detector: Made by TOSOH CORPORATION, RI-8020

[0030] Column: Showa Denko KK, Gelpack GL-A-160-S+GL-A150

[0031] Sample concentration: 120mg / 3mL

[0032] Solvent: Tetrahydrofuran

[0033] Injection volume: 60μL

[0034] Pressure: 294×10 6 Pa(30kgf / cm 2 )

[0035] Flow rate: 1.00mL / min

[0036] The polymerizable composition according to the present embodiment is a polymerizable composition containing a polymerizable compound, which contains (A) a borate anion (hereinafter, referred to as "(A) component" as the case may be), and (B) at least one selected from the group consisting of an aromatic carboxylic acid having two or more hydroxyl groups, a salt of the aromatic carboxylic acid, and a hydrate of the aromatic carboxylic acid (hereinafter, referred to as "(B) component" as the case may be). Hereinafter, the aromatic carboxylic acid having two or more hydroxyl groups is referred to as "aromatic carboxylic acid b".

[0037] The polymerizable composition according to the present embodiment contains at least one polymerizable compound, and as the polymerizable compound, it may contain a compound including the component (A) and at least one selected from the group consisting of the component (B), or it may contain a compound including the component (A) and a polymerizable compound that does not correspond to at least one selected from the group consisting of the component (B). When the compound including the component (A) and at least one selected from the group consisting of the component (B) are polymerizable compounds, the polymerizable composition according to the present embodiment may contain a compound including the component (A) and a polymerizable compound that does not correspond to at least one selected from the group consisting of the component (B).

[0038] The polymerizable composition involved in this embodiment can be used as a thermosetting polymerizable composition. According to the polymerizable composition involved in this embodiment, the reaction start temperature can be lowered. According to the polymerizable composition involved in this embodiment, in the evaluation method described in the examples described later, for example, a reaction start temperature of 84.00°C or less (preferably 80.00°C or less, 75.00°C or less, 70.00°C or less, etc.) can be obtained.

[0039] According to one aspect of the polymerizable composition involved in the present embodiment, as excellent storage stability related to the reaction start temperature, the reaction start temperature can be suppressed from increasing when the polymerizable composition (for example, a film-like polymerizable composition) is stored, for example, the reaction start temperature can be suppressed from increasing when the film-like polymerizable composition is stored at 25° C. for 1 day (24 hours). According to one aspect of the polymerizable composition involved in the present embodiment, in the evaluation method described in the Examples described below, for example, a change rate of the reaction start temperature of 20.00% or less (preferably 15.00% or less, 10.00% or less, 5.00% or less, etc.) can be obtained.

[0040] The use of the polymerizable composition according to this embodiment is not particularly limited, and examples thereof include display devices, semiconductor devices, electronic device components, etc. The polymerizable composition according to this embodiment can be used in micro LEDs (Light Emitting Diodes), micro OLEDs (Organic Light Emitting Diodes), etc.

[0041] The polymerizable composition involved in this embodiment contains a borate anion as the (A) component. The polymerizable composition involved in this embodiment may contain a boron salt containing a borate anion (a salt of the (A) component and the counter cation of the (A) component. Hereinafter, "referred to as the (a1) component"). In the polymerizable composition involved in this embodiment, the (A) component may be bonded to the counter cation or may be free without being bonded to the counter cation.

[0042] From the viewpoint of easily lowering the reaction initiation temperature, the number of boron atoms (in one molecule) in the component (A) may be 1 to 4, 1 to 3, or 1 to 2.

[0043] From the viewpoint of easily lowering the reaction start temperature, the component (A) may contain a borate anion having a naphthalene ring (substituted or unsubstituted naphthyl), may contain a borate anion having a naphthalene ring (substituted or unsubstituted naphthyl) bonded to a boron atom, may contain at least one selected from the group consisting of alkyltriaryl borate anions and tetraaryl borate anions, may contain an alkyltriaryl borate anion, may contain an alkyltrinaphthyl borate anion, may contain a butyltrinaphthyl borate anion, or may contain an n-butyltrinaphthyl borate anion.

[0044] In component (A), from the viewpoint of easily lowering the reaction starting temperature, the number of naphthalene rings (in one molecule) or the number of naphthalene rings bonded to boron atoms (in one molecule) may be 1 to 4, 1 to 3, 2 to 4, 2 to 3 or 3 to 4, or 3.

[0045] The component (A) may have an unsubstituted naphthalene ring or a naphthalene ring having a substituent. Examples of the substituent include a halogen atom, an alkyl group, an aryl group, and an alkoxy group.

[0046] From the viewpoint of easily lowering the reaction starting temperature, the component (A) may have an alkyl group bonded to a boron atom. From the viewpoint of easily lowering the reaction starting temperature, the number of alkyl groups bonded to a boron atom in the component (A) (the number in one molecule) may be 1 to 3 or 1 to 2.

[0047] From the viewpoint of easily lowering the reaction start temperature, the number of carbon atoms of the alkyl group bonded to the boron atom may be within the following range. The number of carbon atoms of the alkyl group may be 1 or more, 2 or more, 3 or more, or 4 or more. The number of carbon atoms of 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 of 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.

[0048] The component (A) may have a functional group other than a naphthalene ring (naphthyl) and an alkyl group as a functional group bonded to a boron atom. Examples of such a functional group include an aryl group (eg, a phenyl group) other than a naphthyl group.

[0049] As the counter cation in (a1) component, quaternary ammonium ion, tertiary ammonium ion, secondary ammonium ion, primary ammonium ion, ammonium ion, imidazolium ion, imidazolinium ion, pyridinium ion, alkali metal ion (sodium ion, potassium ion, etc.), phosphonium cation, sulfonium cation, iodine cation, etc. can be cited. (a1) component may not contain metal ion, or may contain metal ion. As metal ion, alkali metal ion (sodium ion, potassium ion, etc.) can be cited. From the viewpoint of easily lowering the reaction starting temperature, (a1) component may contain quaternary ammonium ion as counter cation.

[0050] Among the quaternary ammonium ions, as a substituent bonded to the nitrogen atom, an alkyl group, an aryl group (e.g., a phenyl group), etc. can be mentioned. From the viewpoint of easily lowering the reaction starting temperature, the component (a1) may contain a quaternary ammonium ion having an alkyl group bonded to the nitrogen atom, or may contain a quaternary ammonium ion having at least one 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 as a counter cation.

[0051] From the viewpoint of easily lowering the reaction start temperature, the number of carbon atoms of the alkyl group bonded to the nitrogen atom may be within the following range. The number of carbon atoms of the alkyl group may be 1 or more, 2 or more, 3 or more, or 4 or more. The number of carbon atoms of 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 of the alkyl group may be 1 to 18, 1 to 8, 1 to 4, 2 to 6, 4 to 18, or 4 to 8.

[0052] Examples of the quaternary ammonium ion include tetraalkylammonium ions, trialkylammonium ions, dialkylammonium ions, monoalkylammonium ions, tetraarylammonium ions, triarylammonium ions, diarylammonium ions, and monoarylammonium ions. From the viewpoint of easily lowering the reaction initiation temperature, the component (a1) may contain a tetraalkylammonium ion as a counter cation.

[0053] Examples of the tetraalkylammonium ion include tetramethylammonium ion, tetraethylammonium ion, tetrapropylammonium ion, tetrabutylammonium ion (e.g., tetra-n-butylammonium ion), tetrahexylammonium ion, triethylmethylammonium ion, tributylethylammonium ion, trimethyldecylammonium ion, etc. From the viewpoint of easily lowering the reaction starting temperature, the component (a1) may contain tetrabutylammonium ion as a counter cation.

[0054] The content of the component (a1) may be within the following range based on the total mass of the polymerizable composition. From the viewpoint of facilitating the lowering of the reaction initiation temperature, the content of the component (a1) may be 0.01% by mass or more, 0.05% by mass or more, 0.10% by mass or more, 0.20% by mass or more, 0.30% by mass or more, 0.40% by mass or more, 0.50% by mass or more, 0.60% by mass or more, 0.70% by mass or more, 0.80% by mass or more, 0.90% by mass or more, 1.00% by mass or more, 1.10% by mass or more, or 1.20% by mass or more. From the viewpoint of adjusting the reaction start temperature, the content of the component (a1) 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, 1.20% by mass or less, 1.10% by mass or less, 1.00% by mass or less, 0.90% by mass or less, 0.80% by mass or less, 0.70% by mass or less, 0.60% by mass or less, 0.50% by mass or less, or 0.40% by mass or less. From these viewpoints, the content of the component (a1) may be 0.01 to 20.00 mass%, 0.30 to 20.00 mass%, 0.70 to 20.00 mass%, 1.00 to 20.00 mass%, 0.01 to 2.00 mass%, 0.30 to 2.00 mass%, 0.70 to 2.00 mass%, 1.00 to 2.00 mass%, 0.01 to 1.00 mass%, 0.30 to 1.00 mass%, or 0.70 to 1.00 mass%.

[0055] The polymerizable composition involved in this embodiment contains at least one selected from the group consisting of aromatic carboxylic acid b, salts of aromatic carboxylic acid b, and hydrates of aromatic carboxylic acid b (excluding compounds corresponding to component (a1)) as component (B). As salts of aromatic carboxylic acid b, alkali metal salts such as sodium salts and potassium salts can be mentioned. At least one selected from the group consisting of aromatic carboxylic acid b, salts of aromatic carboxylic acid b, and hydrates of aromatic carboxylic acid b (excluding compounds corresponding to component (a1)) can be at least one selected from the group consisting of aromatic carboxylic acid b and hydrates of aromatic carboxylic acid b, or can be aromatic carboxylic acid b.

[0056] The aromatic carboxylic acid b has at least one aromatic ring. From the viewpoint of easily lowering the reaction start temperature, the number of aromatic rings (the number in one molecule) may be 1. As the aromatic ring, a benzene ring, a naphthalene ring, etc. may be cited. From the viewpoint of easily lowering the reaction start temperature, the aromatic carboxylic acid may include an aromatic carboxylic acid having a benzene ring.

[0057] The aromatic carboxylic acid b has a carboxyl group bonded to an aromatic ring. From the perspective of easily lowering the reaction starting temperature and easily obtaining excellent storage stability related to the reaction starting temperature, the aromatic carboxylic acid b may include an aromatic carboxylic acid having a hydroxyl group (phenolic hydroxyl group) bonded to an aromatic ring. From the perspective of easily lowering the reaction starting temperature and easily obtaining excellent storage stability related to the reaction starting temperature, the aromatic carboxylic acid b may have a hydroxyl group bonded to the normal position relative to the carboxyl group bonded to the aromatic ring, or may have one or two hydroxyl groups bonded to the meta position relative to the carboxyl group bonded to the aromatic ring.

[0058] From the viewpoint of easily lowering the reaction starting temperature and easily obtaining excellent storage stability related to the reaction starting temperature, the number of carboxyl groups bonded to the aromatic ring in the aromatic carboxylic acid b (the number in one molecule) may be 1. From the viewpoint of easily lowering the reaction starting temperature and easily obtaining excellent storage stability related to the reaction starting temperature, the number of hydroxyl groups (the number in one molecule) or the number of hydroxyl groups bonded to the aromatic ring in the aromatic carboxylic acid b (the number in one molecule) may be 1 to 4, 1 to 3, 1 to 2, 2 to 4, 2 to 3, or 3 to 4, and may be 2 or 3.

[0059] The aromatic ring of the aromatic carboxylic acid b may or may not have a substituent other than a carboxyl group and a hydroxyl group. Examples of the substituent include an alkyl group and an alkoxy group.

[0060] Examples of the aromatic carboxylic acid b include 3,4-dihydroxybenzoic acid (protocatechuic acid), 3,5-dihydroxybenzoic acid (α-resorcinic acid), 2,4-dihydroxybenzoic acid (β-resorcinic acid), 2,6-dihydroxybenzoic acid (γ-resorcinic acid), 2,3-dihydroxybenzoic acid (2-pyrocatechuic acid), 2,5-dihydroxybenzoic acid (gentisic acid), 2,4-dihydroxy-6-methylbenzoic acid (mossic acid), 3,4,5-trihydroxybenzoic acid (gallic acid), and phloroglucinolcarboxylic acid. From the viewpoint of easily lowering the reaction starting temperature and easily obtaining excellent storage stability related to the reaction starting temperature, the aromatic carboxylic acid b may include at least one selected from the group consisting of 3,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 2,3-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid and 3,4,5-trihydroxybenzoic acid, and may also include at least one selected from the group consisting of 3,4-dihydroxybenzoic acid (protocatechuic acid) and 3,4,5-trihydroxybenzoic acid (gallic acid).

[0061] From the viewpoint of easily lowering the reaction starting temperature, the content of the component (B) based on the total amount of the aromatic carboxylic acid, the salt of the aromatic carboxylic acid and the hydrate of the aromatic carboxylic acid contained in the polymerizable composition may be 50.00% by mass or more, more than 50.00% by mass, 70.00% by mass or more, 80.00% by mass or more, 90.00% by mass or more, 92.00% by mass or more, 95.00% by mass or more, 97.00% by mass or more, 98.00% by mass or more, 99.00% by mass or more, or substantially 100.00% by mass.

[0062] The content of the component (B) may be within the following ranges based on the total mass of the polymerizable composition. From the viewpoint of facilitating the lowering of the reaction initiation temperature, the content of the component (B) may be 0.01% by mass or more, 0.05% by mass or more, 0.10% by mass or more, 0.30% by mass or more, 0.50% by mass or more, 0.80% by mass or more, 1.00% by mass or more, 1.20% by mass or more, 1.30% by mass or more, 1.40% by mass or more, 1.50% by mass or more, 1.60% by mass or more, 1.80% by mass or more, or 2.00% by mass or more. From the viewpoint of easily obtaining excellent storage stability related to the reaction start temperature, the content of the component (B) may be 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, 2.00% by mass or less, 1.80% by mass or less, 1.60% by mass or less, 1.50% by mass or less, or 1.40% by mass or less. From these viewpoints, the content of the component (B) may be 0.01 to 10.00% by mass, 0.01 to 2.50% by mass, 0.01 to 2.00% by mass, 1.00 to 10.00% by mass, 1.00 to 2.50% by mass, 1.00 to 2.00% by mass, 1.50 to 10.00% by mass, 1.50 to 2.50% by mass, or 1.50 to 2.00% by mass.

[0063] From the viewpoint of easily lowering the reaction start temperature, the mass ratio R1 ((B) component / (a1) component) of the content of the component (B) to the content of the component (a1) may be within the following range. The mass ratio R1 may be 0.01 or more, 0.05 or more, 0.10 or more, 0.30 or more, 0.50 or more, 0.80 or more, 1.00 or more, 1.20 or more, 1.50 or more, 1.80 or more, 2.00 or more, 2.50 or more, 3.00 or more, 3.50 or more, 4.00 or more, or 5.00 or more. From the viewpoint of easily obtaining excellent storage stability related to the reaction start temperature, the mass ratio R1 may be 10.00 or less, 8.00 or less, 6.00 or less, 5.00 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, 0.01 to 1.50, 1.00 to 10.00, 1.00 to 6.00, 1.00 to 3.00, 1.00 to 1.50, 1.50 to 10.00, 1.50 to 6.00, or 1.50 to 3.00.

[0064] The polymerizable composition according to the present embodiment may contain a polymerizable compound (except for the compound corresponding to the component (a1) or the component (B)) as the component (C).

[0065] As the component (C), there can be mentioned radical polymerizable compounds, cation polymerizable compounds, anion polymerizable compounds, etc. From the viewpoint of easily lowering the reaction initiation temperature, the component (C) may contain a radical polymerizable compound.

[0066] As the component (C), there can be mentioned (meth)acrylate compounds, maleimide compounds, vinyl ether compounds, allyl compounds, styrene compounds, (meth)acrylamide compounds, nadiimide 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 starting temperature, the component (C) may contain a compound having an ethylenically unsaturated bond, or may contain a (meth)acrylate compound.

[0067] Examples of the (meth)acrylate compound include polyurethane (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, Acid, n-hexyl (meth) 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, dipentatriol hexa(meth)acrylate, isocyanuric acid alkylene oxide-modified di(meth)acrylate, isocyanuric acid alkylene oxide-modified tri(meth)acrylate, tricyclodecane (meth)acrylate, dihydroxymethyl tricyclodecane di(meth)acrylate, 2-hydroxy-1,3-di(meth)acryloyloxypropane, 2,2-bis[4-((meth)acryloyloxymethoxy)phenyl]propane, 2,2-bis[4-((meth)acryloyloxypolyethoxy)phenyl]propane, etc. "Polyurethane (meth)acrylate" and "urethane (meth)acrylate" are collectively referred to as "(poly)urethane (meth)acrylate". (C) Component may contain a bifunctional (meth)acrylate compound.

[0068] From the viewpoint of easily lowering the reaction start temperature, the component (C) may include a urethane (meth) acrylate compound having a polycarbonate skeleton (hereinafter referred to as "component (c1)"), 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 (c1).

[0069]

[0070] [Where R 1represents 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.]

[0071] From the viewpoint of easily lowering the reaction starting temperature, in the general formula (c1), j may be 1-2 or 2-3, k may be 2-3 or 3-5, m may be 1-6, 1-4 or 1-2, and n may be 5-6 or 6-7.

[0072] From the viewpoint of easily lowering the reaction start temperature, the weight average molecular weight of the component (c1) may be 1000 or more, 3000 or more, 5000 or more, 8000 or more, 10000 or more, 12000 or more, 13000 or more, 14000 or more, or 15000 or more. From the viewpoint of easily lowering the reaction start temperature, the weight average molecular weight of the component (c1) may be 100000 or less, 50000 or less, 30000 or less, 25000 or less, 20000 or less, 18000 or less, or 15000 or less. From these viewpoints, the weight average molecular weight of the component (c1) may be 1000 to 100000, 5000 to 50000, or 10000 to 30000.

[0073] From the viewpoint of easily lowering the reaction start temperature, the content of the component (c1) may be within the following ranges based on the total mass of the component (C). The content of the component (c1) may be 10.00% by mass or more, 15.00% by mass or more, 20.00% by mass or more, 25.00% by mass or more, 30.00% by mass or more, 35.00% by mass or more, 40.00% by mass or more, 45.00% by mass or more, 50.00% by mass or more, or 55.00% by mass or more. The content of the component (c1) may be 90.00% by mass or less, 85.00% by mass or less, 80.00% by mass or less, 75.00% by mass or less, 70.00% by mass or less, 65.00% by mass or less, or 60.00% by mass or less. From these viewpoints, the content of the component (c1) 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%.

[0074] From the viewpoint of facilitating lowering the reaction start temperature, the content of the component (c1) may be within the following ranges based on the total mass of the polymerizable composition. The content of the component (c1) may be 5.00% by mass or more, 10.00% by mass or more, 15.00% by mass or more, or 20.00% by mass or more. The content of the component (c1) may be 50.00% by mass or less, 45.00% by mass or less, 40.00% by mass or less, 35.00% by mass or less, 30.00% by mass or less, or 25.00% by mass or less. From these viewpoints, the content of the component (c1) 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%.

[0075] From the viewpoint of easily lowering the reaction start temperature, the component (C) may contain isocyanuric acid alkylene oxide-modified di(meth)acrylate (excluding the compound corresponding to the component (c1); hereinafter referred to as "component (c2)") or may contain isocyanuric acid ethylene oxide-modified di(meth)acrylate.

[0076] From the viewpoint of easily lowering the reaction start temperature, the content of the component (c2) may be within the following ranges based on the total mass of the component (C). The content of the component (c2) may be 1.00% by mass or more, 5.00% by mass or more, 10.00% by mass or more, 15.00% by mass or more, or 20.00% by mass or more. The content of the component (c2) may be 50.00% by mass or less, 45.00% by mass or less, 40.00% by mass or less, 35.00% by mass or less, 30.00% by mass or less, or 25.00% by mass or less. From these viewpoints, the content of component (c2) 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%.

[0077] From the viewpoint of facilitating lowering the reaction start temperature, the content of the component (c2) may be within the following ranges based on the total mass of the polymerizable composition. The content of the component (c2) may be 1.00% by mass or more, 3.00% by mass or more, 5.00% by mass or more, 8.00% by mass or more, or 9.00% by mass or more. The content of the component (c2) may be 30.00% by mass or less, 25.00% by mass or less, 20.00% by mass or less, 15.00% by mass or less, or 10.00% by mass or less. From these viewpoints, the content of component (c2) 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%.

[0078] From the viewpoint of easily lowering the reaction starting temperature, the component (C) may contain at least one di(meth)acrylate compound selected from the group consisting of a dicyclopentanyl ester structure and a dicyclopentenyl ester structure (excluding the compound corresponding to the component (c1) or the component (c2); hereinafter referred to as the "component (c3)"), and may also contain at least one selected from the group consisting of dihydroxymethyltricyclodecane di(meth)acrylate and tricyclodecanediol di(meth)acrylate.

[0079] From the viewpoint of easily lowering the reaction start temperature, the content of the component (c3) may be within the following ranges based on the total mass of the component (C). The content of the component (c3) may be 1.00% by mass or more, 5.00% by mass or more, 10.00% by mass or more, 15.00% by mass or more, or 20.00% by mass or more. The content of the component (c3) may be 50.00% by mass or less, 45.00% by mass or less, 40.00% by mass or less, 35.00% by mass or less, 30.00% by mass or less, or 25.00% by mass or less. From these viewpoints, the content of component (c3) 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%.

[0080] From the viewpoint of facilitating lowering the reaction start temperature, the content of the component (c3) may be within the following ranges based on the total mass of the polymerizable composition. The content of the component (c3) may be 1.00% by mass or more, 3.00% by mass or more, 5.00% by mass or more, 8.00% by mass or more, or 9.00% by mass or more. The content of the component (c3) may be 30.00% by mass or less, 25.00% by mass or less, 20.00% by mass or less, 15.00% by mass or less, or 10.00% by mass or less. From these viewpoints, the content of component (c3) 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%.

[0081] From the viewpoint of facilitating lowering the reaction start temperature, 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 10.00% by mass or more, 15.00% by mass or more, 20.00% by mass or more, 25.00% by mass or more, 30.00% by mass or more, 35.00% by mass or more, or 40.00% by mass or more. The content of the component (C) may be 80.00% by mass or less, 75.00% by mass or less, 70.00% by mass or less, 65.00% by mass or less, 60.00% by mass or less, 55.00% by mass or less, 50.00% by mass or less, or 45.00% by mass or less. From these viewpoints, the content of the component (C) 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%.

[0082] The mass ratio R2 ((C) component / (a1) component) of the content of the component (C) to the content of the component (a1) may be within the following range. From the viewpoint of adjusting the reaction start temperature, the mass ratio R2 may be 1.00 or more, 5.00 or more, 10.00 or more, 20.00 or more, 30.00 or more, 40.00 or more, 50.00 or more, 60.00 or more, 80.00 or more, or 100.00 or more. From the viewpoint of easily lowering the reaction start temperature, the mass ratio R2 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 R2 may be 1.00 to 300.00, 1.00 to 120.00, 1.00 to 60.00, 1.00 to 40.00, 20.00 to 300.00, 20.00 to 120.00, 20.00 to 60.00, 20.00 to 40.00, 30.00 to 300.00, 30.00 to 120.00, 30.00 to 60.00, or 30.00 to 40.00.

[0083] The mass ratio R3 of the content of the (C) component relative to the content of the (B) component ((C) component / (B) component) may be within the following range. From the viewpoint of easily obtaining excellent storage stability related to the reaction start temperature, the mass ratio R3 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. From the viewpoint of easily lowering the reaction start temperature, the mass ratio R3 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, 35.00 or less, 30.00 or less, 25.00 or less, or 20.00 or less. From these viewpoints, the mass ratio R3 may be 1.00 to 300.00, 1.00 to 50.00, 1.00 to 30.00, 10.00 to 300.00, 10.00 to 50.00, 10.00 to 30.00, 20.00 to 300.00, 20.00 to 50.00, or 20.00 to 30.00.

[0084] The polymerizable composition involved in this embodiment may contain a polymerization initiator (except for the compound corresponding to component (a1), component (B) or component (C)) as component (D), or may not contain a polymerization initiator. Component (D) may contain a thermal polymerization initiator. Component (D) includes free radical polymerization initiators, cationic polymerization initiators, anionic polymerization initiators, etc. Component (D) may contain a free radical polymerization initiator from the viewpoint of easily lowering the reaction start temperature.

[0085] Examples of the component (D) include ketone peroxides such as methyl ethyl ketone peroxide, cyclohexanone peroxide, and methylcyclohexanone peroxide; peroxyketals such as 1,1-bis(tertiary butylperoxy)cyclohexane, 1,1-bis(tertiary butylperoxy)-2-methylcyclohexane, 1,1-bis(tertiary butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tertiary hexylperoxy)cyclohexane, and 1,1-bis(tertiary hexylperoxy)-3,3,5-trimethylcyclohexane; hydroperoxides such as p-menthane hydroperoxide; α,α'-bis(tertiary butylperoxy)diisopropylbenzene, diisopropylbenzene peroxide, tertiary butylisopropylbenzene peroxide, di-tertiary butylperoxy dialkyl peroxides such as octanoyl peroxide, lauroyl peroxide, stearyl peroxide, benzoyl peroxide, etc.; peroxycarbonates such as bis(4-tert-butylcyclohexyl)peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-3-methoxybutyl peroxycarbonate, etc.; tert-butyl peroxypivalate, tert-hexyl peroxypivalate, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis(2-ethylhexanoyl peroxy)hexane, tert-hexyl peroxy-2-ethylhexanoate, tert-butyl peroxy-2-ethylhexanoic acid Ester, tertiary butyl peroxy isobutyrate, tertiary hexyl peroxy isopropyl monocarbonate, tertiary butyl peroxy-3,5,5-trimethylhexanoate, tertiary butyl peroxy laurate, tertiary butyl peroxy isopropyl monocarbonate, tertiary butyl peroxy-2-ethylhexyl monocarbonate, tertiary butyl peroxy benzoate, tertiary hexyl peroxy benzoate, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane, tertiary butyl peroxy acetate and other peroxy esters; phthalic anhydride, maleic anhydride, trimellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, glutaric anhydride, dimethyl glutaric anhydride, diethyl glutaric anhydride, succinic anhydride, methyl Anhydrides such as hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 4,4'-diphthalic anhydride, 4,4'-carbonyldiphthalic anhydride, 4,4'-sulfonyldiphthalic anhydride, 4,4'-(hexafluoroisopropylidene)diphthalic 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; imidazole compounds, etc.

[0086] From the viewpoint of easily lowering the reaction initiation temperature, the component (D) may contain a peroxide, an organic peroxide, or a diacyl peroxide.

[0087] The content of the component (D) may be within the following ranges based on the total mass of the polymerizable composition. From the viewpoint of easily lowering the reaction start temperature, the content of the component (D) may be 0.10% by mass or more, 0.50% by mass or more, 1.00% by mass or more, 1.50% by mass or more, 2.00% by mass or more, 2.50% by mass or more, 3.00% by mass or more, 3.50% by mass or more, 4.00% by mass or more, or 4.50% by mass or more. From the viewpoint of adjusting the reaction start temperature, the content of the component (D) may be 20.00% by mass or less, 15.00% by mass or less, 10.00% by mass or less, 9.00% by mass or less, 8.00% by mass or less, 7.00% by mass or less, 6.00% by mass or less, or 5.00% by mass or less. From these viewpoints, the content of the component (D) 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%.

[0088] The mass ratio R4 ((D) component / (a1) component) of the content of the component (D) to the content of the component (a1) may be within the following range. From the viewpoint of adjusting the reaction start temperature, the mass ratio R4 may be 0.10 or more, 0.50 or more, 1.00 or more, 2.00 or more, 3.00 or more, 4.00 or more, 5.00 or more, 6.00 or more, 8.00 or more, or 10.00 or more. From the viewpoint of easily lowering the reaction start temperature, the mass ratio R4 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 R4 may be 0.10 to 50.00, 0.10 to 15.00, 0.10 to 6.00, 0.10 to 5.00, 3.00 to 50.00, 3.00 to 15.00, 3.00 to 6.00, 3.00 to 5.00, 5.00 to 50.00, 5.00 to 15.00, or 5.00 to 6.00.

[0089] The mass ratio R5 of the content of the (D) component relative to the content of the (B) component ((D) component / (B) component) may be within the following range. From the viewpoint of easily obtaining excellent storage stability related to the reaction start temperature, the mass ratio R5 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. From the viewpoint of easily lowering the reaction start temperature, the mass ratio R5 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, 4.00 or less, 3.50 or less, 3.00 or less, 2.50 or less, or 2.00 or less. From these viewpoints, the mass ratio R5 may be 0.10 to 50.00, 0.10 to 20.00, 0.10 to 3.00, 1.00 to 50.00, 1.00 to 20.00, 1.00 to 3.00, 2.00 to 50.00, 2.00 to 20.00, or 2.00 to 3.00.

[0090] The mass ratio R6 of the content of the (D) component relative to the content of the (C) component ((D) component / (C) component) may be within the following range. From the viewpoint of easily lowering the reaction start temperature, the mass ratio R6 may be 0.01 or more, 0.03 or more, 0.05 or more, 0.08 or more, or 0.10 or more. From the viewpoint of adjusting the reaction start temperature, the mass ratio R6 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 R6 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.

[0091] The polymerizable composition according to the present embodiment may contain a thermoplastic resin as the component (E), or may not contain a thermoplastic resin.

[0092] As the component (E), there can be mentioned phenoxy resin, polyester, polyurethane (excluding polyester urethane), polyester urethane, ethylene vinyl acetate copolymer, butyral resin, etc. From the viewpoint of easily lowering the reaction starting temperature, the component (E) may include at least one selected from the group consisting of polyester urethane and ethylene vinyl acetate copolymer.

[0093] From the viewpoint of facilitating lowering the reaction initiation temperature, based on the total mass of the polymerizable composition,

[0094] The content of the component (E) may be within the following ranges. The content of the component (E) may be 10.00% by mass or more, 15.00% by mass or more, 20.00% by mass or more, 25.00% by mass or more, 30.00% by mass or more, 35.00% by mass or more, 40.00% by mass or more, 45.00% by mass or more, or 50.00% by mass or more. The content of the component (E) may be 90.00% by mass or less, 85.00% by mass or less, 80.00% by mass or less, 75.00% by mass or less, 70.00% by mass or less, 65.00% by mass or less, 60.00% by mass or less, or 55.00% by mass or less. From these viewpoints, the content of the component (E) 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%.

[0095] The polymerizable composition involved in this embodiment may contain components other than the above components. Examples of such components include water, organic solvents, coupling agents, fillers, softeners, accelerators, degradation inhibitors, colorants, flame retardants, thixotropic viscosity reducing agents, etc. The polymerizable composition involved in this embodiment may contain at least one of these components, or may not contain at least one of these components.

[0096] The polymerizable composition involved in this embodiment can be in the form of a film. The thickness of the film-like polymerizable composition or the thickness of the cured product involved in this embodiment can be in the following range. The thickness can 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 can 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 can 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.

[0097] Example

[0098] Hereinafter, the present invention will be described in more detail using examples and comparative examples, but the present invention is not limited to the following examples.

[0099] <Synthesis of Urethane Acrylate (UA1)>

[0100] Into a reaction container (equipped with a stirrer, a thermometer, a reflux cooling tube with a zirconium chloride drying tube, and a nitrogen inlet tube), 2500 parts by mass (2.50 mol) of poly (1,6-hexanediol carbonate) (product name: DURANATE T5652, manufactured by ASAHIKASEI CORPORATION) and 666 parts by mass (3.00 mol) of isophorone diisocyanate (manufactured by Sigma-Aldrich Co. LLC) were uniformly added dropwise over 3 hours. Next, after nitrogen was fully introduced into the reaction container, the reaction container was heated to 70-75° C. to react. Next, 0.53 parts by mass (4.3 mmol) of hydroquinone monomethyl ether (manufactured by Sigma-Aldrich Co. LLC) and 5.53 parts by mass (8.8 mmol) of dibutyltin dilaurate (manufactured by Sigma-Aldrich Co. LLC) were added to the reaction container, and then 238 parts by mass (2.05 mol) of 2-hydroxyethyl acrylate (manufactured by Sigma-Aldrich Co. LLC) was added, and the mixture was reacted at 70° C. for 6 hours under an air atmosphere. Thus, urethane acrylate (UA1) having a polycarbonate skeleton was obtained. The weight average molecular weight of urethane acrylate (UA1) was 15,000.

[0101] <Synthesis of Polyester Urethane (EU1)>

[0102] After adding 48 parts by mass of isophthalic acid and 37 parts by mass of neopentyl glycol to a stainless steel autoclave with a heater (equipped with a stirrer, a thermometer, a capacitor, a vacuum generator, and a nitrogen inlet pipe), 0.02 parts by mass of tetrabutoxy titanate was added as a catalyst. Next, the temperature was raised to 220°C under a nitrogen flow and stirred directly for 8 hours. After that, the pressure was reduced to atmospheric pressure (760 mmHg) and cooled to room temperature. Thus, a white precipitate was precipitated and the precipitate was taken out. After the precipitate was washed with water, it was vacuum dried to obtain a polyester polyol. After the polyester polyol was fully dried, it was dissolved in MEK (methyl ethyl ketone) and put into a four-necked flask equipped with a stirrer, a dropping funnel, a reflux cooler and a nitrogen inlet pipe. Furthermore, 0.05 parts by mass of dibutyltin dilaurate (catalyst) was added to 100 parts by mass of the polyester polyol, and 50 parts by mass of 4,4'-diphenylmethane diisocyanate was dissolved in MEK to 100 parts by mass of the polyester polyol and added using a dropping funnel. Then, the mixture was stirred at 80°C for 4 hours to obtain polyester urethane (EU1).

[0103] <Preparation of polymerizable composition>

[0104] The obtained product was prepared by mixing a methyl ethyl ketone solution (solid content ratio: 20% by mass) of a boron salt (tetrabutylammonium=butyltrinaphthylborate, manufactured by Showa Denko KK, product name: Karenz N3B), an acid component shown in Table 1, a toluene solution (solid content ratio: 20% by mass) of a polymerization initiator (diacyl peroxide, manufactured by NOF CORPORATION, product name: PEROYL L), urethane acrylate (UA1), isocyanuric acid ethylene oxide-modified diacrylate (manufactured by TOAGOSEICO., LTD., product name: M-215), dimethylol tricyclodecane diacrylate (manufactured by KYOEISHA CHEMICAL Co., LTD., product name: light acrylate DCP-A), a methyl ethyl ketone / toluene mixed solution (mass ratio: 1 / 1, solid content ratio: 40% by mass) of polyester urethane (EU1), an ethylene vinyl acetate copolymer (DuPont deNemours, Inc., product name: EV40W) was added toluene solution (solid content ratio: 30% by mass) to prepare a polymerizable composition. The amount of boron salt and acid component used (solid content, unit: mass parts) is shown in Table 1. The amount of 3,4,5-trihydroxybenzoic acid (gallic acid) used is the amount of 3,4,5-trihydroxybenzoic acid monohydrate used. The amount of polymerization initiator used (solid content) is 5.00 parts by mass, the amount of urethane acrylate (UA1) used is 25.00 parts by mass, the amount of isocyanuric acid ethylene oxide modified diacrylate used is 10.00 parts by mass, the amount of dihydroxymethyl tricyclodecane diacrylate used is 10.00 parts by mass, the amount of polyester urethane (EU1) used (solid content) is 47.50 parts by mass, and the amount of ethylene vinyl acetate copolymer used (solid content) is 7.50 parts by mass.

[0105] In each of the Examples and Comparative Examples, the following acid components shown in "Acid component (type)" in Table 1 were used.

[0106] 3,4-Dihydroxybenzoic acid (protocatechuic acid): manufactured by FUJIFILM Wako Pure Chemical Corporation

[0107] 3,5-Dihydroxybenzoic acid (α-resorcinolic acid): manufactured by Tokyo Chemical Industry Co., Ltd.

[0108] 2,3-Dihydroxybenzoic acid (2-pyrocatechuic acid): manufactured by Tokyo Chemical Industry Co., Ltd.

[0109] 2,4-Dihydroxybenzoic acid (β-resorcinolic acid): manufactured by FUJIFILM Wako Pure Chemical Corporation

[0110] 2,5-Dihydroxybenzoic acid (gentisic acid): manufactured by FUJIFILM Wako Pure Chemical Corporation

[0111] 2,6-Dihydroxybenzoic acid (γ-resorcinolic acid): manufactured by FUJIFILM Wako Pure Chemical Corporation

[0112] 3,4,5-Trihydroxybenzoic acid (gallic acid) (monohydrate): Made by FUJIFILM Wako Pure Chemical Corporation

[0113] Acetic acid: Made by FUJIFILM Wako Pure Chemical Corporation

[0114] Adipic acid: Made by FUJIFILM Wako Pure Chemical Corporation

[0115] Paraben: Made by FUJIFILM Wako Pure Chemical Corporation

[0116] <Production of laminated films>

[0117] The polymerizable composition was applied to a PET film (peel-treated, 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 produce a laminated film having a film-like polymerizable composition with a thickness of 20 μm arranged on the PET film.

[0118] <Determination of reaction starting temperature>

[0119] After peeling off the PET film from the above-mentioned laminated film just produced, the curing exothermic behavior of the film-like polymerizable composition was measured using differential scanning calorimetry (Differential Scanning Calorimetry, hereinafter referred to as "DSC"), and the start temperature of the exothermic peak was obtained as an indicator of the polymerization reaction start temperature. The DSC measurement was carried out under the following conditions to obtain the reaction start temperature T1. In addition, after the above-mentioned laminated film just produced in the embodiment was placed in a nylon plastic bag (manufactured by Fukusuke Kogyo Co., Ltd., product name "Nylon Poly S Type"), the bag was sealed using a vacuum degassing sealer and the laminated film was packaged. In addition, the bag was placed in an aluminum light-shielding bag. In this state, after the laminated film was placed at 25°C for 24 hours, the laminated film was taken out of the light-shielding bag, and the reaction start temperature T2 was obtained in the same order as the above order. Then, as the rate of change (%) of the reaction start temperature, "[(T2-T1) / T1]×100" was calculated. The results are shown in Table 1.

[0120] (DSC measurement conditions)

[0121] Measurement device: manufactured by PerkinElmer Japan Co., Ltd., product name "DSC8500"

[0122] Sample volume: 10.0±0.2mg

[0123] Measuring temperature range: 30~200℃

[0124] Heating rate: 30℃ / min

[0125] Measuring atmosphere: Nitrogen

[0126] [Table 1]

[0127]

Claims

1. A polymerizable composition comprising a polymerizable compound, The polymerizable composition contains (A) a borate anion and (B) at least one selected from the group consisting of an aromatic carboxylic acid having two or more hydroxyl groups, a salt of the aromatic carboxylic acid, and a hydrate of the aromatic carboxylic acid.

2. The polymerizable composition according to claim 1, wherein The component (A) contains a borate anion having a naphthalene ring.

3. The polymerizable composition according to claim 1, wherein The component (A) contains an alkyltriarylborate anion.

4. The polymerizable composition according to claim 1, wherein The number of naphthalene rings in the component (A) is 3.

5. The polymerizable composition according to claim 1, wherein The content of the boron salt contained in the component (A) is 0.01 to 20.00% by mass.

6. The polymerizable composition according to any one of claims 1 to 5, wherein The number of hydroxyl groups in the aromatic carboxylic acid is 2.

7. The polymerizable composition according to any one of claims 1 to 5, wherein The number of hydroxyl groups in the aromatic carboxylic acid is 3.

8. The polymerizable composition according to any one of claims 1 to 5, wherein The content of the component (B) is 0.01 to 10.00% by mass.

9. The polymerizable composition according to any one of claims 1 to 5, wherein The mass ratio of the content of the component (B) to the content of the boron salt including the component (A) is 0.01 to 10.

00.

10. The polymerizable composition according to any one of claims 1 to 5, wherein The polymerizable compound includes a (meth)acrylate compound. 11 . The polymerizable composition according to claim 1 , further comprising a polymerization initiator.

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