Polymerizable composition

Abstract

The polymerizable composition is a polymerizable composition containing a polymerizable compound, and the polymerizable composition contains a photoacid generator and an acid component.

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 have been used for bonding various components. For example, a thermosetting composition containing a polymerizable compound is described in Patent Document 1 below.

[0003] Prior Art Documents

[0004] Patent Documents

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

[0006] Technical Problem to be Solved by the Invention

[0007] In recent years, with the miniaturization and high performance of various devices, there are sometimes cases where a polymerizable composition is thermally cured near a component that needs to avoid exposure to high heat, or a polymerizable composition in contact with a component that needs to avoid exposure to high heat is thermally cured. In these cases, from the viewpoint of avoiding deterioration of the component by performing thermal curing at a low temperature, a lower reaction start temperature is required for the polymerizable composition.

[0008] In response to this, the present inventors have found that sometimes the reaction start temperature during thermal curing is lowered by irradiating the polymerizable composition with light and then thermally curing the polymerizable composition.

[0009] An object of one aspect of the present invention is to provide a polymerizable composition in which the reaction start temperature during thermal curing after light irradiation is lower than the reaction start temperature during thermal curing alone.

[0010] Means for Solving the Technical Problem

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

[11] and the like in several aspects.

[0012] [1] A polymerizable composition, which is a polymerizable composition containing a polymerizable compound,

[0013] The polymerizable composition contains a photoacid generator and an acid component.

[0014] [2] The polymerizable composition according to [1], wherein

[0015] The photoacid generator contains a borate having a borate anion.

[0016] [3] The polymerizable composition according to [2], wherein

[0017] The boron salt further has a sulfonium cation.

[0018] [4] The polymerizable composition according to [3], wherein

[0019] The sulfonium cation has an aryl group bonded to a sulfur atom.

[0020] [5] The polymerizable composition according to any one of [1] to [4], wherein

[0021] The content of the photoacid generator is 0.01 to 20.00% by mass.

[0022] [6] The polymerizable composition according to any one of [1] to [5], wherein

[0023] The acid component contains a phosphorus compound.

[0024] [7] The polymerizable composition according to any one of [1] to [6], wherein

[0025] The acid component contains a phosphorus compound having a P=O(OH) structure.

[0026] [8] The polymerizable composition according to any one of [1] to [7], wherein

[0027] The content of the acid component is 0.01 to 10.00% by mass.

[0028] [9] The polymerizable composition according to any one of [1] to [8], wherein

[0029] The mass ratio of the content of the acid component to the content of the photoacid generator is 0.01 to 10.00.

[0030]

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

[0031] The polymerizable compound contains a (meth)acrylate compound.

[0032]

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

[10] further contains an organic peroxide.

[0033] Advantages of the Invention

[0034] According to one aspect of the present invention, there can be provided a polymerizable composition in which the reaction start temperature during thermal curing after light irradiation is lower than the reaction start temperature during thermal curing alone. Detailed Description

[0035] Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

[0036] In this specification, a 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" of a numerical range means a range of A and more than A. "A or less" of a numerical range means A and less than A. In the numerical ranges described stepwise in this 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 this specification, the upper limit value or the lower limit value of the numerical range can be replaced with the value shown in the examples. Regarding "A or B", either A or B can be included, or both can be included. Regarding the materials exemplified in this specification, unless otherwise specified, one kind can be used alone or two or more kinds can be used in combination. 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 means 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. 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 after removing the volatile components (water, organic solvents, etc.) that can be volatilized. 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, molasses-like, wax-like, etc. at 25°C.

[0037] In this specification, the "weight average molecular weight" can be measured by gel permeation chromatography (GPC) using the following measurement conditions and converted according to the calibration curve using standard polystyrene.

[0038] (Measurement conditions)

[0039] Apparatus: Manufactured by TOSOH CORPORATION, GPC-8020

[0040] Detector: Manufactured by TOSOH CORPORATION, RI-8020

[0041] Column: Manufactured by Showa Denko K.K., Gelpack GL-A-160-S + GL-A150

[0042] Sample concentration: 120 mg / 3 mL

[0043] Solvent: Tetrahydrofuran

[0044] Injection volume: 60 μL

[0045] Pressure: 294×10 6 Pa (30 kgf / cm 2 )

[0046] Flow rate: 1.00 mL / min

[0047] The polymerizable composition according to this embodiment is a polymerizable composition containing a polymerizable compound, and this polymerizable composition contains (A) a photoacid generator (hereinafter, sometimes referred to as "(A) component") and (B) an acid component (hereinafter, sometimes referred to as "(B) component").

[0048] The polymerizable composition according to this embodiment contains at least one polymerizable compound. As the polymerizable compound, it may contain at least one selected from the group consisting of (A) component and (B) component, or may contain a polymerizable compound not corresponding to at least one selected from the group consisting of (A) component and (B) component. When at least one selected from the group consisting of (A) component and (B) component is a polymerizable compound, the polymerizable composition according to this embodiment may contain a polymerizable compound not corresponding to at least one selected from the group consisting of (A) component and (B) component.

[0049] The polymerizable composition according to this embodiment can be used as a thermosetting polymerizable composition. According to the polymerizable composition according to this embodiment, the reaction start temperature T2 during thermosetting after light irradiation can be lowered compared to the reaction start temperature T1 during only thermosetting. According to the polymerizable composition according to this embodiment, in the evaluation method described in the following examples, the absolute value of the temperature difference (T2 - T1) between the reaction start temperature T1 and the reaction start temperature T2 can exceed 0 °C (preferably 1 °C or more, 3 °C or more, 5 °C or more, 8 °C or more, 9 °C or more, etc.). It is presumed that by irradiating light before thermosetting in a state where (A) component and (B) component are used in combination, the amount of energy required for the start of thermosetting is reduced, and thus the reaction start temperature T2 is lowered relative to the reaction start temperature T1. However, the factor for the decrease in the reaction start temperature T2 is not limited to this content.

[0050] The polymerizable composition according to this embodiment only needs to have the characteristic that the reaction start temperature during thermal curing after light irradiation is lower than the reaction start temperature during thermal curing only, and is not limited to the process of thermal curing after light irradiation. It can also be used in processes such as thermal curing without prior light irradiation, simultaneous light irradiation and thermal curing, and light irradiation after thermal curing. The use of the polymerizable composition according to this embodiment is not particularly limited, and examples include display devices, semiconductor devices, components for electronic devices, etc. The polymerizable composition according to this embodiment can also be used in micro LEDs (Light Emitting Diodes), micro OLEDs (Organic Light Emitting Diodes), etc.

[0051] The polymerizable composition according to this embodiment contains a photoacid generator as component (A). A photoacid generator is a general term for compounds that decompose upon irradiation with actinic energy rays to generate an acid. For example, it can be a compound that decomposes upon irradiation with actinic energy rays having a wavelength of 150 to 750 nm (such as a wavelength of 250 to 440 nm) to generate an acid.

[0052] From the viewpoint of easily reducing the reaction start temperature during thermal curing by light irradiation (easily making the reaction start temperature during thermal curing after light irradiation lower than the reaction start temperature during thermal curing only; the same applies hereinafter), component (A) can contain a compound having a borate anion, or can contain a borate salt having a borate anion (a salt of a borate anion and a counter cation. Hereinafter, it is referred to as “component (a1)”). In the polymerizable composition according to this embodiment, the borate anion can be bonded to the counter cation or can be free without being bonded to the counter cation.

[0053] In the borate anion, from the viewpoint of easily reducing the reaction start temperature during thermal curing by light irradiation, the number of boron atoms (the number in one molecule) can be 1 to 4, 1 to 3, or 1 to 2.

[0054] From the viewpoint of easily reducing the reaction start temperature during thermal curing by light irradiation, the borate anion can have a benzene ring (a substituted or unsubstituted phenyl group), or can have a benzene ring (a substituted or unsubstituted phenyl group) bonded to a boron atom. The borate anion may not have a naphthalene ring.

[0055] In the borate anion, from the viewpoint of easily reducing the reaction start temperature during thermal curing by light irradiation, the number of benzene rings (the number in one molecule) or the number of benzene rings bonded to a boron atom (the number in one molecule) can be 1 to 4, 2 to 4, or 3 to 4.

[0056] The borate anion may contain a benzene ring having substituents. Examples of the substituents include a halogen atom (e.g., a fluoro group), an alkyl group, an aryl group, an alkoxy group, etc. From the viewpoint of easily reducing the reaction initiation temperature during thermal curing by light irradiation, the borate anion may have a benzene ring substituted with a fluoro group or may have a benzene ring substituted with five fluoro groups.

[0057] Examples of the borate anion include (C 6 F 5 ) 4 B - (pentafluorophenyl borate anion), (C 6 F 5 ) 3 (C 6 H 5 )B - , (C 6 F 5 ) 2 (C 6 H 5 ) 2 B - , (C 6 F 5 )(C 6 H 5 ) 3 B - , (CN) 4 B - etc.

[0058] Examples of the counter cation in the component (a1) include a sulfonium cation, a quaternary ammonium ion, a tertiary ammonium ion, a secondary ammonium ion, a primary ammonium ion, an ammonium ion, an imidazolium ion, an imidazolinium ion, a pyridinium ion, an alkali metal ion (sodium ion, potassium ion, etc.), a phosphonium cation, an iodonium ion, etc. The component (a1) may not have a metal ion or may have a metal ion. Examples of the metal ion include an alkali metal ion (sodium ion, potassium ion, etc.). From the viewpoint of easily reducing the reaction initiation temperature during thermal curing by light irradiation, the component (a1) may have a sulfonium cation as the counter cation.

[0059] From the viewpoint of easily reducing the reaction initiation temperature during thermal curing by light irradiation, the component (A) may contain a compound having a sulfonium cation or may contain a salt having a sulfonium cation (a salt of a sulfonium cation and a counter anion. Hereinafter, it is referred to as “component (a2)”). In the polymerizable composition according to the present embodiment, the sulfonium cation may be bonded to the counter anion or may be free without being bonded to the counter anion. Examples of the counter anion include a borate anion (for example, various borate anions having the above characteristics related to the component (a1)), SbF 6 - 、AsF6 - , PF 6 - , CH 3 SO 3 - , CF 3 SO 3 - etc. In terms of the view that it is easy to lower the reaction start temperature during thermal curing by light irradiation, the (a2) component may have a borate anion as a counter anion.

[0060] In the sulfonium cation in the (a1) component or the (a2) component, examples of the substituent bonded to the sulfur atom (the sulfur atom with a positive charge) include an alkyl group, an aryl group, etc. Examples of the aryl group include a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted thioxanthone, etc. The substituted phenyl group does not include a substituted or unsubstituted biphenyl group. The substituent bonded to the sulfur atom (the sulfur atom with a positive charge) may be a substituent containing a sulfur atom (a sulfur atom different from the sulfur atom with a positive charge).

[0061] In terms of the view that it is easy to lower the reaction start temperature during thermal curing by light irradiation, the sulfonium cation in the (a1) component or the (a2) component may have an aryl group bonded to the sulfur atom (the sulfur atom with a positive charge). In the sulfonium cation, in terms of the view that it is easy to lower the reaction start temperature during thermal curing by light irradiation, the number of aryl groups bonded to the sulfur atom (the number in one molecule) may be 1 to 3 or 2 to 3. In the sulfonium cation, in terms of the view that it is easy to lower the reaction start temperature during thermal curing by light irradiation, the number of substituted or unsubstituted phenyl groups bonded to the sulfur atom (the number in one molecule) may be 1 to 3, 1 to 2 or 2 to 3.

[0062] In terms of the view that it is easy to lower the reaction start temperature during thermal curing by light irradiation, the sulfonium cation in the (a1) component or the (a2) component may have a substituted or unsubstituted phenyl group as the aryl group bonded to the sulfur atom (the sulfur atom with a positive charge), may have a substituted or unsubstituted biphenyl group, and may also have a substituted or unsubstituted thioxanthone. In terms of the view that it is easy to lower the reaction start temperature during thermal curing by light irradiation, the phenyl group bonded to the sulfur atom (the sulfur atom with a positive charge) may be substituted by a sulfur atom (a sulfur atom different from the sulfur atom with a positive charge), or may be bonded to an aryl group (a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted thioxanthone, etc.) via the sulfur atom.

[0063] In terms of the view that it is easy to lower the reaction start temperature during thermal curing by light irradiation, the content of the (a1) component or the content of the (a2) component 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 based on the total mass of the (A) component.

[0064] (A) The content of the component may be within the following range based on the total mass of the polymerizable composition. In terms of the view that it is easy to lower the reaction start temperature during thermal curing by light irradiation, the content of the (A) component 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, 0.35% by mass or more, 0.40% by mass or more, 0.45% by mass or more, 0.50% by mass or more, 0.55% by mass or more, 0.60% by mass or more, 0.65% by mass or more, 0.70% by mass or more, 0.80% by mass or more, 1.00% by mass or more, 1.20% by mass or more, 1.50% by mass or more, 1.60% by mass or more, 1.80% by mass or more, or 1.90% by mass or more. In terms of the view that it is easy to lower the reaction start temperature during thermal curing by light irradiation, the content of the (A) component may be 20.00% by mass or less, 15.00% by mass or less, 10.00% by mass or less, 8.00% by mass or less, 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, 2.20% by mass or less, 2.00% by mass or less. The content of the (A) component may be 1.90% 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, 0.80% by mass or less, 0.70% by mass or less, 0.65% by mass or less, 0.60% by mass or less, 0.55% by mass or less, or 0.50% by mass or less. In terms of the above view, the content of the (A) component may be 0.01 to 20.00% by mass, 0.30 to 20.00% by mass, 1.00 to 20.00% by mass, 0.01 to 5.00% by mass, 0.30 to 5.00% by mass, 1.00 to 5.00% by mass, 0.01 to 3.00% by mass, 0.30 to 3.00% by mass, 1.00 to 3.00% by mass, 0.01 to 1.00% by mass, or 0.30 to 1.00% by mass.

[0065] The polymerizable composition according to this embodiment contains an acid component (excluding the compound corresponding to the component (A)) as the component (B). As the component (B), at least one selected from the group consisting of an acid and an acid derivative can be used. Examples of the acid include an inorganic acid and an organic acid. Examples of the inorganic acid include phosphoric acid, hydrochloric acid, nitric acid, sulfuric acid, etc. Examples of the organic acid include carboxylic acid, sulfonic acid, etc. Examples of the acid derivative include a salt, an acid anhydride, an ester, etc.

[0066] From the viewpoint of easily reducing the reaction start temperature during thermal curing by light irradiation, the component (B) may contain a phosphorus compound (a compound containing a phosphorus atom), may contain a phosphorus compound having a P-OH structure, or may contain a phosphorus compound having a P=O(OH) structure (hereinafter referred to as the “component (b1)”). In the component (b1), as shown by the following general formula (b1), an oxygen atom is bonded to the phosphorus atom via a double bond, and a hydroxyl group is bonded to the phosphorus atom via a single bond. In the component (b1), the number of P=O(OH) structures (the number in one molecule) may be 1.

[0067]

[0068] [In the formula, b11 represents an integer of 1 to 3, b12 represents an integer of 0 to 2, b11 + b12 is 3, and R b1 represents a monovalent group.]

[0069] From the viewpoint of easily reducing the reaction start temperature during thermal curing by light irradiation, b11 may be 1 to 2 or 2 to 3.

[0070] (The component (b1) may have a monovalent group different from a hydroxyl group (R in the general formula (b1)) b1 ) as a functional group bonded to the phosphorus atom. Examples of the monovalent group include a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group (e.g., a phenyl group), a group containing a (meth)acryloyl group, etc. The group containing a (meth)acryloyl group is a group having at least one selected from the group consisting of an acryloyl group and a methacryloyl group.

[0071] From the viewpoint of easily reducing the reaction start temperature during thermal curing by light irradiation, the component (b1) may contain at least one selected from the group consisting of a (meth)acrylate compound having a P=O(OH) structure, phosphoric acid, and phenylphosphonic acid, may contain a (meth)acrylate compound having a P=O(OH) structure, or may contain a compound represented by the following general formula (b2).

[0072]

[0073] [In the formula, b21 represents an integer of 1 or 2, b22 represents an integer of 1 or 2, b21 + b22 is 3, b23 and b24 each independently represent an integer of 1 or more, and R b2 represents a hydrogen atom or a methyl group.]

[0074] From the viewpoint of easily reducing the reaction initiation temperature during thermal curing by light irradiation, b23 can be 1 to 8, 1 to 6, 1 to 5, 3 to 8, 3 to 6, 3 to 5, 5 to 8, or 5 to 6. From the viewpoint of easily reducing the reaction initiation temperature during thermal curing by light irradiation, b24 can be 1 to 4, 2 to 4, 1 to 3, or 1 to 2.

[0075] The component (B) may contain at least one organic acid component selected from the group consisting of organic acids and organic acid derivatives. The component (B) may also contain at least one selected from the group consisting of aliphatic carboxylic acids, salts of aliphatic carboxylic acids, and hydrates of aliphatic carboxylic acids as the organic acid component, and may also contain at least one selected from the group consisting of aliphatic carboxylic acids having at least one selected from the group consisting of a hydroxyl group and an ether group, salts of the aliphatic carboxylic acids, and hydrates of the aliphatic carboxylic acids. Examples of the aliphatic carboxylic acids include hydroxy acids such as malic acid, citric acid, glycolic acid, tartaric acid, lactic acid, glyceric acid, hydroxybutyric acid, and adipic acid; ether-based dicarboxylic acids (dicarboxylic acids having an ether group) such as diglycolic acid; and alkoxyacetic acids such as methoxyacetic acid and ethoxyacetic acid. The component (B) may contain at least one selected from the group consisting of aromatic carboxylic acids, salts of aromatic carboxylic acids, and hydrates of aromatic carboxylic acids as the organic acid component, and may also contain 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. Examples of the aromatic carboxylic acids include protocatechuic acid, α-dihydroxybenzoic acid, β-dihydroxybenzoic acid, γ-dihydroxybenzoic acid, 2-catecholcarboxylic acid, gentisic acid, orsellinic acid, gallic acid, phloroglucinolcarboxylic acid, etc. Examples of other organic acid components include phthalic anhydride, maleic anhydride, trimellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylnadic anhydride, nadic anhydride, glutaric anhydride, dimethylglutaric anhydride, diethylglutaric anhydride, succinic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 4,4'-biphthalic anhydride, 4,4'-carbonylbiphthalic anhydride, 4,4'-sulfonylbiphthalic anhydride, 4,4'-(hexafluoroisopropylidene)biphthalic anhydride, 4,4'-oxybiphthalic anhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, etc.

[0076] In terms of the viewpoint that the reaction initiation temperature during thermal curing can be easily decreased by light irradiation, the content of the (b1) component can 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 based on the total mass of the (B) component or the phosphorus compound (phosphorus compound corresponding to the (B) component) contained in the polymerizable composition.

[0077] In terms of the viewpoint that the reaction initiation temperature during thermal curing can be easily decreased by light irradiation, the content of the (B) component can be within the following range based on the total mass of the polymerizable composition. The content of the (B) component 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, or 0.90% by mass or more. The content of the (B) component 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, or 1.00% by mass or less. In terms of the above viewpoint, the content of the (B) component can be 0.01 - 10.00% by mass, 0.01 - 2.00% by mass, 0.01 - 1.00% by mass, 0.10 - 10.00% by mass, 0.10 - 2.00% by mass, 0.10 - 1.00% by mass, 0.30 - 10.00% by mass, 0.30 - 2.00% by mass, or 0.30 - 1.00% by mass.

[0078] The mass ratio R1 ((B) component / (A) component) of the content of the (B) component relative to the content of the (A) component can be within the following ranges. From the perspective of easily reducing the reaction start temperature during thermal curing by light irradiation, the mass ratio R1 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, or 0.45 or more. The mass ratio R1 can be 0.50 or more, 0.60 or more, 0.70 or more, 0.80 or more, 0.90 or more, 1.00 or more, 1.20 or more, 1.50 or more, or 1.80 or more. From the perspective of easily reducing the reaction start temperature during thermal curing by light irradiation, the mass ratio R1 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, 2.00 or less, 1.80 or less, 1.50 or less, 1.20 or less, 1.00 or less, 0.90 or less, 0.80 or less, 0.70 or less, 0.60 or less, or 0.50 or less. From the above perspective, the mass ratio R1 can be 0.01 to 10.00, 0.01 to 3.00, 0.01 to 1.00, 0.10 to 10.00, 0.10 to 3.00, 0.10 to 1.00, 0.50 to 10.00, or 0.50 to 3.00.

[0079] The polymerizable composition according to the present embodiment may contain a polymerizable compound (excluding the compound corresponding to the (A) component or the (B) component) as the (C) component.

[0080] Examples of the (C) component include a radical polymerizable compound, a cationic polymerizable compound, an anionic polymerizable compound, etc. From the perspective of easily reducing the reaction start temperature during thermal curing by light irradiation, the (C) component may contain a radical polymerizable compound. In the polymerizable composition according to the present embodiment, a photoacid generator can be used in a radical curing system using a radical polymerizable compound.

[0081] Examples of the (C) component include (meth)acrylate compounds, maleimide compounds, vinyl ether compounds, allyl compounds, styrene compounds, (meth)acrylamide compounds, imide (Nadiimide) compounds, natural rubber, isoprene rubber, butyl rubber, nitrile rubber, butadiene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, carboxy nitrile rubber, epoxy compounds, oxetane compounds, lactone compounds, etc. From the perspective of easily reducing the reaction start temperature during thermal curing by light irradiation, the (C) component may contain a compound having an ethylenic unsaturated bond, and may also contain a (meth)acrylate compound.

[0082] 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, 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, alkylene oxide-modified diisocyanurate di(meth)acrylate, alkylene oxide-modified diisocyanurate tri(meth)acrylate, tricyclodecyl (meth)acrylate, dimethyloltricyclodecane di(meth)acrylate, 2-hydroxy-1,3-di(meth)acryloxypropane, 2,2-bis[4-((meth)acryloxymethoxy)phenyl]propane, 2,2-bis[4-((meth)acryloxy polyethoxy)phenyl]propane, etc. "Polyurethane (meth)acrylate" and "urethane (meth)acrylate" are collectively referred to as "(poly)urethane (meth)acrylate". From the viewpoint of easily reducing the reaction initiation temperature during thermal curing by light irradiation,

[0083] The component (C) may contain a bifunctional (meth)acrylate compound.

[0084] From the viewpoint of easily reducing the reaction initiation temperature during thermal curing by light irradiation, the component (C) may contain a urethane (meth)acrylate compound having a polycarbonate skeleton (hereinafter referred to as "(c1) 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 (c1).

[0085]

[0086] [In the formula, R 1 represents a hydrogen atom or a methyl group, j represents an integer of 1 to 3, k represents an integer of 2 to 7, m represents an integer of 1 to 8, and n represents an integer of 5 to 7.]

[0087] In the general formula (c1), from the viewpoint of easily reducing the reaction start temperature during thermal curing by light irradiation, 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.

[0088] From the viewpoint of easily reducing the reaction start temperature during thermal curing by light irradiation, the weight average molecular weight of the component (c1) 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 start temperature during thermal curing by light irradiation, the weight average molecular weight of the component (c1) 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 the above viewpoints, the weight average molecular weight of the component (c1) can be 1000 to 100000, 5000 to 50000, or 10000 to 30000.

[0089] From the viewpoint of easily reducing the reaction start temperature during thermal curing by light irradiation, the content of the component (c1) can be within the following ranges based on the total mass of the component (C). The content of the component (c1) 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 component (c1) 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 the above viewpoints, the content of the component (c1) 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.

[0090] In terms of the view that it is easy to lower the reaction start temperature during thermal curing by light irradiation, the content of the (c1) component can be within the following ranges based on the total mass of the polymerizable composition. The content of the (c1) component 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 the (c1) component 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. In terms of the above view, the content of the (c1) component can be 5.00 - 50.00% by mass, 5.00 - 40.00% by mass, 5.00 - 30.00% by mass, 10.00 - 50.00% by mass, 10.00 - 40.00% by mass, 10.00 - 30.00% by mass, 20.00 - 50.00% by mass, 20.00 - 40.00% by mass, or 20.00 - 30.00% by mass.

[0091] In terms of the view that it is easy to lower the reaction start temperature during thermal curing by light irradiation, the (C) component may contain isocyanuric acid alkylene oxide-modified di(meth)acrylate (excluding the compound corresponding to the (c1) component, hereinafter referred to as the "(c2) component"), and may also contain isocyanuric acid ethylene oxide-modified di(meth)acrylate.

[0092] In terms of the view that it is easy to lower the reaction start temperature during thermal curing by light irradiation, the content of the (c2) component can be within the following ranges based on the total mass of the (C) component. The content of the (c2) component 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 (c2) component 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. In terms of the above view, the content of the (c2) component can be 1.00 - 50.00% by mass, 1.00 - 40.00% by mass, 1.00 - 30.00% by mass, 10.00 - 50.00% by mass, 10.00 - 40.00% by mass, 10.00 - 30.00% by mass, 20.00 - 50.00% by mass, 20.00 - 40.00% by mass, or 20.00 - 30.00% by mass.

[0093] In terms of the viewpoint of easily reducing the reaction initiation temperature during thermal curing by light irradiation, the content of the (c2) component can be within the following ranges based on the total mass of the polymerizable composition. The content of the (c2) component can be 1.00% by mass or more, 3.00% by mass or more, 5.00% by mass or more, 7.00% by mass or more, 8.00% by mass or more, or 9.00% by mass or more. The content of the (c2) component 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. In terms of the above viewpoint, the content of the (c2) component can be 1.00 - 30.00% by mass, 1.00 - 20.00% by mass, 1.00 - 10.00% by mass, 5.00 - 30.00% by mass, 5.00 - 20.00% by mass, 5.00 - 10.00% by mass, 7.00 - 30.00% by mass, 7.00 - 20.00% by mass, or 7.00 - 10.00% by mass.

[0094] In terms of the viewpoint of easily reducing the reaction initiation temperature during thermal curing by light irradiation, the (C) component 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 the compound corresponding to the (c1) component or the (c2) component, hereinafter referred to as the "(c3) component"), and may also contain at least one selected from the group consisting of dimethylol tricyclodecane di(meth)acrylate and tricyclodecane diol di(meth)acrylate.

[0095] In terms of the viewpoint of easily reducing the reaction initiation temperature during thermal curing by light irradiation, the content of the (c3) component can be within the following ranges based on the total mass of the (C) component. The content of the (c3) component 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 (c3) component 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. In terms of the above viewpoint, the content of the (c3) component can be 1.00 - 50.00% by mass, 1.00 - 40.00% by mass, 1.00 - 30.00% by mass, 10.00 - 50.00% by mass, 10.00 - 40.00% by mass, 10.00 - 30.00% by mass, 20.00 - 50.00% by mass, 20.00 - 40.00% by mass, or 20.00 - 30.00% by mass.

[0096] In terms of the view that it is easy to lower the reaction start temperature during thermal curing by light irradiation, the content of the (c3) component can be within the following ranges based on the total mass of the polymerizable composition. The content of the (c3) component can be 1.00% by mass or more, 3.00% by mass or more, 5.00% by mass or more, 7.00% by mass or more, 8.00% by mass or more, or 9.00% by mass or more. The content of the (c3) component 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. In terms of the above view, the content of the (c3) component 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.

[0097] In terms of the view that it is easy to lower the reaction start temperature during thermal curing by light irradiation, the content of the (C) component can be within the following ranges based on the total mass of the polymerizable composition. The content of the (C) 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, 38.00% by mass or more, or 40.00% by mass or more. The content of the (C) component can 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, 45.00% by mass or less, or 43.00% by mass or less. In terms of the above view, the content of the (C) component can 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.

[0098] The mass ratio R2 ((C) component / (A) component) of the content of the (C) component to the content of the (A) component can be within the following ranges. From the perspective of easily reducing the reaction start temperature during thermal curing by light irradiation, the mass ratio R2 can be 1.00 or more, 5.00 or more, 10.00 or more, 15.00 or more, or 20.00 or more. The mass ratio R2 can be 25.00 or more, 30.00 or more, 40.00 or more, 50.00 or more, 60.00 or more, 70.00 or more, or 80.00 or more. From the perspective of easily reducing the reaction start temperature during thermal curing by light irradiation, the mass ratio R2 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, 90.00 or less, 85.00 or less, 80.00 or less, 70.00 or less, 60.00 or less, 50.00 or less, 40.00 or less, 30.00 or less, or 25.00 or less. From the above perspective, the mass ratio R2 can be 1.00 to 300.00, 1.00 to 120.00, 1.00 to 50.00, 10.00 to 300.00, 10.00 to 120.00, 10.00 to 50.00, 30.00 to 300.00, or 30.00 to 120.00.

[0099] From the perspective of easily reducing the reaction start temperature during thermal curing by light irradiation, the mass ratio R3 ((C) component / (B) component) of the content of the (C) component to the content of the (B) component can be within the following ranges. The mass ratio R3 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, or 45.00 or more. The mass ratio R3 can be 500.00 or less, 450.00 or less, 400.00 or less, 350.00 or less, 300.00 or less, 250.00 or less, 200.00 or less, 180.00 or less, 150.00 or less, 120.00 or less, 100.00 or less, 80.00 or less, 60.00 or less, or 50.00 or less. From the above perspective, the mass ratio R3 can be 1.00 to 500.00, 1.00 to 100.00, 1.00 to 50.00, 10.00 to 500.00, 10.00 to 100.00, 10.00 to 50.00, 30.00 to 500.00, 30.00 to 100.00, or 30.00 to 50.00.

[0100] The polymerizable composition according to this embodiment may contain a polymerization initiator (excluding compounds corresponding to the component (A), component (B), or component (C)) as the component (D). The component (D) may contain a thermal polymerization initiator. Examples of the component (D) include radical polymerization initiators, cationic polymerization initiators, anionic polymerization initiators, etc. In terms of the viewpoint of easily reducing the reaction initiation temperature during thermal curing by light irradiation, the component (D) may contain a radical polymerization initiator. In the polymerizable composition according to this embodiment, a photoacid generator can be used in a radical curing system using a radical polymerization initiator.

[0101] Examples of the component (D) 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, and 1,1-bis(tert-hexylperoxy)-3,3,5-trimethylcyclohexane; peroxides such as terpinyl hydroperoxide; dialkyl peroxides such as α,α'-bis(tert-butylperoxy)diisopropylbenzene, diisopropylbenzene peroxide, tert-butylisopropylbenzene peroxide, and di-tert-butyl peroxide; diacyl peroxides such as octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, and benzoyl peroxide; peroxycarbonates such as bis(4-tert-butylcyclohexyl) peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, and di-3-methoxybutyl peroxydicarbonate; peresters such as tert-butyl peroxy-2-ethylhexanoate, tert-hexyl peroxy-2-ethylhexanoate, 1,1,3,3-tetramethylbutyl peroxy-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 peroxy laurate, tert-butyl peroxyisopropyl monocarbonate, tert-butyl peroxy-2-ethylhexyl monocarbonate, tert-butyl peroxybenzoate, tert-hexyl peroxybenzoate, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane, and tert-butyl peroxyacetate; 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.

[0102] In terms of the view that it is easy to lower the reaction start temperature during thermal curing by light irradiation, the polymerizable composition according to the present embodiment may contain a peroxide as the component (D), may contain an organic peroxide, or may contain a diacyl peroxide.

[0103] In terms of the view that it is easy to lower the reaction start temperature during thermal curing by light irradiation, the content of the component (D) may be within the following ranges based on the total mass of the polymerizable composition. The content of the component (D) may be 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 (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. In terms of the above view, the content of the component (D) may be 0.10 to 20.00% by mass, 0.10 to 10.00% by mass, 0.10 to 6.00% by mass, 1.00 to 20.00% by mass, 1.00 to 10.00% by mass, 1.00 to 6.00% by mass, 3.00 to 20.00% by mass, 3.00 to 10.00% by mass, or 3.00 to 6.00% by mass.

[0104] The mass ratio R4 ((D) component / (A) component) of the content of the component (D) to the content of the component (A) may be within the following ranges. In terms of the view that it is easy to lower the reaction start temperature during thermal curing by light irradiation, the mass ratio R4 may be 0.10 or more, 0.50 or more, 1.00 or more, 1.50 or more, or 2.00 or more. The mass ratio R4 may be 2.50 or more, 3.00 or more, 4.00 or more, 5.00 or more, 6.00 or more, 8.00 or more, 8.50 or more, or 9.00 or more. In terms of the view that it is easy to lower the reaction start temperature during thermal curing by light irradiation, the mass ratio R4 may be 50.00 or less, 30.00 or less, 20.00 or less, 15.00 or less, 12.00 or less, 10.00 or less, 9.00 or less, 8.50 or less, 8.00 or less, 6.00 or less, 5.00 or less, 4.00 or less, 3.00 or less, or 2.50 or less. In terms of the above view, the mass ratio R4 may be 0.10 to 50.00, 0.10 to 15.00, 0.10 to 8.00, 1.00 to 50.00, 1.00 to 15.00, 1.00 to 8.00, 5.00 to 50.00, or 5.00 to 15.00.

[0105] In terms of the view that it is easy to lower the reaction start temperature during thermal curing by light irradiation, the mass ratio R5 ((D) component / (B) component) of the content of the (D) component to the content of the (B) component can be within the following ranges. The mass ratio R5 can 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, or 5.00 or more. The mass ratio R5 can be 50.00 or less, 30.00 or less, 25.00 or less, 20.00 or less, 18.00 or less, 15.00 or less, 12.00 or less, 10.00 or less, 8.00 or less, 6.00 or less, or 5.00 or less. In terms of the above view, the mass ratio R5 can be 0.10 to 50.00, 0.10 to 30.00, 0.10 to 10.00, 1.00 to 50.00, 1.00 to 30.00, 1.00 to 10.00, 3.00 to 50.00, 3.00 to 30.00, or 3.00 to 10.00.

[0106] In terms of the view that it is easy to lower the reaction start temperature during thermal curing by light irradiation, the mass ratio R6 ((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 R6 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 R6 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. In terms of the above view, the mass ratio R6 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.

[0107] The polymerizable composition according to this embodiment may contain a thermoplastic resin as the (E) component.

[0108] Examples of the (E) component include phenoxy resin, polyester, polyurethane (excluding polyester urethane), polyester urethane, ethylene-vinyl acetate copolymer, butyral resin, etc. In terms of the view that it is easy to lower the reaction start temperature during thermal curing by light irradiation, the (E) component may contain at least one selected from the group consisting of polyester urethane and ethylene-vinyl acetate copolymer.

[0109] In terms of the view that it is easy to lower the reaction initiation temperature during thermal curing by light irradiation, the content of component (E) can be within the following ranges based on the total mass of the polymerizable composition. The content of component (E) 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 component (E) 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. In terms of the above view, the content of component (E) can be 10.00 - 90.00% by mass, 10.00 - 70.00% by mass, 10.00 - 60.00% by mass, 30.00 - 90.00% by mass, 30.00 - 70.00% by mass, 30.00 - 60.00% by mass, 40.00 - 90.00% by mass, 40.00 - 70.00% by mass, or 40.00 - 60.00% by mass.

[0110] The polymerizable composition according to this embodiment may contain components other than the above components. Examples of such components include water, organic solvents, coupling agents, fillers, softeners, promoters, deterioration inhibitors, colorants, flame retardants, thixotropic agents, etc. The polymerizable composition according to this embodiment may contain at least one of these components, or may not contain at least one of these components.

[0111] The polymerizable composition according to this embodiment may be in the form of a film. The thickness of the film-like polymerizable composition or the thickness of the cured product according to this embodiment can be within the following ranges. 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. In terms of the above view, the thickness can be 1 - 500 μm, 1 - 100 μm, 1 - 50 μm, 5 - 500 μm, 5 - 100 μm, 5 - 50 μm, 10 - 500 μm, 10 - 100 μm, or 10 - 50 μm.

[0112] Examples

[0113] 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.

[0114] <Synthesis of Urethane Acrylate (UA1)>

[0115] Into 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) (product name: DURAN OL 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. Then, after sufficiently introducing nitrogen into the reaction vessel, the inside of the reaction vessel was heated to 70 - 75 °C to cause a reaction. 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 vessel, and then 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 under an air atmosphere. Thus, a urethane acrylate (UA1) having a polycarbonate skeleton was obtained. The weight - average molecular weight of the polyurethane acrylate (UA1) was 15000.

[0116] <Synthesis of Polyester Urethane (EU1)>

[0117] Into a stainless - steel autoclave with a heater equipped with a stirrer, a thermometer, a capacitor, 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, and then 0.02 parts by mass of tetrabutyl titanate was charged as a catalyst. Then, the temperature was raised to 220 °C under a nitrogen stream, and stirring was carried out in this state for 8 hours. After that, the pressure was reduced to atmospheric pressure (760 mmHg), and it was 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 charged into a four - necked flask equipped with a stirrer, a dropping funnel, a reflux condenser, and a nitrogen inlet tube. And, 0.05 parts by mass of dibutyltin dilaurate (catalyst) was added relative to 100 parts by mass of the polyester polyol, and 50 parts by mass of 4,4'-diphenylmethane diisocyanate was dissolved in MEK and added to the four - necked flask using a dropping funnel relative to 100 parts by mass of the polyester polyol. Then, polyester urethane (EU1) was obtained by stirring at 80 °C for 4 hours.

[0118] <Preparation of Polymerizable Composition>

[0119] (Examples 1 and 2)

[0120] A photoacid generator (a sulfonium cation having three aromatic groups bonded to a positively charged sulfur atom and having (C 6 F 5 ) 4 B - anionic compound, manufactured by San-Apro Ltd., product name: CPI-410B), acid component (phosphate containing methacryloyl group, phosphorus compound having P=O(OH) structure, manufactured by Nippon Kayaku Co., Ltd., product name: PM-21), urethane acrylate (UA1), isocyanuric acid ethylene oxide modified diacrylate (manufactured by TOAGOSEI CO., LTD., product name: M-215), dimethylol tricyclodecane diacrylate (manufactured by KYOEISHA CHEMICAL Co., LTD., product name: LIGHTACRYLATE DCP-A), polymerization initiator (diacyl peroxide, manufactured by NOF CORPORATION, product name: PEROYL L) in toluene solution (solid content ratio: 20 mass %), polyester urethane (EU1) in methyl ethyl ketone / toluene mixed solution (mass ratio: 1 / 1, solid content ratio: 40 mass %), and ethylene vinyl acetate copolymer (manufactured by DOW-MITSUIPOLYCHEMICALS CO., LTD., product name: EV40W) in toluene solution (solid content ratio: 30 mass %) were mixed to prepare a polymerizable composition. The amount of the photoacid generator used (unit: mass parts) is shown in Table 1. The amount of the acid component used was 1.00 parts by mass, the amount of urethane acrylate (UA1) used was 25.00 parts by mass, the amount of isocyanuric acid ethylene oxide-modified diacrylate used was 10.00 parts by mass, the amount of dihydroxymethyltricyclodecane diacrylate used was 10.00 parts by mass, the amount of the polymerization initiator used (solid content) was 5.00 parts by mass, the amount of polyester urethane (EU1) used (solid content) was 47.50 parts by mass, and the amount of ethylene vinyl acetate copolymer used (solid content) was 7.50 parts by mass.

[0121] (Comparative Example 1)

[0122] A polymerizable composition was prepared in the same manner as in Example 1 except that no photoacid generator was used.

[0123] <Production of laminated films>

[0124] After coating the above-mentioned polymerizable composition onto a PET film (subjected to a peeling treatment, thickness: 50 μm) using a bar coater (manufactured by YASUI SEIKI CO., LTD., product name "KNIFE COATERSN C-300"), it was dried in an oven at 60 °C for 3 minutes, thereby producing a laminated film having a film-like polymerizable composition with a thickness of 20 μm disposed on the PET film.

[0125] <Measurement of the reaction start temperature>

[0126] (Without light irradiation)

[0127] After peeling the PET film from the above-mentioned laminated film, a differential scanning calorimeter (Differential Scanning Calorinetry, hereinafter referred to as "DSC") was used to measure the curing exothermic behavior of the film-like polymerizable composition, and the start temperature of the exothermic peak was obtained as an index of the reaction start temperature of the polymerization. The DSC measurement was carried out under the following conditions, and the reaction start temperature T1 was obtained. The results are shown in Table 1.

[0128] [DSC measurement conditions]

[0129] Measurement device: Manufactured by PerkinElmer Japan Co., Ltd., product name "DSC8500"

[0130] Sample amount: 10.0 ± 0.5 mg

[0131] Measurement temperature range: 25 - 200 °C

[0132] Heating rate: 30 °C / min

[0133] Measurement atmosphere gas: Nitrogen

[0134] (With light irradiation)

[0135] The PET film was peeled from the above-mentioned laminated film. Then, using a fiber light source type LED spot UV irradiation device "SpotCure SPL-2" manufactured by Ushio Inc., the film-like polymerizable composition was irradiated with ultraviolet rays (wavelength: 365 nm) at 25 °C for 5 seconds (irradiation intensity: 150 mW / cm 2 ) and then the film-like polymerizable composition was allowed to stand at 25 °C for 5 minutes.

[0136] The heat generation behavior during curing of the above-mentioned film-like polymerizable composition after light irradiation was measured by DSC, and the onset temperature of the exothermic peak was obtained as an index of the reaction onset temperature of polymerization. DSC measurement was carried out under the same conditions as the above reaction onset temperature T1, and the reaction onset temperature T2 was obtained. Moreover, the temperature difference (T2 - T1) between the reaction onset temperature T1 and the reaction onset temperature T2 was calculated. The results are shown in Table 1.

[0137] [Table 1]

[0138]

Claims

1. A polymerizable composition comprising a polymerizable compound, wherein the polymerizable composition comprises a photoacid generator and an acid component.

2. The polymerizable composition according to claim 1, in, The photoacid generator includes a boron salt having a borate anion.

3. The polymerizable composition according to claim 2, in, The boron salt further has a sulfonium cation.

4. The polymerizable composition according to claim 3, in, The sulfonium cation has an aromatic group bonded to a sulfur atom.

5. The polymerizable composition according to any one of claims 1 to 4, in, The content of the photoacid generator is 0.01 to 20.00 mass %.

6. The polymerizable composition according to any one of claims 1 to 4, in, The acid component contains a phosphorus compound.

7. The polymerizable composition according to any one of claims 1 to 4, in, The acid component includes a phosphorus compound having a P═O(OH) structure.

8. The polymerizable composition according to any one of claims 1 to 4, in, The content of the acid component is 0.01 to 10.00% by mass.

9. The polymerizable composition according to any one of claims 1 to 4, in, The mass ratio of the content of the acid component to the content of the photo-acid generator is 0.01 to 10.

00.

10. The polymerizable composition according to any one of claims 1 to 4, in, The polymerizable compound contains a (meth)acrylate compound. 11 . The polymerizable composition according to claim 1 , further comprising an organic peroxide.

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