Polymerizable composition

Abstract

A polymerizable composition containing a polymerizable compound, the polymerizable composition containing: (A) a borate anion; (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; and (C) a phosphorus compound having a P = O (OH) structure.

Description

Technical Field

[0001] The present invention relates to a polymerizable composition and the like. Background Art

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

[0003] Prior Art Documents

[0004] Patent Documents

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

[0006] Technical Problem to be Solved by the Invention

[0007] With the miniaturization and high performance of various devices in recent years, when thermally curing a polymerizable composition near a component that should be avoided from being exposed to high heat, there are sometimes cases where the polymerizable composition in contact with the component that should be avoided from being exposed to high heat is thermally cured. In such cases, from the viewpoint of avoiding deterioration of the component by performing thermal curing at a low temperature, a reduction in the reaction initiation temperature is required for the polymerizable composition.

[0008] Moreover, a phosphorus compound is sometimes used as a component contained in the polymerizable composition. For such a polymerizable composition containing a phosphorus compound, a reduction in the reaction initiation temperature is also required.

[0009] An object of one aspect of the present invention is to provide a polymerizable composition containing a phosphorus compound and capable of reducing the reaction initiation temperature.

[0010] Means for Solving the Technical Problem

[0011] The present invention relates to the following [1] to

[13] and the like in some aspects.

[0012] [1] A polymerizable composition, which is a polymerizable composition containing a polymerizable compound, and contains: (A) a borate anion; (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; and (C) a phosphorus compound having a P═O(OH) structure.

[0013] [2] The polymerizable composition according to [1], wherein

[0014] the component (A) contains a borate anion having a naphthalene ring.

[0015] [3] The polymerizable composition according to [1] or [2], wherein

[0016] The component (A) contains an alkyltriaryltrihydroxyborate anion.

[0017] [4] The polymerizable composition according to any one of [1] to [3], wherein

[0018] the number of naphthalene rings in the component (A) is 3.

[0019] [5] The polymerizable composition according to any one of [1] to [4], wherein

[0020] the content of the borate salt containing the component (A) is 0.01 to 20.00% by mass.

[0021] [6] The polymerizable composition according to any one of [1] to [5], wherein

[0022] the number of hydroxyl groups in the aromatic carboxylic acid is 2.

[0023] [7] The polymerizable composition according to any one of [1] to [5], wherein

[0024] the number of hydroxyl groups in the aromatic carboxylic acid is 3.

[0025] [8] The polymerizable composition according to any one of [1] to [7], wherein

[0026] the content of the component (B) is 0.01 to 10.00% by mass.

[0027] [9] The polymerizable composition according to any one of [1] to [8], wherein

[0028] the mass ratio of the content of the component (B) to the content of the borate salt containing the component (A) is 0.01 to 10.00.

[0029]

[10] The polymerizable composition according to any one of [1] to [9], wherein

[0030] the component (C) contains a (meth)acrylate compound having a P=O(OH) structure.

[0031]

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

[10] , wherein

[0032] the content of the component (C) is 0.01 to 10.00% by mass.

[0033]

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

[11] , wherein

[0034] The polymerizable compound contains a (meth)acrylate compound.

[0035]

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

[12] further contains a polymerization initiator.

[0036] Advantages of the Invention

[0037] According to one aspect of the present invention, a polymerizable composition containing a phosphorus compound and capable of reducing the reaction initiation temperature can be provided. Detailed Description of the Invention

[0038] Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

[0039] In the present specification, the numerical range represented by "~" means a range including the numerical values described before and after "~" as the minimum value and the maximum value, respectively. "A or more" in the numerical range means a range of A and more than A. "A or less" in the numerical range means a range of A and less than A. In the numerical ranges described stepwise in the present specification, the upper limit value or the lower limit value of a certain stepwise numerical range can be arbitrarily combined with the upper limit value or the lower limit value of other stepwise numerical ranges. In the numerical ranges described in the present specification, the upper limit value or the lower limit value of the numerical range can be replaced with the values shown in the examples. "A or B" can include either A or B, or both. Unless otherwise specified, the materials exemplified in the present specification can be used alone or in combination of two or more. When there are multiple substances corresponding to each component in the composition, unless otherwise specified, the content of each component in the composition represents the total amount of the multiple substances present in the composition. "(Meth)acrylate" means at least one of acrylate and the corresponding methacrylate. The same applies to other similar expressions such as "(meth)acrylic acid". The content of the (meth)acrylate compound means the total amount of the acrylate compound and the methacrylate compound. Unless otherwise specified, "alkyl" can be linear, branched, or cyclic. "Hydroxyl" does not include the OH group contained in the carboxyl group. "The total mass of the polymerizable composition" is based on the total mass of the solid components of the polymerizable composition. The solid components of the polymerizable composition refer to the non-volatile components obtained by removing the volatile components (water, organic solvents, etc.) that can volatilize. That is, the solid components refer to the components that do not volatilize and remain during the drying of the polymerizable composition, and also include components that are liquid, syrupy, waxy, etc. at 25°C.

[0040] In the present specification, the "weight average molecular weight" can be measured by a gel permeation chromatograph (GPC) under the following measurement conditions and converted according to the calibration curve using standard polystyrene.

[0041] (Measurement Conditions)

[0042] Apparatus: GPC - 8020, manufactured by Tosoh Corporation

[0043] Detector: RI - 8020, manufactured by Tosoh Corporation

[0044] Column: Gelpack GL - A - 160 - S + GL - A150, manufactured by Resonac Corporation

[0045] Sample concentration: 120 mg / 3 mL

[0046] Solvent: Tetrahydrofuran

[0047] Injection volume: 60 μL

[0048] Pressure: 294×10 6 Pa (30 kgf / cm 2 )

[0049] Flow rate: 1.00 mL / minute

[0050] The polymerizable composition of the present embodiment is a polymerizable composition containing a polymerizable compound, which contains: (A) borate anion (hereinafter, sometimes referred to as "(A) component"); (B) at least one selected from the group consisting of aromatic carboxylic acids having two or more hydroxyl groups, salts of the aromatic carboxylic acids, and hydrates of the aromatic carboxylic acids (hereinafter, sometimes referred to as "(B) component"); and (C) a phosphorus compound having a P=O(OH) structure (hereinafter, sometimes referred to as "(C) component"). Hereinafter, the aromatic carboxylic acid having two or more hydroxyl groups is referred to as "aromatic carboxylic acid b".

[0051] The polymerizable composition of the present embodiment contains at least one polymerizable compound, and as the polymerizable compound, it may contain at least one selected from the group consisting of a compound containing (A) component, (B) component, and (C) component, or may contain a polymerizable compound that does not belong to the group consisting of a compound containing (A) component, (B) component, and (C) component. When at least one selected from the group consisting of a compound containing (A) component, (B) component, and (C) component is a polymerizable compound, the polymerizable composition of the present embodiment may contain a polymerizable compound that does not belong to the group consisting of a compound containing (A) component, (B) component, and (C) component.

[0052] The polymeric composition of the present embodiment can be used as a thermosetting polymeric composition. The polymeric composition according to the present embodiment can lower the reaction initiation temperature. In the evaluation method described in the examples below, the polymeric composition according to the present embodiment can obtain a reaction initiation temperature of, for example, 84.00 °C or lower (preferably 80.00 °C or lower, 75.00 °C or lower, 70.00 °C or lower, 65.00 °C or lower, 60.00 °C or lower, etc.).

[0053] In one aspect of the polymeric composition according to the present embodiment, as an excellent storage stability related to the reaction initiation temperature, when storing the polymeric composition (for example, a film-like polymeric composition), an increase in the reaction initiation temperature can be suppressed. For example, when storing a film-like polymeric composition at 25 °C for 1 day (24 hours), an increase in the reaction initiation temperature can be suppressed. In one aspect of the polymeric composition according to the present embodiment, in the evaluation method described in the examples below, a change rate of the reaction initiation temperature of, for example, 50.00% or lower (preferably 40.00% or lower, 30.00% or lower, 20.00% or lower, 10.00% or lower, etc.) can be obtained.

[0054] In one aspect of the polymeric composition according to the present embodiment, excellent adhesive strength between adherends can be obtained in a state where a cured product of the polymeric composition is interposed between the adherends. For example, excellent adhesive strength can be obtained in a state where a cured product of the polymeric composition is interposed between a resin film (such as a polyimide film) and a glass plate. In one aspect of the polymeric composition according to the present embodiment, in the evaluation method described in the examples below, an adhesive strength of, for example, 3.0 N / cm or more (preferably 3.5 N / cm or more, 4.0 N / cm or more, 4.5 N / cm or more, 5.0 N / cm or more, 5.5 N / cm or more, etc.) can be obtained.

[0055] As the use of the polymeric composition of the present embodiment, there is no particular limitation, and examples include display devices, semiconductor devices, components for electronic devices, etc. The polymeric composition of the present embodiment can be used in micro LEDs (Light Emitting Diodes), micro OLEDs (Organic Light Emitting Diodes), etc.

[0056] The polymeric composition of the present embodiment contains a borate anion as component (A). The polymeric composition of the present embodiment may contain a borate salt containing a borate anion (a salt of component (A) and the counter cation of component (A). Hereinafter, it is referred to as “component (a1)”). In the polymeric composition of the present embodiment, component (A) may be bonded to the counter cation or may be free without being bonded to the counter cation.

[0057] In the component (A), from the viewpoint of easily reducing the reaction initiation temperature, the number of boron atoms (the number in one molecule) can be 1 to 4, 1 to 3, or 1 to 2.

[0058] From the viewpoint of easily reducing the reaction initiation 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 an alkyltriarylborate anion and a tetraarylborate anion, may contain an alkyltriarylborate anion, may contain an alkyltrinaphthylborate anion, may contain a butyltrinaphthylborate anion, and may contain a n-butyltrinaphthylborate anion.

[0059] From the viewpoint of easily reducing the reaction initiation temperature, in the component (A), the number of naphthalene rings (the number in one molecule) or the number of naphthalene rings (the number in one molecule) bonded to a boron atom can be 1 to 4, 1 to 3, 2 to 4, 2 to 3, or 3 to 4, and can also be 3.

[0060] (A) The component may have an unsubstituted naphthalene ring or a naphthalene ring containing a substituent. Examples of the substituent include a halogen atom, an alkyl group, an aryl group, an alkoxy group, etc.

[0061] From the viewpoint of easily reducing the reaction initiation temperature, the component (A) may have an alkyl group bonded to a boron atom. From the viewpoint of easily reducing the reaction initiation temperature, in the component (A), the number of alkyl groups bonded to a boron atom (the number in one molecule) can be 1 to 3 or 1 to 2.

[0062] From the viewpoint of easily reducing the reaction initiation temperature, the number of carbon atoms of the alkyl group bonded to a boron atom can be within the following range. The number of carbon atoms of the alkyl group can be 1 or more, 2 or more, 3 or more, or 4 or more. The number of carbon atoms of the alkyl group can 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 can 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.

[0063] (A) The component 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 other than a naphthyl group (for example, a phenyl group), etc.

[0064] As the counter cation in the component (a1), quaternary ammonium ions, tertiary ammonium ions, secondary ammonium ions, primary ammonium ions, ammonium ions, imidazolium ions, imidazolinium ions, pyridinium ions, alkali metal ions (such as sodium ions, potassium ions, etc.), phosphonium cations, sulfonium cations, iodonium cations, etc. can be cited. The component (a1) may not contain metal ions or may contain metal ions. As the metal ions, alkali metal ions (such as sodium ions, potassium ions, etc.) can be cited. From the viewpoint of easily reducing the reaction initiation temperature, the component (a1) may contain quaternary ammonium ions as the counter cation.

[0065] In the quaternary ammonium ions, as the substituents bonded to the nitrogen atom, alkyl groups, aryl groups (such as phenyl groups), etc. can be cited. From the viewpoint of easily reducing the reaction initiation temperature, as the counter cation, the component (a1) may contain quaternary ammonium ions having an alkyl group bonded to the nitrogen atom, or may contain quaternary ammonium ions 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.

[0066] From the viewpoint of easily reducing the reaction initiation temperature, the number of carbon atoms of the alkyl group bonded to the nitrogen atom can be within the following range. The number of carbon atoms of the alkyl group can be 1 or more, 2 or more, 3 or more, or 4 or more. The number of carbon atoms of the alkyl group can 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 can be 1 to 18, 1 to 8, 1 to 4, 2 to 6, 4 to 18, or 4 to 8.

[0067] As the quaternary ammonium ions, tetraalkylammonium ions, trialkylammonium ions, dialkylammonium ions, monoalkylammonium ions, tetraarylammonium ions, triarylammonium ions, diarylammonium ions, monoarylammonium ions, etc. can be cited. From the viewpoint of easily reducing the reaction initiation temperature, the component (a1) may contain tetraalkylammonium ions as the counter cation.

[0068] As the tetraalkylammonium ions, tetramethylammonium ions, tetraethylammonium ions, tetrapropylammonium ions, tetrabutylammonium ions (such as tetra-n-butylammonium ions), tetrahexylammonium ions, triethylmethylammonium ions, tributylethylammonium ions, trimethyldecylammonium ions, etc. can be cited. From the viewpoint of easily reducing the reaction initiation temperature, the component (a1) may contain tetrabutylammonium ions as the counter cation.

[0069] From the viewpoint of easily reducing the reaction initiation temperature, based on the total mass of the polymerizable composition, the content of the component (a1) can be within the following ranges. The content of the component (a1) can 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, 1.15% by mass or more, or 1.20% by mass or more. The content of the component (a1) can 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) can 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 2.00% by mass, 0.30 to 2.00% by mass, 0.70 to 2.00% by mass, 0.01 to 1.00% by mass, 0.30 to 1.00% by mass, or 0.70 to 1.00% by mass. The adhesive strength can also be adjusted by adjusting the content of the component (a1).

[0070] The polymerizable composition of the present embodiment contains at least one selected from the group consisting of an aromatic carboxylic acid b, a salt of the aromatic carboxylic acid b, and a hydrate of the aromatic carboxylic acid b (however, excluding the compound belonging to the component (a1)) as the component (B). Examples of the salt of the aromatic carboxylic acid b include alkali metal salts such as sodium salt and potassium salt. At least one selected from the group consisting of an aromatic carboxylic acid b, a salt of the aromatic carboxylic acid b, and a hydrate of the aromatic carboxylic acid b (however, excluding the compound belonging to the component (a1)) can be at least one selected from the group consisting of an aromatic carboxylic acid b and a hydrate of the aromatic carboxylic acid b, or can be an aromatic carboxylic acid b.

[0071] The aromatic carboxylic acid b has at least one aromatic ring. From the viewpoint of easily reducing the reaction initiation temperature, the number of aromatic rings (the number in one molecule) can be 1. Examples of the aromatic ring include a benzene ring and a naphthalene ring. From the viewpoint of easily reducing the reaction initiation temperature, the aromatic carboxylic acid b can include an aromatic carboxylic acid having a benzene ring.

[0072] Aromatic carboxylic acid b has a carboxyl group bonded to an aromatic ring. From the viewpoints of easily reducing the reaction initiation temperature and easily obtaining excellent storage stability (excellent storage stability related to the reaction initiation temperature; the same hereinafter), aromatic carboxylic acid b may contain an aromatic carboxylic acid having a hydroxyl group (phenolic hydroxyl group) bonded to an aromatic ring. From the viewpoints of easily reducing the reaction initiation temperature, easily obtaining excellent storage stability, and easily obtaining excellent adhesive strength, aromatic carboxylic acid b may have a hydroxyl group bonded to the para-position relative to the carboxyl group bonded to the aromatic ring, may have one or two hydroxyl groups bonded to the ortho-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.

[0073] From the viewpoints of easily reducing the reaction initiation temperature and easily obtaining excellent storage stability, in aromatic carboxylic acid b, the number of carboxyl groups (the number in one molecule) bonded to the aromatic ring may be 1. From the viewpoints of easily reducing the reaction initiation temperature and easily obtaining excellent storage stability, in aromatic carboxylic acid b, the number of hydroxyl groups (the number in one molecule) or the number of hydroxyl groups bonded to the aromatic ring (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, may also be 2, or may also be 3.

[0074] The aromatic ring of aromatic carboxylic acid b may have substituents other than carboxyl and hydroxyl groups, or may not have substituents other than carboxyl and hydroxyl groups. Examples of the substituents include alkyl groups, alkoxy groups, etc.

[0075] Examples of the aromatic carboxylic acid b include dihydroxybenzoic acids such as 3,4-dihydroxybenzoic acid (protocatechuic acid), 3,5-dihydroxybenzoic acid (α-resorcylic acid), 2,3-dihydroxybenzoic acid (2-pyrocatechuic acid), 2,4-dihydroxybenzoic acid (β-resorcylic acid), 2,4-dihydroxy-6-methylbenzoic acid (orsellinic acid), 2,5-dihydroxybenzoic acid (gentisic acid), and 2,6-dihydroxybenzoic acid (γ-resorcylic acid); and trihydroxybenzoic acids such as 3,4,5-trihydroxybenzoic acid (gallic acid) and 2,4,6-trihydroxybenzoic acid (phloroglucinol carboxylic acid). From the viewpoints of easily reducing the reaction initiation temperature, easily obtaining excellent storage stability, and easily obtaining excellent adhesive strength, the aromatic carboxylic acid b may contain 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, and 3,4,5-trihydroxybenzoic acid, or may contain at least one selected from the group consisting of 3,4-dihydroxybenzoic acid and 3,4,5-trihydroxybenzoic acid. From the viewpoint of easily obtaining excellent storage stability, the aromatic carboxylic acid b may contain 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, and 3,4,5-trihydroxybenzoic acid, or may contain at least one selected from the group consisting of 3,4-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, and 3,4,5-trihydroxybenzoic acid, or may contain 3,4-dihydroxybenzoic acid. From the viewpoint of easily reducing the reaction initiation temperature, the aromatic carboxylic acid b may contain 3,4,5-trihydroxybenzoic acid. From the viewpoint of easily obtaining excellent adhesive strength, the aromatic carboxylic acid b may contain at least one selected from the group consisting of 3,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 2,3-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, and 3,4,5-trihydroxybenzoic acid.

[0076] From the viewpoint of easily reducing the reaction initiation temperature, 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, the content of the component (B) 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.

[0077] Based on the total mass of the polymeric composition, the content of component (B) can be within the following ranges. From the perspective of easily reducing the reaction initiation temperature, the content of component (B) can 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, 1.90% by mass or more, 2.00% by mass or more, 2.50% by mass or more, 3.00% by mass or more, or 3.50% by mass or more. From the perspective of easily obtaining excellent storage stability, the content of component (B) can 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, 3.50% by mass or less, 3.00% by mass or less, 2.50% by mass or less, 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 perspectives, the content of component (B) can be 0.01 - 10.00% by mass, 0.01 - 2.50% by mass, 0.01 - 2.00% by mass, 1.00 - 10.00% by mass, 1.00 - 2.50% by mass, 1.00 - 2.00% by mass, 1.50 - 10.00% by mass, 1.50 - 2.50% by mass, or 1.50 - 2.00% by mass. The adhesive strength can also be adjusted by adjusting the content of component (B).

[0078] From the viewpoint of easily lowering the reaction initiation temperature, the mass ratio R1 ((B) component / (a1) component) of the content of the (B) component to the content of the (a1) component can be within the following ranges. The mass ratio R1 can 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 4.50 or more. The mass ratio R1 can 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 can be 0.01 to 10.00, 0.01 to 6.00, 0.01 to 3.00, 1.00 to 10.00, 1.00 to 6.00, 1.00 to 3.00, 1.50 to 10.00, 1.50 to 6.00, or 1.50 to 3.00.

[0079] The polymerizable composition of the present embodiment contains a phosphorus compound having a P═O(OH) structure (however, excluding compounds belonging to the (a1) component or the (B) component) as the (C) component. By using the (C) component, it is easy to improve the adhesion between the polymerizable composition or its cured product and a substrate (a substrate containing a metal material (e.g., aluminum), glass, etc.). In the 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 hydroxyl group is bonded to the phosphorus atom via a single bond. From the viewpoints of easily lowering the reaction initiation temperature and easily obtaining excellent adhesive strength, in the (C) component, the number of P═O(OH) structures (the number in one molecule) can be 1.

[0080]

[0081] [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.]

[0082] From the viewpoints of easily lowering the reaction initiation temperature and easily obtaining excellent adhesive strength, c11 can be 1 to 2 or 2 to 3.

[0083] (C) component may have a monovalent group different from the hydroxyl group (R in the general formula (c1)) c1) As a functional group bonded to a phosphorus atom. As such a monovalent group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group (e.g., phenyl group), a group containing (meth)acryloyl group, etc. may be mentioned. The group containing (meth)acryloyl group is a group having at least one selected from the group consisting of acryloyl group and methacryloyl group.

[0084] From the viewpoints of easily reducing the reaction initiation temperature and easily obtaining excellent adhesive strength, the component (C) may contain at least one selected from the group consisting of (meth)acrylate compounds having a P=O(OH) structure, phosphoric acid, and phenylphosphonic acid, may contain a (meth)acrylate compound having a P=O(OH) structure, or may contain a compound represented by the following general formula (c2).

[0085]

[0086] [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. ]

[0087] From the viewpoints of easily reducing the reaction initiation temperature and easily obtaining excellent adhesive strength, 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 viewpoints of easily reducing the reaction initiation temperature and easily obtaining excellent adhesive strength, c24 may be 1 to 4, 2 to 4, 1 to 3, or 1 to 2.

[0088] From the viewpoints of easily reducing the reaction initiation temperature and easily obtaining excellent adhesive strength, based on the total mass of the phosphorus-containing compound (compound containing a phosphorus atom) contained in 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%.

[0089] From the viewpoints of easily reducing the reaction initiation temperature and easily obtaining excellent adhesive strength, based on the total mass of the polymerizable composition, the content of component (C) can be within the following ranges. The content of component (C) can 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, 1.20% by mass or more, 1.50% by mass or more, or 1.80% by mass or more. The content of component (C) can 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, 2.00% by mass or less, 1.80% by mass or less, 1.50% by mass or less, 1.20% 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 component (C) can be 0.01 to 10.00% by mass, 0.01 to 2.00% by mass, 0.01 to 1.00% by mass, 0.20 to 10.00% by mass, 0.20 to 2.00% by mass, 0.20 to 1.00% by mass, 0.50 to 10.00% by mass, 0.50 to 2.00% by mass, or 0.50 to 1.00% by mass.

[0090] From the viewpoints of easily reducing the reaction initiation temperature and easily obtaining excellent storage stability, the mass ratio R21 ((C) component / (a1) component) of the content of the (C) component to the content of the (a1) component can be within the following ranges. The mass ratio R21 can 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, 0.45 or more, 0.50 or more, 0.60 or more, 0.80 or more, 1.00 or more, 1.20 or more, 1.30 or more, 1.50 or more, 1.80 or more, 2.00 or more, or 2.30 or more. The mass ratio R21 can 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, 2.30 or less, 2.00 or less, 1.80 or less, 1.50 or less, 1.30 or less, 1.20 or less, 1.00 or less, 0.80 or less, 0.60 or less, 0.50 or less, 0.45 or less, or 0.40 or less. From these viewpoints, the mass ratio R21 is 0.01 to 10.00, 0.01 to 5.00, 0.01 to 2.00, 0.50 to 10.00, 0.50 to 5.00, 0.50 to 2.00, 1.00 to 10.00, 1.00 to 5.00, or 1.00 to 2.00.

[0091] From the viewpoints of easily reducing the reaction initiation temperature and easily obtaining excellent adhesive strength,

[0092] The mass ratio R22 ((C) component / (B) component) of the content of the (C) component relative to the content of the (B) component can be within the following ranges. The mass ratio R22 can 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, 0.70 or more, 0.75 or more, 0.80 or more, 0.85 or more, 0.90 or more, or 1.00 or more. The mass ratio R22 can 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, 0.75 or less, 0.70 or less, 0.65 or less, 0.60 or less, 0.55 or less, 0.50 or less, 0.45 or less, 0.40 or less, 0.35 or less, 0.30 or less, 0.25 or less, 0.20 or less, or 0.15 or less. From these viewpoints, the mass ratio R22 can 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.

[0093] The polymerizable composition of the present embodiment may contain a polymerizable compound (however, excluding compounds belonging to the (a1) component, (B) component, or (C) component) as the (D) component.

[0094] Examples of the (D) component include a radical polymerizable compound, a cationic polymerizable compound, an anionic polymerizable compound, etc. From the viewpoint of easily reducing the reaction initiation temperature, the (D) component may contain a radical polymerizable compound.

[0095] Examples of component (D) include (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. Among these compounds, compounds belonging to both (meth)acrylate compounds and other compounds belong to (meth)acrylate compounds. From the viewpoint of easily lowering the reaction initiation temperature, component (D) may contain compounds having an ethylenically unsaturated bond, and may also contain (meth)acrylate compounds. From the viewpoint of easily lowering the reaction initiation temperature, component (D) may contain compounds different from epoxy compounds, and may also contain compounds not having an epoxy group.

[0096] 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, 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, 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, pentaerythritol tetra(meth)acrylate, polyethylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenoxyethyl (meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol (meth)acrylate, dipentaerythritol hexa(meth)acrylate, isocyanuric acid alkylene oxide modified di(meth)acrylate, isocyanuric acid alkylene oxide modified tri(meth)acrylate, tricyclodecyl (meth)acrylate, dimethylol tricyclodecane di(meth)acrylate, 2-hydroxy-1,3-di(meth)acryloyloxypropane, 2,2-bis[4-((meth)acryloxymethoxy)phenyl]propane, 2,2-bis[4-((meth)acryloxypolyethoxy)phenyl]propane, etc. "Polyurethane (meth)acrylate" and "urethane (meth)acrylate" are collectively referred to as "(poly)urethane (meth)acrylate". The component (D) may contain a bifunctional (meth)acrylate compound.

[0097] From the viewpoint of easily reducing the reaction initiation temperature, the component (D) may contain a urethane (meth)acrylate compound having a polycarbonate skeleton (hereinafter referred to as "(d1) component"), may contain a urethane (meth)acrylate compound having a structure derived from a polycarbonate polyol, or may contain a compound represented by the following general formula (d1).

[0098]

[0099] [In the formula, R1 represents a hydrogen atom or a methyl group, j represents an integer from 1 to 3, k represents an integer from 2 to 7, m represents an integer from 1 to 8, and n represents an integer from 5 to 7.

[0100] From the viewpoint of easily reducing the reaction initiation temperature, in the general formula (d1), j can be 1 to 2 or 2 to 3, k can be 2 to 3 or 3 to 5, m can be 1 to 6, 1 to 4 or 1 to 2, and n can be 5 to 6 or 6 to 7.

[0101] From the viewpoint of easily reducing the reaction initiation temperature, the weight-average molecular weight of the (d1) component can 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 reducing the reaction initiation temperature, the weight-average molecular weight of the (d1) component can 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 (d1) component can be 1000 to 100000, 5000 to 50000, or 10000 to 30000.

[0102] From the viewpoint of easily reducing the reaction initiation temperature, based on the total mass of the (D) component, the content of the (d1) component can be within the following ranges. The content of the (d1) component can 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 (d1) component can 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 (d1) component can be 10.00 to 90.00% by mass, 10.00 to 80.00% by mass, 10.00 to 70.00% by mass, 20.00 to 90.00% by mass, 20.00 to 80.00% by mass, 20.00 to 70.00% by mass, 40.00 to 90.00% by mass, 40.00 to 80.00% by mass, or 40.00 to 70.00% by mass.

[0103] From the viewpoint of easily lowering the reaction initiation temperature, based on the total mass of the polymerizable composition, the content of component (d1) can be within the following ranges. The content of component (d1) can 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 component (d1) can 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 (d1) can be 5.00 to 50.00% by mass, 5.00 to 40.00% by mass, 5.00 to 30.00% by mass, 10.00 to 50.00% by mass, 10.00 to 40.00% by mass, 10.00 to 30.00% by mass, 20.00 to 50.00% by mass, 20.00 to 40.00% by mass, or 20.00 to 30.00% by mass.

[0104] From the viewpoint of easily lowering the reaction initiation temperature, component (D) may contain an isocyanuric acid alkylene oxide-modified di(meth)acrylate (excluding compounds belonging to component (d1); hereinafter, referred to as "component (d2)"), and may also contain an isocyanuric acid ethylene oxide-modified di(meth)acrylate.

[0105] From the viewpoint of easily lowering the reaction initiation temperature, based on the total mass of component (D), the content of component (d2) can be within the following ranges. The content of component (d2) can 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 component (d2) can 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 (d2) can be 1.00 to 50.00% by mass, 1.00 to 40.00% by mass, 1.00 to 30.00% by mass, 10.00 to 50.00% by mass, 10.00 to 40.00% by mass, 10.00 to 30.00% by mass, 20.00 to 50.00% by mass, 20.00 to 40.00% by mass, or 20.00 to 30.00% by mass.

[0106] From the viewpoint of easily reducing the reaction initiation temperature, based on the total mass of the polymerizable composition, the content of the component (d2) can be within the following ranges. The content of the component (d2) can 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 (d2) can 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 the component (d2) can be 1.00 to 30.00% by mass, 1.00 to 20.00% by mass, 1.00 to 10.00% by mass, 5.00 to 30.00% by mass, 5.00 to 20.00% by mass, 5.00 to 10.00% by mass, 7.00 to 30.00% by mass, 7.00 to 20.00% by mass, or 7.00 to 10.00% by mass.

[0107] From the viewpoint of easily reducing the reaction initiation temperature, the component (D) may contain a di(meth)acrylate compound having at least one selected from the group consisting of a dicyclopentyl structure and a dicyclopentenyl structure (excluding compounds belonging to the component (d1) or the component (d2); hereinafter, referred to as “component (d3)”), and may also contain at least one selected from the group consisting of dimethylol tricyclodecane di(meth)acrylate and tricyclodecane diol di(meth)acrylate.

[0108] From the viewpoint of easily reducing the reaction initiation temperature, based on the total mass of the component (D), the content of the component (d3) can be within the following ranges. The content of the component (d3) can 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 (d3) can 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 (d3) can be 1.00 to 50.00% by mass, 1.00 to 40.00% by mass, 1.00 to 30.00% by mass, 10.00 to 50.00% by mass, 10.00 to 40.00% by mass, 10.00 to 30.00% by mass, 20.00 to 50.00% by mass, 20.00 to 40.00% by mass, or 20.00 to 30.00% by mass.

[0109] From the viewpoint of easily reducing the reaction initiation temperature, based on the total mass of the polymeric composition, the content of component (d3) may be within the following ranges. The content of component (d3) 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 component (d3) 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 (d3) may be 1.00 to 30.00% by mass, 1.00 to 20.00% by mass, 1.00 to 10.00% by mass, 5.00 to 30.00% by mass, 5.00 to 20.00% by mass, 5.00 to 10.00% by mass, 7.00 to 30.00% by mass, 7.00 to 20.00% by mass, or 7.00 to 10.00% by mass.

[0110] From the viewpoint of easily reducing the reaction initiation temperature, based on the total mass of the polymeric composition,

[0111] (D) The content of the component may be within the following ranges. The content of component (D) 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 component (D) 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 component (D) may be 10.00 to 80.00% by mass, 10.00 to 60.00% by mass, 10.00 to 50.00% by mass, 30.00 to 80.00% by mass, 30.00 to 60.00% by mass, 30.00 to 50.00% by mass, 35.00 to 80.00% by mass, 35.00 to 60.00% by mass, or 35.00 to 50.00% by mass.

[0112] From the viewpoint of easily reducing the reaction initiation temperature, the mass ratio R31 ((D) component / (a1) component) of the content of the (D) component to the content of the (a1) component can be within the following ranges. The mass ratio R31 can 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. The mass ratio R31 can 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 can 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.

[0113] (D) component / (B) component) of the content of the (D) component to the content of the (B) component can be within the following ranges. From the viewpoint of easily obtaining excellent storage stability, the mass ratio R32 can 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 reducing the reaction initiation temperature, the mass ratio R32 can 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, 20.00 or less, or 15.00 or less. From these viewpoints, the mass ratio R32 can 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.

[0114] From the viewpoint of easily reducing the reaction initiation temperature, the mass ratio R33 ((D) component / (C) component) of the content of the (D) component to the content of the (C) component can be within the following ranges. The mass ratio R33 can 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, 45.00 or more, 50.00 or more, 60.00 or more, 70.00 or more, 80.00 or more, 90.00 or more, or 100.00 or more. The mass ratio R33 can 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, 90.00 or less, 80.00 or less, 70.00 or less, 60.00 or less, 50.00 or less, 45.00 or less, 40.00 or less, 35.00 or less, 30.00 or less, or 25.00 or less. From these viewpoints, the mass ratio R33 can 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.

[0115] The polymerizable composition of the present embodiment may contain a polymerization initiator (however, compounds belonging to the (a1) component, (B) component, (C) component, or (D) component are excluded) as the (E) component. The (E) component may contain a thermal polymerization initiator. Examples of the (E) component include a radical polymerization initiator, a cationic polymerization initiator, and an anionic polymerization initiator. From the viewpoint of easily reducing the reaction initiation temperature, the (E) component may contain a radical polymerization initiator.

[0116] As the component (E), examples thereof include ketone peroxides such as methyl ethyl ketone peroxide, cyclohexanone peroxide, and methyl cyclohexanone 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, 1,1-bis(tert-hexylperoxy)-3,3,5-trimethylcyclohexane; hydroperoxides such as p-menthane hydroperoxide; dialkyl peroxides such as α,α'-bis(tert-butylperoxy)diisopropylbenzene, diisopropylbenzene peroxide, tert-butyl isopropylbenzene peroxide, di-tert-butyl peroxide; diacyl peroxides such as dioctanoyl peroxide, dilauroyl peroxide, distearoyl peroxide, dibenzoyl peroxide; peroxycarbonates such as bis(4-tert-butylcyclohexyl) peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-3-methoxybutyl peroxymonocarbonate; peroxy esters such as tert-butyl peroxypivalate, tert-hexyl peroxypivalate, 1,1,3,3-tetramethylbutyl peroxyl-2-ethylhexanoate, 2,5-dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane, tert-hexyl peroxy-2-ethylhexanoate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxyisobutyrate, tert-hexyl peroxyisopropyl monocarbonate, tert-butyl peroxy-3,5,5-trimethylhexanoate, tert-butyl peroxylaurate, tert-butyl peroxyisopropyl monocarbonate, tert-butyl peroxy-2-ethylhexyl monocarbonate, tert-butyl peroxybenzoate, tert-hexyl peroxybenzoate, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane, tert-butyl peroxyacetate; acid anhydrides such as 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 hexahydrophthalic anhydride, methyl tetrahydrophthalic 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, 2,3,6,7-naphthalenetetracarboxylic dianhydride; azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2'-dimethylvaleronitrile); iodide salts; sulfonium salts; phosphonium salts; imidazole compounds, etc.

[0117] From the viewpoints of easily lowering the reaction initiation temperature, easily obtaining excellent storage stability, and easily obtaining excellent adhesive strength, the component (E) may contain a peroxide, may contain an organic peroxide, may contain at least one selected from the group consisting of a ketone peroxide and a diacyl peroxide, may contain a ketone peroxide, may contain 1,1-bis(tert-butylperoxy)cyclohexane, may contain a diacyl peroxide, and may contain dilauroyl peroxide.

[0118] Based on the total mass of the polymerizable composition, the content of the component (E) may be within the following ranges. From the viewpoint of lowering the reaction initiation temperature, the content of the component (E) 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. The content of the component (E) 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 (E) may be 0.10 to 20.00% by mass, 0.10 to 10.00% by mass, 0.10 to 5.00% by mass, 1.00 to 20.00% by mass, 1.00 to 10.00% by mass, 1.00 to 5.00% by mass, 3.00 to 20.00% by mass, 3.00 to 10.00% by mass, or 3.00 to 5.00% by mass.

[0119] From the viewpoint of easily lowering the reaction initiation temperature, the mass ratio R41 ((E) component / (a1) component) of the content of the component (E) to the content of the component (a1) may be within the following ranges. 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, 4.00 or more, 5.00 or more, 6.00 or more, 8.00 or more, or 10.00 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, 3.00 to 50.00, 3.00 to 15.00, 3.00 to 6.00, 5.00 to 50.00, 5.00 to 15.00, or 5.00 to 6.00.

[0120] (E) The mass ratio R42 ((E) component / (B) component) of the content of the (E) component to the content of the (B) component can be within the following ranges. From the viewpoint of easily obtaining excellent storage stability, the mass ratio R42 can 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 reducing the reaction initiation temperature, the mass ratio R42 can 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, 2.00 or less, or 1.50 or less. From these viewpoints, the mass ratio R42 can 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.

[0121] From the viewpoints of easily reducing the reaction initiation temperature and easily obtaining excellent storage stability, the mass ratio R43 ((E) component / (C) component) of the content of the (E) component to the content of the (C) component can be within the following ranges. The mass ratio R43 can 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, 5.00 or more, 5.50 or more, 6.00 or more, 6.50 or more, 7.00 or more, 8.00 or more, 9.00 or more, 10.00 or more, or 12.00 or more. The mass ratio R43 can 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, 5.00 or less, 4.50 or less, 4.00 or less, 3.50 or less, 3.00 or less, or 2.50 or less. From these viewpoints, the mass ratio R43 can 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.

[0122] From the viewpoint of easily reducing the reaction initiation temperature, the mass ratio R44 ((E) component / (D) component) of the content of the (E) component to the content of the (D) component can be within the following ranges. The mass ratio R44 can 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 can 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 can 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.

[0123] The polymerizable composition of the present embodiment may contain a thermoplastic resin as the (F) component.

[0124] Examples of the (F) component include phenoxy resin, polyester, polyurethane (excluding polyester urethane), polyester urethane, ethylene-vinyl acetate copolymer, butyral resin, etc. From the viewpoint of easily reducing the reaction initiation temperature, the (F) component may contain at least one selected from the group consisting of polyester urethane and ethylene-vinyl acetate copolymer.

[0125] From the viewpoint of easily reducing the reaction initiation temperature, based on the total mass of the polymerizable composition, the content of the (F) component can be within the following ranges. The content of the (F) component can 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 (F) component can 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 (F) component can be 10.00 to 90.00% by mass, 10.00 to 70.00% by mass, 10.00 to 60.00% by mass, 30.00 to 90.00% by mass, 30.00 to 70.00% by mass, 30.00 to 60.00% by mass, 40.00 to 90.00% by mass, 40.00 to 70.00% by mass, or 40.00 to 60.00% by mass.

[0126] The polymerizable composition of the present embodiment may contain components other than the above components. Examples of such components include water, organic solvents, coupling agents, fillers, softeners, accelerators (e.g., polymerization accelerators), deterioration inhibitors, colorants, flame retardants, thixotropic agents, etc. The polymerizable composition of the present embodiment may contain at least one of these components, or may not contain at least one of these components. The polymerizable composition of the present embodiment may not contain a filler, or may not contain an inorganic filler. Based on the total mass of the polymerizable composition, the content of the filler or the content of the inorganic filler may be 50% by mass or less, less than 50% by mass, 10% by mass or less, 1% by mass or less, 0.1% by mass or less, or 0.01% by mass or less, or may be substantially 0% by mass.

[0127] The polymerizable composition of the present embodiment may be in the form of a film. The thickness of the film-like polymerizable composition or the thickness of the cured product of the present embodiment may be within 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.

[0128] Examples

[0129] Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.

[0130] <Synthesis of urethane acrylate (UA1)>

[0131] To a reaction vessel (equipped with a stirrer, a thermometer, a reflux condenser with a calcium chloride drying tube, and a nitrogen inlet tube), 2500 parts by mass (2.50 mol) of poly(1,6-hexanediol carbonate) (trade name: DURANOL T5652, manufactured by Asahi Kasei Corp.) and 666 parts by mass (3.00 mol) of isophorone diisocyanate (manufactured by Sigma-Aldrich Co., LLC) were uniformly added dropwise over 3 hours. Subsequently, after sufficiently introducing nitrogen into the reaction vessel, the inside of the reaction vessel was heated to 70 - 75 °C to cause a reaction. Then, 0.53 part 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 vessel. After that, 238 parts by mass (2.05 mol) of 2-hydroxyethyl acrylate (manufactured by Sigma-Aldrich Co., LLC) was added, and the reaction was carried out at 70 °C for 6 hours in an air atmosphere. Thus, a urethane acrylate (UA1) having a polycarbonate backbone was obtained. The weight-average molecular weight of the urethane acrylate (UA1) was 15000.

[0132] <Synthesis of polyester urethane (EU1)>

[0133] To a stainless-steel autoclave with a heater equipped with a stirrer, a thermometer, a condenser, a vacuum generating device, and a nitrogen inlet tube, 48 parts by mass of isophthalic acid and 37 parts by mass of neopentyl glycol were charged. Then, 0.02 part by mass of tetrabutoxytitanate was charged as a catalyst. Subsequently, it was heated to 220 °C under a nitrogen stream and stirred in this state 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 washing the precipitate with water, it was dried under vacuum to obtain a polyester polyol. After sufficiently drying the polyester polyol, it was dissolved in MEK (methyl ethyl ketone), and the solution was charged into a four-necked flask equipped with a stirrer, a dropping funnel, a reflux condenser, and a nitrogen inlet tube. And 0.05 part by mass (catalyst) of dibutyltin dilaurate was added in an amount relative to 100 parts by mass of the polyester polyol. 50 parts by mass of 4,4'-diphenylmethane diisocyanate relative to 100 parts by mass of the polyester polyol was dissolved in MEK and added using the dropping funnel. Then, polyester urethane (EU1) was obtained by stirring at 80 °C for 4 hours.

[0134] <Preparation of polymerizable composition>

[0135] (Examples A1 to A14 and Examples B1 to B15)

[0136] A polymerizable composition was prepared by mixing a methyl ethyl ketone solution of a boron salt (tetrabutylammonium = butyltrinaphthyl borate, manufactured by Resonac Corporation, trade name: Karenz N3B) (solid component ratio: 20% by mass), an acid component shown in Table 1 or Table 2, a phosphorus compound (a phosphorus compound having a P=O(OH) structure, a phosphate ester containing a methacryloyl group, manufactured by Nippon Kayaku Co., Ltd., trade name: PM-21), a urethane acrylate (UA1), an isocyanuric acid ethylene oxide-modified diacrylate (manufactured by TOAGOSEI CO., LTD., trade name: M-215), a dimethyloltricyclodecane diacrylate (manufactured by KYOEISHACHEMICAL Co., LTD., trade name: LIGHT ACRYLATE DCP-A), a polymerization initiator (a toluene solution of polymerization initiator A (dilauroyl peroxide, manufactured by NOF CORPORATION., trade name: PEROYL L) (solid component ratio: 20% by mass) or a solution of polymerization initiator B (a solution of 1,1-bis(tert-butylperoxy)cyclohexane, manufactured by NOF CORPORATION., trade name: PERHEXA C, solid component ratio: 80% by mass), a methyl ethyl ketone / toluene mixed solution of a polyester urethane (EU1) (mass ratio: 1 / 1, solid component ratio: 40% by mass) and a toluene solution of an ethylene vinyl acetate copolymer (manufactured by DuPont, trade name: EV40W) (solid component ratio: 30% by mass). The amounts of the boron salt, acid component and phosphorus compound used (solid component amount, unit: parts by mass) are shown in Tables 1 and 2. The amount of 3,4,5-trihydroxybenzoic acid used is the amount of 3,4,5-trihydroxybenzoic acid monohydrate used. 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 dimethyloltricyclodecane diacrylate used is 10.00 parts by mass, the amount of polymerization initiator used (solid component amount) is 5.00 parts by mass, the amount of polyester urethane (EU1) used (solid component amount) is 47.50 parts by mass, and the amount of ethylene vinyl acetate copolymer used (solid component amount) is 7.50 parts by mass.As the acid component, 3,4-dihydroxybenzoic acid (protocatechuic acid, manufactured by FUJIFILM Wako Pure Chemical Corporation), 2,3-dihydroxybenzoic acid (2-catecholcarboxylic acid, manufactured by FUJIFILM Wako Pure Chemical Corporation), 2,4-dihydroxybenzoic acid (β-resorcylic acid, manufactured by FUJIFILM Wako Pure Chemical Corporation), 2,5-dihydroxybenzoic acid (gentisic acid, manufactured by FUJIFILM Wako Pure Chemical Corporation), 3,5-dihydroxybenzoic acid (α-resorcylic acid, manufactured by FUJIFILM Wako Pure Chemical Corporation), or 3,4,5-trihydroxybenzoic acid (gallic acid, monohydrate, manufactured by FUJIFILM Wako Pure Chemical Corporation) was used.

[0137] (Comparative Example 1)

[0138] A polymerizable composition was prepared in the same manner as in Example A1 except that the acid component and the phosphorus compound were not used.

[0139] <Evaluation>

[0140] (Reaction initiation temperature)

[0141] The above polymerizable composition was coated on a PET film (after peeling treatment, thickness: 50 μm) using a bar coater (manufactured by YASUI SEIKI CO., LTD., trade name "KNIFE COATER SNC-300"), and then dried in an oven at 60°C for 3 minutes to produce a laminated film having a 20-μm-thick film-like polymerizable composition disposed on the PET film.

[0142] After peeling the PET film from the above-mentioned laminated film just after production, the heat generation behavior of the film-like polymerizable composition was measured by differential scanning calorimetry (hereinafter referred to as "DSC"), and the initiation temperature of the exothermic peak, which is an index of the polymerization reaction initiation temperature, was obtained. The DSC measurement was carried out under the following conditions to obtain the reaction initiation temperature T1. Further, after putting the above-mentioned laminated film just after production in the example into 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 to enclose the laminated film. Then, the bag was put into an aluminum light-shielding bag. In this state, after leaving the laminated film at 25 °C for 24 hours, the laminated film was taken out from the light-shielding bag, and the reaction initiation temperature T2 was obtained by the same procedure as the above steps. Then, as the change rate (%) of the reaction initiation temperature, "[(T2 - T1) / T1]×100" was calculated. The results are shown in Tables 1 and 2.

[0143] (DSC Measurement Conditions)

[0144] Measuring device: manufactured by PerkinElmer Japan G.K., product name "DSC8500"

[0145] Sample amount: 10.0 ± 0.2 mg

[0146] Measuring temperature range: 30 - 200 °C

[0147] Heating rate: 30 °C / minute

[0148] Measuring atmosphere gas: nitrogen

[0149] (Adhesion Strength)

[0150] Using a bar coater (manufactured by YASUI SEIKI CO., LTD., product name: "KNIFE COATER SNC-300"), the above polymerizable composition was coated on a PET film (subjected to a peeling treatment, thickness: 50 μm), and then dried in an oven at 60 °C for 3 minutes, thereby producing a laminated film A having a film-like polymerizable composition with a thickness of 20 μm disposed on the PET film. After obtaining a laminated film B by cutting the laminated film A into a width of 1 mm and a length of 5 cm, the laminated film B was disposed on a polyimide film (thickness: 25 μm). After peeling the PET film from the laminated film B, a glass plate (thickness: 1.1 mm) was brought into contact with the film-like polymerizable composition, thereby interposing the film-like polymerizable composition between the polyimide film and the glass plate. Using a hot pressing device (manufactured by Takahashi Koki Co., Ltd.), heating and pressing were performed at 90 °C and 3 MPa for 30 seconds, thereby obtaining a test piece.

[0151] Using the above test piece, the adhesive strength was measured in accordance with JIS Z 0237 by the 90-degree peeling method (peeling speed: 50 mm / minute, 10 mm width, 25 °C). As the measuring device for the adhesive strength, a small tabletop testing machine "EZ-LX" of SHIMADZU CORPORATION was used. The results are shown in Tables 1 and 2.

[0152] [Table 1]

[0153]

[0154] [Table 2]

[0155]

Claims

1. A polymerizable composition, which is a polymerizable composition containing a polymerizable compound, and contains: (A) A borate anion; (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; and (C) a phosphorus compound having a P=O(OH) structure.

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 borate salt containing 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 borate salt containing the component (A) is 0.01 to 10.

00.

10. The polymerizable composition according to any one of claims 1 to 5, wherein the component (C) contains a (meth)acrylate compound having a P=O(OH) structure.

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

12. The polymerizable composition according to any one of claims 1 to 5, wherein the polymerizable compound contains a (meth)acrylate compound.

13. The polymerizable composition according to any one of claims 1 to 5, which further contains a polymerization initiator.

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