Overlapping composition

Abstract

The present invention provides a polymerizable composition, which is reduced in the amount of a low-molecular-weight compound such as low-molecular-weight compound that can be easily released into an environment, is hydrophilic and water-soluble and has a harmful effect in radical polymerization, and which contains 2-allyloxymethylacrylic acid and / or a salt thereof. The present invention is a polymerizable composition comprising (A) a cyclized polymerizable carboxylic acid having a partial structure represented by formula (1) and / or a salt thereof, (B) a β-oxycarboxylic acid having a partial structure represented by any one of formulae (2) to (4) (wherein R and R' each independently represent a hydrogen atom or a saturated hydrocarbon group having 4 or less carbon atoms) and / or a salt thereof; and (C) a radically polymerizable compound that is different from the cyclized polymerizable carboxylic acid and / or the salt thereof (A) or the β-oxycarboxylic acid and / or the salt thereof (B), in which the molar ratio of a partial structure contained in the polymerizable composition in a largest molar amount in the polymerizable composition, among the partial structures respectively represented by formulae (2) to (4), is 1.5 or less relative to the molar amount, i.e., 100, of the partial structure represented by formula (1).

Description

[Technical Field]

[0001] The present invention relates to a polymerizable composition containing a cyclopolymerizable compound. [Background technology]

[0002] In the radical polymerization of vinyl compounds, it is known that ordinary allyl ether groups and allyl ester groups are prone to degenerative chain transfer (e.g., Non-Patent Document 1), resulting in problems such as failure to obtain high-molecular-weight polymers and low monomer conversion. Furthermore, it is known that α-substituted methyl acrylic acid esters have a low polymerization termination rate, and therefore may produce high-molecular-weight polymers, but have a low polymerization rate, i.e., low polymerization activity (e.g., Non-Patent Documents 2 and 3). However, 2-allyloxymethylacrylic acid and metal salts of 2-allyloxymethylacrylic acid, which are compounds having an allyl ether group and an α-substituted methylacrylic acid structure, are known to possess cyclopolymerization properties and thus have radical polymerizability similar to that of (meth)acrylic acid and its metal salts (e.g., Patent Documents 1 and 2).

[0003] On the other hand, regulations on new low-molecular-weight chemical substances are becoming increasingly stricter due to their susceptibility to release into the environment and the high risk of adverse effects on living organisms, and the amount of low-molecular-weight compounds in products whose safety is unknown is strictly limited. It is therefore required to keep the amount of such low-molecular-weight compounds as low as possible. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2012-107208 [Patent Document 2] Japanese Patent Application Laid-Open No. 2014-181252 [Non-patent literature]

[0005] [Non-Patent Document 1] Akira Matsumoto, Thermosetting Resins, 1987, Vol.8, No.2, p.99-113 [Non-patent document 2] B. Yamada and S. Kobatake, Prog. Polym. Sci., 119, 1089 (1994). [Non-patent document 3] Yamada Bunichiro, Adhesion Technology, 14, 1 (1995). Summary of the Invention [Problem to be solved by the invention]

[0006] As mentioned above, it is known that 2-allyloxymethylacrylic acid and 2-allyloxymethylacrylic acid metal salts can be synthesized via hydrolysis of 2-allyloxymethylacrylic acid ester with a base; however, the side reactions and by-products that occur during this process were not known.

[0007] Therefore, an object of the present invention is to provide a polymerizable composition containing 2-allyloxymethylacrylic acid and / or a salt thereof, which is hydrophilic, water-soluble, and easily released into the environment, and in which the amount of low-molecular-weight compounds that have adverse effects on radical polymerization is reduced. [Means for solving the problem]

[0008] The present inventors have conducted various studies to achieve the above-mentioned object and have found that, during the production of 2-allyloxymethylacrylic acid or a 2-allyloxymethylacrylic acid salt, a β-hydroxycarboxylic acid and / or a salt thereof having a specific partial structure is generated as a by-product, and that the amount of such a β-hydroxycarboxylic acid and / or a salt thereof can be quantified by measuring the amount of the specific partial structure. They have also found a polymerizable composition containing 2-allyloxymethylacrylic acid and / or a 2-allyloxymethylacrylic acid salt that has a low content of such by-products, has good radical polymerizability, and is suitable as a raw material for polymers used in various applications, and have arrived at the present invention. That is, the present invention is described in the following [1] to [5]. [1] The following formula (1);

[0009] [ka]

[0010] (A) a cyclopolymerizable carboxylic acid and / or a salt thereof having a partial structure represented by the following formula: The following formulas (2) to (4):

[0011] [ka]

[0012] (wherein R and R' each independently represent a hydrogen atom or a saturated hydrocarbon group having 4 or less carbon atoms), and / or a salt thereof (B), a polymerizable composition comprising (A) the cyclopolymerizable carboxylic acid and / or its salt and (C) a radical polymerizable compound other than (B) the β-hydroxycarboxylic acid and / or its salt, A polymerizable composition, wherein the molar ratio of the partial structure represented by any one of formulas (2) to (4) contained in the polymerizable composition in the largest molar amount is 1.5 or less relative to 100 molar amount of the partial structure represented by formula (1). [2] The polymerizable composition according to the above [1], wherein the radical polymerizable compound (C) is one or more compounds selected from the group consisting of a compound having a (meth)acryloyl group, a compound having a 2-(meth)allyloxymethylacryloyl group other than the cyclopolymerizable carboxylic acid and / or its salt (A), N-vinylamides, (meth)acrylonitrile, aromatic vinyls, vinyl ethers, and vinyl esters. [3] The polymerizable composition according to the above [1] or [2], wherein R and R' in the above formulas (2) to (4) are each independently a hydrogen atom, a methyl group, or an ethyl group. [4] The polymerizable composition according to any one of the above [1] to [3], wherein the total molar amount of the partial structures represented by any one of the above formulas (2) to (4) is 4 or less per 100 molar amount of the partial structure represented by the above formula (1). [5] A polymer obtained by polymerizing the polymerizable composition according to any one of the above [1] to [4] under radical-generating conditions. [Effects of the Invention]

[0013] The polymerizable composition of the present invention has a reduced amount of hydrophilic, water-soluble low-molecular-weight compounds that are likely to be released into the environment. Furthermore, since the polymerizable composition of the present invention has a reduced amount of low-molecular-weight compounds that have adverse effects on radical polymerization, it has good radical polymerizability and can be suitably used for various applications, such as components of curable compositions used in various coatings, adhesion, sealing, and three-dimensional modeling, and copolymer raw materials. [Brief explanation of the drawings]

[0014] [Figure 1] FIG. 1 is a diagram showing peaks of carboxylate ions having partial structures (1) to (4) in an electropherogram obtained by analyzing the polymerizable composition of Comparative Example 3 with a capillary electrophoresis system. DETAILED DESCRIPTION OF THE INVENTION

[0015] Preferred embodiments of the present invention will be specifically described below, but the present invention is not limited to the following description and can be appropriately modified and applied within the scope of the present invention. A combination of two or more of the individual preferred embodiments of the present invention described below also falls within the scope of the present invention. Furthermore, (meth)acrylic means acrylic or methacrylic. (Meth)allyl means allyl or methallyl.

[0016] The polymerizable composition of the present invention is a polymerizable composition having the following formula (1):

[0017] [ka]

[0018] (A) a cyclopolymerizable carboxylic acid and / or a salt thereof having a partial structure represented by the following formula: The following formulas (2) to (4):

[0019] [ka]

[0020] (wherein R and R' each independently represent a hydrogen atom or a saturated hydrocarbon group having 4 or less carbon atoms), and a radical polymerizable compound (C) other than the cyclopolymerizable carboxylic acid and / or salt thereof (A) and the β-hydroxycarboxylic acid and / or salt thereof (B), wherein the molar ratio of the partial structure represented by any of the formulas (2) to (4) that is contained in the polymerizable composition in the largest molar amount is 1.5 or less per 100 molar amount of the partial structure represented by the formula (1).

[0021] The polymerizable composition of the present invention is hydrophilic and water-soluble, and is easily released into the environment. In addition, the polymerizable composition of the present invention contains a reduced amount of low-molecular-weight compounds that have adverse effects on radical polymerization. Therefore, the polymerizable composition of the present invention has a reduced risk of adverse effects on living organisms and is excellent in radical polymerizability. The present invention will be described in detail below.

[0022] <Cyclopolymerizable Carboxylic Acid and / or Salt Thereof (A)> The polymerizable composition of the present disclosure contains a cyclopolymerizable carboxylic acid and / or a salt thereof (A) (hereinafter, sometimes simply referred to as a cyclopolymerizable carboxylic acid compound (A)) having a partial structure represented by the following formula (1) (hereinafter, also referred to as partial structure (1)). The partial structure is a part of the structure of a compound, and refers to a structure that can bond with other parts to form a compound. The bond may be any of an ionic bond, a covalent bond, etc.

[0023] [ka]

[0024] When the cyclopolymerizable carboxylic acid compound (A) is a carboxylic acid, the cyclopolymerizable carboxylic acid compound (A) is 2-allyloxymethylacrylic acid.

[0025] When the cyclopolymerizable carboxylic acid compound (A) is a carboxylate, the cation constituting the carboxylate may be an inorganic cation or an organic cation, and may be appropriately selected depending on the purpose and application.

[0026] Examples of inorganic cations include metal ions or metal oxide ions. Specific examples of the element or metal oxide include Group 1 elements of the periodic table, such as lithium, sodium, and potassium; Group 2 elements of the periodic table, such as magnesium, calcium, and barium; transition metal elements or transition metal oxides, such as lanthanum, zirconium oxide, iron, cobalt, nickel, and copper; and typical metal elements of Groups 12 to 15 of the periodic table, such as zinc, aluminum, tin, lead, and bismuth. However, the cations are not limited to these examples, and may be a combination of ions of two or more metals or metal oxides. From the viewpoint of rendering the polymerizable composition of the present disclosure colorless, the metal ion portion of the metal carboxylate is preferably an ion of a typical metal element, a metal belonging to Groups 3 or 4 of the periodic table, or a metal oxide thereof. Taking into account availability and toxicity, lithium, sodium, potassium, magnesium, calcium, zinc, and aluminum are more preferred.

[0027] Examples of organic cations include cations containing nonmetallic elements of Group 15 of the periodic table. Examples of nonmetallic elements of Group 15 of the periodic table include nitrogen, phosphorus, and arsenic. Preferred examples include ions in which a nitrogen atom is cationized (ammonium ion, protonated amine, quaternary ammonium ion) and ions in which a phosphorus atom is cationized (phosphonium ion, protonated phosphine, quaternary phosphonium ion). From the viewpoints of biological safety and availability, ions in which a nitrogen atom is cationized are more preferred.

[0028] Specific examples of protonated amines that are named using the name of the amine before protonation include methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, ethanolamine, diethanolamine, triethanolamine, tris(2-aminoethyl)amine, hexamethylenediamine, iminobispropylamine, methyliminobispropylamine, 3,6,9,12-tetraoxa-tetradecane-1,14diamine, N,N'-bis(2-hydroxyethyl)ethylenediamine, 1,3-bisaminomethylcyclohexane, 1,4-bisaminomethylcyclohexane, 3-aminomethyl-3,5,6-trimethylcyclohexylamine, isophoronediamine, 2,5(or 2,6)-bis(aminomethyl )bicyclo[2,2,1]heptane, 2,6 (or 2,7)-bis(aminomethyl)bicyclo[3,2,1]octane, 2,5 (or 2,6)-bis(aminomethyl)-7-dimethylbicyclo[2,2,1]heptane, 2,6-bis(aminomethyl)adamantane, m-xylylenediamine, p-phenylenediamine, bis(4-aminophenyl)methane, 1,4 (or 2,6 or 2,7)-bis(aminomethyl)naphthalene, piperazine, aminoethylpiperazine, bisaminopropylpiperazine, 2,4,6-triamino-1,3,5-triazine, polyethyleneimine, and various other amines having primary, secondary, or higher amine valencies and primary to tertiary nitrogen atom moieties, are listed, but the present disclosure is not limited to these examples.

[0029] Specific examples of quaternary ammonium ions include tetramethylammonium ion, tetraethylammonium ion, tetrabutylammonium ion, benzyltrimethylammonium ion, and hexadecyltrimethylammonium ion, but the present disclosure is not limited to these examples.

[0030] When the cyclopolymerizable carboxylic acid compound (A) is a carboxylate, the anion constituting the carboxylate may be only the carboxylate ion having the partial structure (1), i.e., the 2-allyloxymethyl acrylate ion, or may contain other anions. Such an anion may be an inorganic or organic anion, but an organic anion is preferred from the viewpoint of solubility in organic substances, and a carboxylate ion having a double bond conjugated with a carboxyl group is preferred from the viewpoint of radical polymerizability. Examples of such anion include a (meth)acrylate ion, a 2-methallyloxymethyl acrylate ion, and a (meth)acrylic acid-based polymerizable carboxylate ion having a structure in which a polybasic acid anhydride is added to a hydroxyl group-containing (meth)acrylic acid ester (e.g., a 2-(meth)acryloyloxyethyl succinate ion), and the like. An appropriate anion may be selected depending on the purpose and application.

[0031] When the cyclopolymerizable carboxylic acid compound (A) is a carboxylate, the carboxylate may be a compound consisting of one type of cation and one type of anion, or may be a compound consisting of one type of cation and two or more types of anions, etc. Examples of the form of the carboxylate of the cyclopolymerizable carboxylic acid compound (A) that may be present in the polymerizable composition of the present disclosure include a salt formed from the partial structure (1) and a cation, and a salt formed from the partial structure (1) and another anion and a cation.

[0032] Furthermore, the polymerizable composition of the present invention may contain one type of cyclopolymerizable carboxylic acid compound (A), or may contain two or more types of cyclopolymerizable carboxylic acid compounds (A).

[0033] The content of the partial structure (1) of the cyclopolymerizable carboxylic acid compound (A) contained in the polymerizable composition of the present disclosure is preferably 3 parts by mass or more and 90 parts by mass or less, more preferably 5 parts by mass or more and 85 parts by mass or less, and even more preferably 10 parts by mass or more and 80 parts by mass or less, relative to 100 parts by mass of the polymerizable composition of the present disclosure.

[0034] Methods for analyzing the partial structure (1) of the cyclopolymerizable carboxylic acid compound (A) contained in the polymerizable composition of the present disclosure and the content of cations include gas chromatography; liquid chromatography based on various separation modes such as partition, adsorption, ion exchange, ion exclusion, size exclusion, and affinity; capillary electrophoresis; 1 Spectroscopic techniques such as H-NMR, ICP emission spectroscopy, atomic absorption spectroscopy, and X-ray fluorescence; and the like, but are not limited to these examples.

[0035] From the viewpoint of being able to directly detect the content of the partial structure (1) or cations as ions, ion chromatography and capillary electrophoresis are preferred. From the viewpoint of being able to perform the measurement in a short time, 1 H-NMR is preferred. Among these, in the present disclosure, measurement is performed by capillary electrophoresis from the viewpoint of sensitivity and ease of maintenance of the device.

[0036] <β-Hydroxycarboxylic acid and / or its salt (B)> The polymerizable composition of the present disclosure contains one or more β-hydroxycarboxylic acids and / or salts thereof (B) (hereinafter, sometimes simply referred to as β-hydroxycarboxylic acid compounds (B)) having a partial structure represented by any of the following formulas (2) to (4):

[0037] [ka]

[0038] (In the formula, R and R' each independently represent a hydrogen atom or a saturated hydrocarbon group having 4 or less carbon atoms.) Although not particularly limited, the β-hydroxycarboxylic acid compound (B) is usually a compound that is non-polymerizable or poorly polymerizable in the radical polymerization of a vinyl compound.

[0039] Compounds having the partial structure represented by the above formula (2) (hereinafter also referred to as partial structure (2)) are allyl ether compounds known to be prone to degenerative chain transfer. Compounds having the partial structure represented by the above formula (3) (hereinafter also referred to as partial structure (3)) do not have a vinyl group and are non-polymerizable. Compounds having the partial structure represented by the above formula (4) (hereinafter also referred to as partial structure (4)) are compounds in the same structural category as α-substituted methyl acrylate esters, which are known to have a low polymerization rate, i.e., low polymerization activity, although they may produce high-molecular-weight polymers due to their low polymerization termination rate.

[0040] As will be described later, the cyclopolymerizable carboxylic acid compound (A) is preferably produced via a process of hydrolyzing a lower ester of 2-allyloxymethylacrylic acid with a base, and the lower ester of 2-allyloxymethylacrylic acid used as the raw material is preferably an ester of a saturated hydrocarbon having four or fewer carbon atoms, with methyl 2-allyloxymethylacrylate and ethyl 2-allyloxymethylacrylate being particularly preferred. The β-hydroxycarboxylic acid compound (B) is mainly produced by a side reaction in the hydrolysis process, and the alkoxide moiety (RO-, R'-O-) in the structure is presumed to be derived from water or an alcohol, which is a component of the ester moiety of the 2-allyloxymethylacrylic acid ester. Therefore, when a saturated hydrocarbon ester of 2-allyloxymethylacrylic acid having 4 or less carbon atoms is used as a raw material, R and R' in formulas (2) to (4) are hydrogen atoms or saturated hydrocarbon groups having 4 or less carbon atoms, and when methyl 2-allyloxymethylacrylate or ethyl 2-allyloxymethylacrylate is used as a raw material, R and R' in formulas (2) to (4) are hydrogen atoms or methyl or ethyl groups.

[0041] The content of the β-hydroxycarboxylic acid compound (B) in the polymerizable composition of the present disclosure is expressed as the content of the partial structure represented by any one of the above formulas (2) to (4), and is an amount such that the molar ratio of the partial structure represented by any one of the above formulas (2) to (4) that is contained in the polymerizable composition in the largest molar amount is 1.5 or less per 100 molar amount of the partial structure represented by the above formula (1).

[0042] The content of the partial structure of the β-hydroxycarboxylic acid compound (B) most abundant in the polymerizable composition is 1.5 or less, preferably 1.2 or less, and more preferably 0.9 or less, per 100 molar amount of the partial structure (1) of the cyclopolymerizable carboxylic acid compound (A) represented by the above formula (1). The lower limit of the content of the partial structure of the β-hydroxycarboxylic acid compound (B) most abundant in the polymerizable composition is not particularly limited, and a lower limit is preferable. However, the content may be 0 or more, 0.01 or more, or 0.1 or more, per 100 molar amount of the partial structure (1). That is, the content of the partial structure of the β-hydroxycarboxylic acid compound (B) most abundant in the polymerizable composition is preferably 0 or more and 1.5 or less, more preferably 0.01 or more and 1.2 or less, and even more preferably 0.1 or more and 0.9 or less, per 100 molar amount of the partial structure (1) of the cyclopolymerizable carboxylic acid compound (A) represented by the above formula (1).

[0043] The total molar amount of the partial structures (2) to (4) of the β-hydroxycarboxylic acid compound (B) contained in the polymerizable composition is preferably 4 or less, more preferably 3.5 or less, even more preferably 3 or less, and most preferably 2.5 or less, relative to 100 molar amount of the partial structure (1) of the cyclopolymerizable carboxylic acid compound (A). The lower limit of the total amount of the partial structures of the β-hydroxycarboxylic acid compound (B) contained in the polymerizable composition is preferably lower, and is not particularly limited. However, the molar amount may be 0 or more, 0.01 or more, or even 0.1 or more, relative to 100 molar amount of the partial structure (1). That is, the total molar amount of the partial structures represented by any of the formulas (2) to (4) contained in the polymerizable composition is preferably 0 or more and 4 or less, more preferably 0.01 or more and 3.5 or less, even more preferably 0.1 or more and 3 or less, and most preferably 0.1 or more and 2.5 or less, relative to 100 molar amount of the partial structure (1) represented by the formula (1).

[0044] 2-Allyloxymethylacrylic acid and 2-allyloxymethylacrylic acid metal salts can be synthesized, for example, via hydrolysis of 2-allyloxymethylacrylic ester with a base, but the β-hydroxycarboxylic acid compound (B), which is presumably produced as a by-product in this process, tends to inhibit radical polymerization. Furthermore, from the viewpoint of safety, the content of the β-hydroxycarboxylic acid compound (B) in a polymerizable composition is strictly limited, and therefore the content of the β-hydroxycarboxylic acid compound (B) is required to be low.

[0045] Methods for analyzing the content of the partial structures (2) to (4) and cations of the β-hydroxycarboxylic acid compound (B) contained in the polymerizable composition of the present disclosure include gas chromatography; liquid chromatography based on various separation modes such as partition, adsorption, ion exchange, ion exclusion, size exclusion, and affinity; capillary electrophoresis; 1 Spectroscopic techniques such as H-NMR, ICP emission spectroscopy, atomic absorption spectroscopy, and X-ray fluorescence; and the like, but are not limited to these examples.

[0046] From the viewpoint of being able to directly detect the content of the partial structures (2) to (4) and cations as ions, ion chromatography and capillary electrophoresis are preferred. From the viewpoint of being able to perform the measurement in a short time, 1 H-NMR is preferred. Among these, in the present disclosure, measurement is performed by capillary electrophoresis from the viewpoint of sensitivity and ease of maintenance of the device.

[0047] <Radical polymerizable compound (C)> The polymerizable composition of the present disclosure contains a radically polymerizable compound (C) other than the above-mentioned cyclopolymerizable carboxylic acid and / or salt thereof (A) and β-hydroxycarboxylic acid and / or salt thereof (B). The radically polymerizable compound (C) can be classified into monofunctional radically polymerizable monomers, which are compounds having one radically polymerizable group in the same molecule, and polyfunctional radically polymerizable compounds, which are compounds having two or more radically polymerizable groups in the same molecule.

[0048] The radical polymerizable group is preferably a carbon-carbon double bond, more preferably a carbon-carbon double bond adjacent to a functional group that activates the carbon-carbon double bond. Preferred examples of the functional group that activates the carbon-carbon double bond include a carbonyl group, an amide group, a cyano group, an aromatic ring, an alkoxy group, an acyloxy group, a carbon-carbon double bond, and a halogen atom. Only one functional group may be adjacent to the carbon-carbon double bond, or two or more groups of two or more types may be adjacent to the carbon-carbon double bond. Examples of functional groups that activate carbon-carbon double bonds and corresponding compounds are shown below, but the present disclosure is not limited to these examples.

[0049] Examples of compounds that have only one functional group that activates a carbon-carbon double bond, and that functional group is a carbonyl group, include compounds having a (meth)acryloyl group, such as (meth)acrylic acid, (meth)acrylic acid esters, and (meth)acrylamide; compounds having a 2-hydroxymethylacryloyl group, such as 2-hydroxymethylacrylic acid and 2-hydroxymethylacrylic acid esters; and compounds having a 2-(meth)allyloxymethylacryloyl group, such as 2-(meth)allyloxymethylacrylic acid and 2-(meth)allyloxymethylacrylic acid esters.

[0050] Examples of compounds that have only one functional group that activates a carbon-carbon double bond, and that functional group is an amide group, include N-vinylamides.

[0051] An example of a compound having only one functional group that activates a carbon-carbon double bond, which is a cyano group, is (meth)acrylonitrile.

[0052] Compounds having only one functional group that activates a carbon-carbon double bond and that is an aromatic ring include, for example, aromatic vinyls.

[0053] Examples of compounds that have only one functional group that activates a carbon-carbon double bond, and that is an alkoxy group, include vinyl ethers.

[0054] Examples of compounds that have only one functional group that activates a carbon-carbon double bond, and that is an acyloxy group, include vinyl esters.

[0055] Examples of compounds having one or more functional groups that activate a carbon-carbon double bond, one of which is a carbon-carbon double bond, include conjugated dienes.

[0056] Examples of compounds having one or more halogens as functional groups that activate carbon-carbon double bonds include vinyl halides.

[0057] Examples of compounds having two or more carbonyl groups as functional groups that activate carbon-carbon double bonds include unsaturated polycarboxylic acids, unsaturated polycarboxylic acid esters, anhydrides of unsaturated polycarboxylic acids, N-substituted maleimides, and methylenemalonic acid esters.

[0058] An example of a compound having one cyano group and one carbonyl group as functional groups that activate a carbon-carbon double bond is 2-cyanoacrylate.

[0059] The radical polymerizable compound (C) may be selected appropriately depending on the purpose and application, but from the viewpoints of polymerization activity, compatibility with the salt-type cyclopolymerizable carboxylic acid compound (A), and availability, compounds having a (meth)acryloyl group, compounds having a 2-(meth)allyloxymethylacryloyl group other than the cyclopolymerizable carboxylic acid compound (A), N-vinylamides, (meth)acrylonitrile, aromatic vinyls, vinyl ethers, and vinyl esters are preferred, and these may be monofunctional radical polymerizable monomers, which are compounds having one radical polymerizable group in the same molecule, or polyfunctional radical polymerizable compounds, which are compounds having two or more radical polymerizable groups in the same molecule. These may be used alone or in combination.

[0060] From the viewpoints of ease of compounding with the cyclopolymerizable carboxylic acid compound (A) and of being able to form a solvent-free polymerizable composition, the radical polymerizable compound (C) is preferably liquid at room temperature and has a viscosity of 1500 mPa·s or less, more preferably 1000 mPa·s or less, even more preferably 500 mPa·s or less, and most preferably 200 mPa·s or less.

[0061] The content of the radical polymerizable compound (C) may be appropriately selected depending on the purpose and application, but from the viewpoint of exerting the effect of the cyclopolymerizable carboxylic acid compound (A), it is preferably 1 to 3,000 parts by mass, more preferably 2 to 2,000 parts by mass, even more preferably 3 to 1,000 parts by mass, and most preferably 4 to 700 parts by mass per 100 parts by mass of the cyclopolymerizable carboxylic acid compound (A).

[0062] Furthermore, in the following, the above-mentioned compound group will be exemplified by specific compound names or product names, but the present disclosure is not limited to only these examples.

[0063] [Monofunctional radically polymerizable monomer] The monofunctional radical polymerizable compound is a compound having one radical polymerizable group in the same molecule, and the radical polymerizable group is preferably a carbon-carbon double bond, more preferably a carbon-carbon double bond adjacent to a functional group that activates the carbon-carbon double bond. As described above, specific compounds include compounds having a (meth)acryloyl group, compounds having a 2-(meth)allyloxymethylacryloyl group (excluding the cyclopolymerizable carboxylic acid compound (A)), N-vinylamides, (meth)acrylonitrile, aromatic vinyls, vinyl ethers, and vinyl esters, but the present disclosure is not limited to these examples.

[0064] Examples of (meth)acrylic acid esters include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, n-amyl (meth)acrylate, sec-amyl (meth)acrylate, tert-amyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, tridecyl (meth)acrylate, cyclohexyl (meth)acrylate, cyclohexylmethyl (meth)acrylate, octyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, tricyclodecanyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, Examples of the carboxylated (meth)acrylic acid esters include 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, phenoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, (3,4-epoxycyclohexyl)methyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, 3-(trimethoxysilyl)propyl (meth)acrylate, mono(2-acryloyloxyethyl) succinate, and mono(2-methacryloyloxyethyl) succinate, but the present disclosure is not limited to these examples. These (meth)acrylic acid esters may be used alone or in combination of two or more kinds.

[0065] Examples of (meth)acrylamides include N,N-dimethyl(meth)acrylamide, N-methylol(meth)acrylamide, acryloylmorpholine, etc., but the present disclosure is not limited to these examples. These (meth)acrylamides may be used alone or in combination of two or more.

[0066] Examples of 2-(meth)allyloxymethyl acrylate esters include methyl 2-(meth)allyloxymethyl acrylate, ethyl 2-(meth)allyloxymethyl acrylate, n-propyl 2-(meth)allyloxymethyl acrylate, isopropyl 2-(meth)allyloxymethyl acrylate, n-butyl 2-(meth)allyloxymethyl acrylate, sec-butyl 2-(meth)allyloxymethyl acrylate, tert-butyl 2-(meth)allyloxymethyl acrylate, n-amyl 2-(meth)allyloxymethyl acrylate, and 2-(meth)allyloxymethyl acrylate. sec-Amyl allyloxymethylacrylate, tert-Amyl 2-(meth)allyloxymethylacrylate, neopentyl 2-(meth)allyloxymethylacrylate, n-Hexyl 2-(meth)allyloxymethylacrylate, sec-Hexyl 2-(meth)allyloxymethylacrylate, n-Heptyl 2-(meth)allyloxymethylacrylate, n-Octyl 2-(meth)allyloxymethylacrylate, sec-Octyl 2-(meth)allyloxymethylacrylate, tert-Octyl 2-(meth)allyloxymethylacrylate, 2-( 2-Ethylhexyl meth)allyloxymethylacrylate, Capryl 2-(meth)allyloxymethylacrylate, Nonyl 2-(meth)allyloxymethylacrylate, Decyl 2-(meth)allyloxymethylacrylate, Undecyl 2-(meth)allyloxymethylacrylate, Lauryl 2-(meth)allyloxymethylacrylate, Tridecyl 2-(meth)allyloxymethylacrylate, Myristyl 2-(meth)allyloxymethylacrylate, Pentadecyl 2-(meth)allyloxymethylacrylate, 2-(meth)allyloxymethylacrylic acid Cetyl, heptadecyl 2-(meth)allyloxymethylacrylate, stearyl 2-(meth)allyloxymethylacrylate, nonadecyl 2-(meth)allyloxymethylacrylate, eicosyl 2-(meth)allyloxymethylacrylate, ceryl 2-(meth)allyloxymethylacrylate, melissyl 2-(meth)allyloxymethylacrylate, crotyl 2-(meth)allyloxymethylacrylate, 1,1-dimethyl-2-propenyl 2-(meth)allyloxymethylacrylate, 2-methylbutenyl 2-(meth)allyloxymethylacrylate2-(meth)allyloxymethylacrylate 3-methyl-2-butenyl, 2-(meth)allyloxymethylacrylate 3-methyl-3-butenyl, 2-(meth)allyloxymethylacrylate 2-methyl-3-butenyl, 2-(meth)allyloxymethylacrylate oleyl, 2-(meth)allyloxymethylacrylate linoleyl, 2-(meth)allyloxymethylacrylate linolene, 2-(meth)allyloxymethylacrylate cyclopentyl, 2-(meth)allyloxymethylacrylate cyclopentylmethyl, 2-(meth)allyloxymethylacrylate Cyclohexyl acrylate, cyclohexylmethyl 2-(meth)allyloxymethyl acrylate, 4-methylcyclohexyl 2-(meth)allyloxymethyl acrylate, 4-tert-butylcyclohexyl 2-(meth)allyloxymethyl acrylate, tricyclodecanyl 2-(meth)allyloxymethyl acrylate, isobornyl 2-(meth)allyloxymethyl acrylate, adamantyl 2-(meth)allyloxymethyl acrylate, dicyclopentanyl 2-(meth)allyloxymethyl acrylate, dicyclopentanyl 2-(meth)allyloxymethyl acrylate Clopentenyl, 2-(meth)allyloxymethyl phenyl acrylate, 2-(meth)allyloxymethyl methyl acrylate, 2-(meth)allyloxymethyl dimethyl phenyl acrylate, 2-(meth)allyloxymethyl trimethylphenyl acrylate, 2-(meth)allyloxymethyl acrylate 4-tert-butylphenyl acrylate, 2-(meth)allyloxymethyl benzyl acrylate, 2-(meth)allyloxymethyl diphenylmethyl acrylate, 2-(meth)allyloxymethyl diphenylethyl acrylate, 2-(meth)allyloxy Triphenylmethyl methylacrylate, cinnamyl 2-(meth)allyloxymethylacrylate, naphthyl 2-(meth)allyloxymethylacrylate, anthranil 2-(meth)allyloxymethylacrylate, methoxyethyl 2-(meth)allyloxymethylacrylate, methoxyethoxyethyl 2-(meth)allyloxymethylacrylate, methoxyethoxyethoxyethyl 2-(meth)allyloxymethylacrylate, 3-methoxybutyl 2-(meth)allyloxymethylacrylate, ethoxyethyl 2-(meth)allyloxymethylacrylate,Ethoxyethoxyethyl 2-(meth)allyloxymethylacrylate, cyclopentoxyethyl 2-(meth)allyloxymethylacrylate, cyclohexyloxyethyl 2-(meth)allyloxymethylacrylate, cyclopentoxyethoxyethyl 2-(meth)allyloxymethylacrylate, cyclohexyloxyethoxyethyl 2-(meth)allyloxymethylacrylate, dicyclopentenyloxyethyl 2-(meth)allyloxymethylacrylate, phenoxyethyl 2-(meth)allyloxymethylacrylate, phenoxyethoxyethyl 2-(meth)allyloxymethylacrylate, glycidyl 2-(meth)allyloxymethylacrylate, β-methylglycidyl 2-(meth)allyloxymethylacrylate, 2-(meth)allyloxymethylacrylate Examples of suitable 2-(meth)allyloxymethyl acrylates include β-ethylglycidyl allyloxymethyl acrylate, 3,4-epoxycyclohexylmethyl 2-(meth)allyloxymethyl acrylate, 2-oxetanemethyl 2-(meth)allyloxymethyl acrylate, 3-methyl-3-oxetanemethyl 2-(meth)allyloxymethyl acrylate, 3-ethyl-3-oxetanemethyl 2-(meth)allyloxymethyl acrylate, tetrahydrofuranyl 2-(meth)allyloxymethyl acrylate, tetrahydrofurfuryl 2-(meth)allyloxymethyl acrylate, tetrahydropyranyl 2-(meth)allyloxymethyl acrylate, dioxazolanyl, and dioxanyl 2-(meth)allyloxymethyl acrylate, but the present disclosure is not limited to these examples. These 2-(meth)allyloxymethyl acrylates may be used alone or in combination of two or more.

[0067] Examples of N-vinylamides include, but are not limited to, N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylformamide, and N-vinylacetamide. These N-vinylamides may be used alone or in combination of two or more.

[0068] Examples of aromatic vinyl compounds include, but are not limited to, styrene, α-methylstyrene, vinyltoluene, methoxystyrene, N-vinylimidazole, cinnamic acid, vinylbenzoic acid, etc. These aromatic vinyl compounds may be used alone or in combination of two or more.

[0069] Examples of vinyl ethers include methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, methoxyethoxyethyl vinyl ether, methoxypolyethylene glycol vinyl ether, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, etc., but the present disclosure is not limited to these examples. These vinyl ethers may be used alone or in combination of two or more.

[0070] Examples of vinyl esters include, but are not limited to, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, etc. These vinyl esters may be used alone or in combination of two or more.

[0071] Examples of conjugated dienes include 1,3-butadiene, isoprene, chloroprene, etc., but the present disclosure is not limited to these examples. These conjugated dienes may be used alone or in combination of two or more.

[0072] Examples of unsaturated polycarboxylic acids, unsaturated polycarboxylic acid esters, and unsaturated polycarboxylic acid anhydrides include, but are not limited to, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, and alkyl esters and anhydrides thereof. These unsaturated polycarboxylic acid esters and unsaturated polycarboxylic acid anhydrides may be used alone or in combination of two or more.

[0073] Examples of N-substituted maleimides include, but are not limited to, methylmaleimide, ethylmaleimide, isopropylmaleimide, cyclohexylmaleimide, phenylmaleimide, benzylmaleimide, naphthylmaleimide, etc. These N-substituted maleimides may be used alone or in combination of two or more.

[0074] [Polyfunctional radically polymerizable compound] A polyfunctional radical polymerizable compound is a compound having two or more radical polymerizable groups in the same molecule. The radical polymerizable group is preferably a carbon-carbon double bond, more preferably a carbon-carbon double bond adjacent to a functional group that activates the carbon-carbon double bond. As described above, specific compounds include compounds having a (meth)acryloyl group, compounds having a 2-(meth)allyloxymethylacryloyl group (excluding the cyclopolymerizable carboxylic acid compound (A)), N-vinylamides, (meth)acrylonitrile, aromatic vinyls, vinyl ethers, and vinyl esters, but the present disclosure is not limited to these examples.

[0075] Examples of general-purpose polyfunctional radical polymerizable compounds include polyfunctional (meth)acrylic compounds such as polyfunctional (meth)acrylic esters, vinyl ether group-containing (meth)acrylic esters, allyl group-containing (meth)acrylic esters, polyfunctional (meth)acryloyl group-containing isocyanurates, and polyfunctional urethane (meth)acrylates; polyfunctional 2-(meth)allyloxymethyl acrylic esters; polyfunctional maleimide compounds; polyfunctional vinyl ethers; polyfunctional allyl compounds; and polyfunctional aromatic vinyls, but the present disclosure is not limited to these examples. These polyfunctional radical polymerizable compounds may be used alone or in combination of two or more.

[0076] Examples of polyfunctional (meth)acrylic acid esters include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, hexanediol di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, bisphenol A alkylene oxide di(meth)acrylate, bisphenol F alkylene oxide di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, glycerin tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethylene oxide-added trimethylolpropane tri ... Examples of such an alkyl group include hydroxyl group-added ditrimethylolpropane tetra(meth)acrylate, ethylene oxide-added pentaerythritol tetra(meth)acrylate, ethylene oxide-added dipentaerythritol hexa(meth)acrylate, propylene oxide-added trimethylolpropane tri(meth)acrylate, propylene oxide-added ditrimethylolpropane tetra(meth)acrylate, propylene oxide-added pentaerythritol tetra(meth)acrylate, propylene oxide-added dipentaerythritol hexa(meth)acrylate, ε-caprolactone-added trimethylolpropane tri(meth)acrylate, ε-caprolactone-added ditrimethylolpropane tetra(meth)acrylate, ε-caprolactone-added pentaerythritol tetra(meth)acrylate, and ε-caprolactone-added dipentaerythritol hexa(meth)acrylate, but the present disclosure is not limited to these examples. These polyfunctional (meth)acrylic acid esters may be used alone or in combination of two or more kinds.

[0077] Examples of vinyl ether group-containing (meth)acrylic acid esters include 2-vinyloxyethyl (meth)acrylate, 3-vinyloxypropyl (meth)acrylate, 1-methyl-2-vinyloxyethyl (meth)acrylate, 2-vinyloxypropyl (meth)acrylate, 4-vinyloxybutyl (meth)acrylate, 4-vinyloxycyclohexyl (meth)acrylate, 5-vinyloxypentyl (meth)acrylate, 6-vinyloxyhexyl (meth)acrylate, 4-vinyloxymethylcyclohexylmethyl (meth)acrylate, p-vinyloxymethylphenylmethyl (meth)acrylate, 2-(vinyloxyethoxy)ethyl (meth)acrylate, and 2-(vinyloxyethoxyethoxyethoxy)ethyl (meth)acrylate, but the present disclosure is not limited to these examples. These vinyl ether group-containing (meth)acrylic acid esters may be used alone or in combination of two or more. Examples of allyl group-containing (meth)acrylic acid esters include allyl (meth)acrylate, but the present disclosure is not limited to these examples.

[0078] Examples of polyfunctional (meth)acryloyl group-containing isocyanurates include tri(acryloyloxyethyl)isocyanurate, tri(methacryloyloxyethyl)isocyanurate, alkylene oxide-added tri(acryloyloxyethyl)isocyanurate, alkylene oxide-added tri(methacryloyloxyethyl)isocyanurate, etc., but the present disclosure is not limited to these examples. These polyfunctional (meth)acryloyl group-containing isocyanurates may be used alone or in combination of two or more types.

[0079] Examples of polyfunctional urethane (meth)acrylates include polyfunctional urethane (meth)acrylates obtained by reacting a polyfunctional isocyanate such as tolylene diisocyanate, isophorone diisocyanate, or xylylene diisocyanate with a hydroxyl group-containing (meth)acrylic acid ester such as 2-hydroxyethyl (meth)acrylate or 2-hydroxypropyl (meth)acrylate, but the present disclosure is not limited to these examples.

[0080] Examples of polyfunctional 2-(meth)allyloxymethyl acrylate esters include, but are not limited to, the polyfunctional 2-(meth)allyloxymethyl acrylate esters described in Japanese Patent No. 05689628. These polyfunctional 2-(meth)allyloxymethyl acrylate esters may be used alone or in combination of two or more.

[0081] Examples of polyfunctional maleimide compounds include 4,4'-diphenylmethane bismaleimide, m-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6-bismaleimide-(2,2,4-trimethyl)hexane, and phenylmethane maleimide oligomer, but the present disclosure is not limited to these examples. These polyfunctional maleimide compounds may be used alone or in combination of two or more.

[0082] Examples of polyfunctional vinyl ethers include ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether, bisphenol F alkylene oxide divinyl ether, trimethylolpropane trivinyl ether, ditrimethylolpropane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether, ethylene oxide-added trimethylolpropane trivinyl ether, ethylene oxide-added ditrimethylolpropane tetravinyl ether, ethylene oxide-added pentaerythritol tetravinyl ether, and ethylene oxide-added dipentaerythritol hexavinyl ether, but the present disclosure is not limited to these examples. These polyfunctional vinyl ethers may be used alone or in combination of two or more.

[0083] Examples of polyfunctional allyl compounds include ethylene glycol diallyl ether, diethylene glycol diallyl ether, polyethylene glycol diallyl ether, propylene glycol diallyl ether, butylene glycol diallyl ether, hexanediol diallyl ether, bisphenol A alkylene oxide diallyl ether, bisphenol F alkylene oxide diallyl ether, trimethylolpropane triallyl ether, ditrimethylolpropane tetraallyl ether, glycerin triallyl ether, pentaerythritol tetraallyl ether, and dipentaerythritol pentaallyl ether. Examples of suitable allyl compounds include polyfunctional allyl ethers such as dipentaerythritol hexaallyl ether, ethylene oxide-added trimethylolpropane triallyl ether, ethylene oxide-added ditrimethylolpropane tetraallyl ether, ethylene oxide-added pentaerythritol tetraallyl ether, and ethylene oxide-added dipentaerythritol hexaallyl ether; polyfunctional allyl group-containing isocyanurates such as triallyl isocyanurate; polyfunctional allyl esters such as diallyl phthalate and diallyl diphenate; and bisallyl nadimide compounds, but the present disclosure is not limited to these examples. These polyfunctional allyl compounds may be used alone or in combination of two or more.

[0084] Examples of polyfunctional aromatic vinyls include divinylbenzene, but the present disclosure is not limited to these examples.

[0085] The polyfunctional radical polymerizable compound may be an oligomer or polymer having a repeating unit based on a monomer in the skeleton portion other than the radical polymerizable group. When the molecular weight of the polyfunctional radical polymerizable compound is less than 1000, it is classified as an oligomer, and when the molecular weight is 1000 or more, it is classified as a polymer.

[0086] Examples of the backbone of the oligomer or polymer of the polyfunctional radically polymerizable compound include polyester-based backbone, polyether-based backbone, polyurethane-based backbone, conjugated diene-based polymer backbone such as polybutadiene or polyisoprene, poly(meth)acrylate-based backbone, phenolic resin backbone, aniline resin backbone, polyolefin-based backbone, polyamide-based backbone, cycloolefin-based polymer backbone, and polysiloxane-based backbone, but the present disclosure is not limited to these examples. Among these backbone, polyester-based backbone, polyether-based backbone, polyurethane-based backbone, conjugated diene-based polymer backbone, poly(meth)acrylate-based backbone, phenolic resin backbone, and aniline resin backbone are preferred. The backbone portion and the radically polymerizable group may be bonded by a covalent bond, but are preferably bonded via an ester bond and / or a urethane bond.

[0087] Examples of oligomers or polymers of polyfunctional radical polymerizable compounds include urethane (meth)acrylate polymerizable oligomers in which a (meth)acryloyl group is bonded to a skeleton portion via a urethane bond, urethane (meth)acrylate polymers in which a (meth)acryloyl group is bonded to a skeleton portion via a urethane bond, epoxy (meth)acrylate polymerizable oligomers having a structure in which (meth)acrylic acid is added to an epoxy resin (oligomer or polymer having an epoxy group), epoxy (meth)acrylate polymers having a structure in which (meth)acrylic acid is added to an epoxy resin (oligomer or polymer having an epoxy group), and polys in which a (meth)acryloyl group is bonded to a polyester skeleton via an ester bond. Examples of such polymerizable oligomers include ester (meth)acrylate polymerizable oligomers, polyester (meth)acrylate polymers in which a (meth)acryloyl group is bonded to a polyester skeleton via an ester bond, phenylmethane (meth)acrylate polymerizable oligomers in which a (meth)acryloyl group is bonded to a phenolic resin skeleton via an ester bond, phenylmethane (meth)acrylate polymers in which a (meth)acryloyl group is bonded to a phenolic resin skeleton via an ester bond, phenylmethane maleimide polymerizable oligomers in which a maleimide group is bonded directly to an aniline resin skeleton, and phenylmethane maleimide polymers in which a maleimide group is bonded directly to an aniline resin skeleton, but the present disclosure is not limited to these examples.

[0088] The polyfunctional radical polymerizable compound can be easily obtained commercially. Examples of the polyfunctional radical polymerizable compound that can be easily obtained commercially include, for example, products manufactured by Kyoeisha Chemical Co., Ltd. under the trade names: Light Acrylate 3EG-A, Light Acrylate 4EG-A, Light Acrylate 9EG-A, Light Acrylate 14EG-A, Light Acrylate NP-A, Light Acrylate 1,6-HX-A, Light Acrylate 1,9ND-A, Light Acrylate DCP-A, Light Acrylate BP-4EA, Light Acrylate BP-4PA, Light Acrylate TMP-A, Light Acrylate TMP-3EO-A, Light Acrylate TMP-6EO-3A, ​​Light Acrylate PE-3A, Light Acrylate PE-4A, Light Acrylate DPE-6A, Light Acrylate BA-134, Light Acrylate HPP-A, Light Acrylate PTMGA-250, Light Acrylate DTMP-4A, Light Ester EG, Light Ester 2EG, Light Ester 3EG, Light Ester 4EG, Light Ester 9EG, Light Ester 14EG, Light Ester NP, Light Ester 1·3BG, Light Ester 1,4-BG, Light Ester 1,6-HX, Light Ester 1,9ND, Light Ester 1·10DC, Light Ester TMP, Light Ester G-101P, Light Ester G-201P, Light Ester BP-2EM, Epoxy Ester 40EM, Epoxy Ester 70PA, Epoxy Ester 200PA, Epoxy Ester 80MFA, Epoxy Ester 3002M, Epoxy Ester 3002A, Epoxy Ester 1600A, Epoxy Ester 3000M, Epoxy Ester 3000A, Epoxy Ester 200EA, Epoxy Ester 400EA, AH-600, AT-600, UA-306H, AI-600, UA-101T, UA-101I, UA-306T, UA-306I, etc.;

[0089] Manufactured by SARTOMER, product numbers: SR212, SR213, SR230, SR238F, SR247, SR259, SR268, SR272, SR306H, SR344, SR349, CD406, SR508, CD536, CD560, CD561, CD562, CD564, CD580, CD581, CD582, SR601, SR602, SR610, CD802, SR833, SR9003, CD9038, CD9043, SR9045, SR9209A, SR101, SR150, SR205, SR206, SR209, SR210, SR214 , SR239, SR248, SR252, CD262, SR297, SR348, CD401, SR480, CD540, SR541, CD542, SR603, SR644, SR740, SR9036, SR351S, SR368, SR415, SR444, SR454, SR 492, SR499, CD501, SR502, SR9020, 9021, SR9035, SR350, SR9009, SR9011, SR295, SR355, SR494, SR399, SR9041, SR9012, CD9051, CD9053, CN929, CN940, CN944B85, CN959, CN961, CN961E75, CN961H81, CN962, CN963, CN963A80, CN963B80, CN963E75, CN963E80, CN963J75, CN964, CN964A85, CN964E75, CN965 , CN965A80, CN966, CN966A80, CN966B85, CN966H90, CN966J75, CN966R60, CN968, CN980, CN981, CN981A75, CN981B88, CN982, CN982A75, CN982B88, CN98 2E75, CN982P90, CN983, CN985B88, CN989, CN991, CN996, CN9001, CN9002, CN9004, CN9005, CN9006, CN9007, CN9008, CN9009, CN9010, CN9011, CN9014, C N9178, CN9788, CN9893, CN902J75, CN970A60, CN970E60, CN970H75, CN971, CN971A80, CN972, CN973, CN973A80, CN973H85, CN973J75, CN975, CN977C70,CN978, CN992, CN994, CN997, CN999, CN9165, CN9782, CN9783, CN1963, CN2901, CN2902, CN2920, CN2921, CN32 10, CN3211, CN104, CN104A80, CN104B80, CN104D80, CN111US, CN112C60, CN113D70, CN115, CN116, CN117, CN11 8, CN119, CN120, CN120A75, CN120B60, CN120B80, CN120C60, CN120C80, CN120D80, CN120E50, CN120M50, CN12 1, CN132, CN133, CN136, CN137, CN151, CN152, CNUVE151, CNUVE150 / 80, CN160, CN2100, CN2101, CN2102E, CN29 2, CN293, CN394, CN296, CN299, CN2200, CN2203, CN2250, CN2251, CN2252, CN2253, CN2254, CN2255, CN2256, C N2257, CN2258, CN2259, CN2260, CN2261, CN2262, CN2270, CN2271E, CN2272, CN2273, CN2276, CN2278, CN2279, CN2280, CN2281, CN2282, CN2285, CN2297A, CN2298, CN2470, CN2300, CN2301, CN2302, CN2303, CN2304, CN147, CN301, CN303, CN307, CN371, CN501, CN550, CN551, CN2201, CN736, CN738, CN9101, CN2600, CN990, CN9800, etc.;

[0090] Osaka Organic Chemical Industry Co., Ltd., trade names: Viscoat #195, Viscoat #230, Viscoat #260, Viscoat #310HP, Viscoat #335HP, Viscoat #700, Viscoat #540, Viscoat #295, Viscoat #300, Viscoat #400, Viscoat #360, Viscoat #802, Viscoat #1000, Viscoat #1020, Viscoat #3PA, Viscoat #3PMA, STAR-501, BAC-15, BAC-45, UV-4108F, UV-4117F, and the like;

[0091] Manufactured by Nippon Gosei Kagaku Kogyo Co., Ltd., product name: Shiko UV-1700B, Shiko UV-6300B, Shiko UV-7550B, Shiko UV-7600B, Shiko UV-7605B, Shiko UV-7610B, Shiko UV-7620EA, Shiko UV-7630B, Shiko UV-7640B, Shiko UV-7650B, Shiko UV-6630B, Shiko UV-7000B , Shiko UV-7510B, Shiko UV-7461TE, Shiko UV-2000B, Shiko UV-2750B, Shiko UV-3000B, Shiko UV-3200B, Shiko UV-32 10EA, Shikou UV-3300B, Shikou UV-3310B, Shikou UV-3500BA, Shikou UV-3520TL, Shikou UV-3700B, Shikou UV-6640B, etc;

[0092] Manufactured by Toagosei Co., Ltd., trade names: Aronix M-208, Aronix M-211B, Aronix M-215, Aronix M-220, Aronix M-225, Aronix M-270, Aronix M-240, Aronix M-309, Aronix M-310, Aronix M-321, Aronix M-350, Aronix M-360, Aronix M-313, Aronix M-315, Aronix M-306, Aronix M-305, Aronix M-303, Aronix M-452, Aronix M-450, Aronix M-408, Aronix M-403, Aronix M -400, Aronix M-402, Aronix M-404, Aronix M-406, Aronix M-405, Aronix M-460, Aronix M-510, Aronix M-520, Aronix M-1100, Aronix M-1200, Aronix M-6100, Aronix M-6200, Aronix M-6250, Aronix M-6500, Aronix M-7100, Aronix M-7300K, Aronix M-8030, Aronix M-8060, Aronix M-8100, Aronix M-8530, Aronix M-8560, Aronix M-9050, etc.;

[0093] Examples of suitable polyfunctional radical polymerizable compounds include those manufactured by Nippon Shokubai Co., Ltd. under the trade names VEEA and VEEM; those manufactured by Kuraray Co., Ltd. under the product number UC-203; those manufactured by Daiwa Kasei Kogyo Co., Ltd. under the product numbers BMI-1000, BMI-2000, BMI-2300, BMI-3000, BMI-4000, BMI-5100, BMI-7000, and BMI-TMH; and those manufactured by Maruzen Petrochemical Co., Ltd. under the product numbers BANI-X and BANI-M. However, the present disclosure is not limited to these examples. These polyfunctional radical polymerizable compounds may be used alone or in combination of two or more.

[0094] <Other ingredients> The polymerizable composition of the present disclosure may contain components other than the above-described cyclopolymerizable carboxylic acid compound (A), β-hydroxycarboxylic acid compound (B), and radically polymerizable compound (C), depending on the intended use, application, etc. Examples of such components include radical polymerization inhibitors, radical polymerization initiators, compounds having a reactive group other than radically polymerizable, organic solvents, thermoplastic resins, organic or inorganic fine particles, fillers, quantum dots, dyes, pigments, dispersants, UV absorbers, leveling agents, surface conditioners, antistatic agents, adhesion improvers, coupling agents, mold release agents, and viscosity modifiers, but the present disclosure is not limited to these. Among the other components, the main ones are specifically shown below, but the present disclosure is not limited to these examples.

[0095] [Radical polymerization inhibitors] From the viewpoint of suppressing undesired radical polymerization during storage, transportation, and various operations in the preparation and processing of the composition, the polymerizable composition of the present disclosure may contain an appropriate amount of a primary antioxidant having a radical chain inhibitory property and / or a secondary antioxidant having a peroxide decomposition property.

[0096] Examples of primary antioxidants include hydroquinones, benzoquinones, phenols, aromatic amines, phenothiazines, dithiocarbamic acid metal salts, and nitroso compounds, but the present disclosure is not limited to these examples. Examples of secondary antioxidants include phosphorus-based compounds such as phosphine and phosphites, and sulfur-based compounds such as thioethers, mercaptobenzimidazole, and thiourea, but the present disclosure is not limited to these examples. The primary antioxidants and secondary antioxidants may be used alone, but it is more preferable to use them in combination.

[0097] Among primary antioxidants, phenols are preferred from the viewpoint of inhibiting coloration, and among secondary antioxidants, thioethers are preferred from the viewpoint of acid resistance and hydrolysis resistance.

[0098] Examples of phenols include monoetherified hydroquinones, hindered phenols and their polymers (including dimers) or derivatives of the polymers, and semi-hindered phenols and their polymers (including dimers) or derivatives of the polymers, but the present disclosure is not limited to these examples. These phenols may be used alone or in combination of two or more.

[0099] Examples of monoetherified hydroquinones include hydroquinone monomethyl ether, hydroquinone mono-n-butyl ether, hydroquinone monobenzyl ether, hydroquinone monocyclohexyl ether, 4-methoxy-1-naphthol, etc., but the present disclosure is not limited to these examples. These monoetherified hydroquinones may be used alone or in combination of two or more.

[0100] Examples of hindered phenols include 2,6-bis(tert-butyl)-4-methylphenol, octadecyl-3-(3,5-ditert-butyl-4-hydroxyphenyl)propionate, isooctyl-3-(3,5-ditert-butyl-4-hydroxyphenyl)propionate, 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-ditert-butylanilino)-1,3,5-triazine, and 3,5-ditert-butyl-4-hydroxybenzylphosphonate-diethyl ester, but the present disclosure is not limited to these examples.

[0101] Examples of oligomers or derivatives of oligomers of hindered phenols include pentaerythrityl tetrakis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propionate], 2,2-thio-diethylenebis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-ditert-butyl-4-hydroxyhydrocinnamamide), 1,6-hexanediol-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propionate], tris-(3,5-ditert-butyl-4-hydroxybenzyl)isocyanurate, and 1,3,5-trimethyl-2,4,6-tris(3,5-ditert-butyl-4-hydroxybenzyl)benzene, but the present disclosure is not limited to these examples. The hindered phenols and their polymers (including dimers) or derivatives of the polymers may be used either alone or in combination of two or more kinds.

[0102] Examples of semi-hindered phenols include 6-tert-butyl-o-cresol, 6-tert-butyl-2,4-xylenol, 2,4,8,10-tetra-tert-butyl-6-[3-(3-methyl-4-hydroxy-5-t-butylphenyl)propoxy]dibenzo[d,f][1,3,2]dioxaphosphepine, 2,4-dimethyl-6-(1-methylpentadecyl)phenol, 2,4-bis(octylthiomethyl)-o-cresol, 2,4-bis(dodecylthiomethyl)-o-cresol, 2-tert-butylphenol, 2,4-di-tert-butylphenol, 2-tert-amylphenol, and 2,4-di-tert-amylphenol, but the present disclosure is not limited to these examples.

[0103] Examples of the polymerized products or derivatives of polymerized products of semi-hindered phenols include methylenebis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate], triethylene glycol bis[β-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 4,4'-thiobis(2-methyl-6-tert-butylphenol), bis(3-methyl-4-hydroxy-5-tert-butylbenzyl)sulfide, terephthaloyl-di(2,6-dimethyl-4-tert-butyl-3-hydroxybenzyl sulfide), 3,9-bis[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, 4,4'-butyl ... Examples of the hydroxybenzoates include 2,2'-methylenebis(6-tert-butyl-3-methylphenol), 4,4'-thiobis(6-tert-butyl-3-methylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 2,2'-thiobis(4-methyl-6-tert-butylphenol), 2-[1-(2-hydroxy-3,5-ditert-pentylphenyl)ethyl]-4,6-ditert-pentylphenyl acrylate, and 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate, but the present disclosure is not limited to these examples. The semi-hindered phenols and their polymers (including dimers) or derivatives of the polymers may be used either alone or in combination of two or more kinds.

[0104] Examples of phosphines include triethylphosphine, tributylphosphine, tris(2-ethylhexyl)phosphine, triphenylphosphine, etc., but the present disclosure is not limited to these examples. These phosphines may be used alone or in combination of two or more.

[0105] Examples of phosphites include diethyl hydrogen phosphite, bis(2-ethylhexyl) hydrogen phosphite, dilauryl hydrogen phosphite, dioleyl hydrogen phosphite, diphenyl hydrogen phosphite, triethyl phosphite, tributyl phosphite, tris(2-ethylhexyl) phosphite, triisodecyl phosphite, trilauryl phosphite, tris(tridecyl phosphite), trioleyl phosphite, tristearyl phosphite, phenyl diisodecyl phosphite, Sodecyl phosphite, diphenyl methyl phosphite, 2-ethylhexyl diphenyl phosphite, isodecyl diphenyl phosphite, tridecyl diphenyl phosphite, bis(2,4-ditert-butyl-6-methylphenyl)ethyl phosphite, triphenyl phosphite, tricresyl phosphite, tris(nonylphenyl) phosphite, tris(2,4-ditert-butylphenyl) phosphite, bis(isodecyl)pentaerythritol diphosphite, bis(tridecyl)pentaerythritol Diphosphite, bis(stearyl)pentaerythritol diphosphite, bis(nonylphenyl)pentaerythritol diphosphite, bis(2,4-ditert-butylphenyl)pentaerythritol diphosphite, bis(2,6-ditert-butyl-6-methylphenyl)pentaerythritol diphosphite, 4,4'-butylidenebis(3-methyl-6-tert-butylphenyldiisotridecyl)phosphite, tetraphenyldipropylene glycol diphosphite, tetraphenyl tetra Tetra(tridecyl)pentaerythritol tetraphosphite, tetra(C12-C15 alkyl)-4,4'-isopropylidenediphenyl phosphite, tetra(tridecyl)-1,1,3-tris(2-methyl-5-tert-butyl-4-hydroxyphenyl)butane diphosphite, 2,4,8,10-tetra-tert-butyl-6-[3-(3-methyl-4-hydroxy-5-tert-butylphenyl)propoxy]dibenzo[d,f][1,3,2]dioxaphosphepine, 2,2-methylenebis(4,Examples of suitable phosphites include (6-tert-butylphenyl)-2-ethylhexyl phosphite and trilauryl trithiophosphite, but the present disclosure is not limited to these examples. These phosphites may be used alone or in combination of two or more.

[0106] Examples of thioethers include 2,2'-thiodiglycolic acid, (ethylenedithio)diacetic acid, 2,2'-(ethylenedithio)diethanol, 3,3'-thiodipropionic acid, dimethyl 3,3'-thiodipropionate, 3-laurylthiopropionic acid, methyl 3-laurylthiopropionate, (3-octylthiopropionic acid) pentaerythritol tetraester, (3-decylthiopropionic acid) pentaerythritol tetraester, (3-laurylthiopropionic acid) pentaerythritol tetraester, (3-oleylthiopropionic acid) pentaerythritol tetraester, (3-stearylthiopropionic acid) pentaerythritol tetraester, (3-laurylthiopropionic acid) pentaerythritol tetraester, Examples of thioethers include 4,4'-thiodi(3-methyl-5-tert-butyl-4-phenol) ester of laurylthiopropionic acid, dioctyl thiodipropionate, didecyl thiodipropionate, dilauryl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, laurylstearyl thiodipropionate, distearyl-β,β'-thiodibutyrate, dimethyl sulfide, methyl dodecyl sulfide, dilauryl sulfide, distearyl sulfide, 2,4-bis(octylthiomethyl)-o-cresol, and 2,4-bis(dodecylthiomethyl)-o-cresol, but the present disclosure is not limited to these examples. These thioethers may be used alone or in combination of two or more.

[0107] The amount of the radical polymerization inhibitor is preferably 0.005 to 2 parts by mass, more preferably 0.01 to 1 part by mass, and even more preferably 0.02 to 0.5 parts by mass, per 100 parts by mass of the total of the radically polymerizable components, from the viewpoint of suppressing undesired radical polymerization during various operations in storage, transportation, composition preparation, and processing, while also ensuring radical polymerizability appropriate for the application. In this specification, the radically polymerizable components refer to the two components, the cyclopolymerizable carboxylic acid compound (A) and the radically polymerizable compound (C), described above.

[0108] [Radical polymerization initiator] Radical polymerization initiators can be classified into photoradical initiators that generate radicals upon irradiation with active energy rays and thermal radical initiators that generate radicals upon heating. They can be selected according to the application and purpose, and photoradical initiators and thermal radical initiators may be used in combination.

[0109] Examples of photoradical initiators include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether; acetophenone compounds such as acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one; anthraquinone compounds such as 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-chloroanthraquinone, and 2-amylanthraquinone; and 2,4-diethylthioxane. Examples of suitable thioxanthone compounds include thioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, and [3-(3,4-dimethyl-9-oxothioxanthen-2-yl)oxy-2-hydroxypropyl]-trimethylazanium chloride; ketal compounds include acetophenone dimethyl ketal and benzil dimethyl ketal; benzophenone compounds include benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide and 4,4'-bismethylaminobenzophenone; phosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; and mixtures thereof. These compounds may be used alone or in combination of two or more.

[0110] As the thermal radical initiator, an organic peroxide initiator or an azo initiator is suitable, and specific examples thereof include the following. Methyl ethyl ketone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide, methyl acetoacetate peroxide, acetylacetate peroxide, 1,1-bis(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-hexylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)-2-methylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane Cyclohexane, 1,1-bis(t-butylperoxy)cyclododecane, 1,1-bis(t-butylperoxy)butane, 2,2-bis(4,4-di-t-butylperoxycyclohexyl)propane, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-hexyl hydroperoxide, t-butyl hydroperoxide, α,α'-bis(t-butylperoxy)diisopropylbenzene, diisopropylbenzene Cumyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, t-butylcumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexyne-3, isobutyryl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, succinic acid peroxide, m-toluoylbenzoyl peroxide, benzoyl peroxide, di-n-propyl peroxide Oxydicarbonate, diisopropyl peroxydicarbonate, bis(4-t-butylcyclohexyl) peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, di-2-ethoxyhexyl peroxydicarbonate, di-3-methoxybutyl peroxydicarbonate, di-s-butyl peroxydicarbonate, di(3-methyl-3-methoxybutyl) peroxydicarbonate, α,α'-bis(neodecanoylperoxy)diisopropylbenzene, cumyl peroxyneodecanoate, 1,1,3,3,-Tetramethylbutylperoxyneodecanoate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, t-hexylperoxyneodecanoate, t-butylperoxyneodecanoate, t-hexylperoxypivalate, t-butylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexanoate, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-hexylperoxyisopropyl monocarbonate, t-butylperoxyisobutyrate, t-butylperoxymalate, t-butylperoxy-3, Organic peroxide initiators such as 5,5-trimethylhexanoate, t-butyl peroxylaurate, t-butylperoxyisopropyl monocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate, t-butyl peroxyacetate, t-butylperoxy-m-toluylbenzoate, t-butyl peroxybenzoate, bis(t-butylperoxy)isophthalate, 2,5-dimethyl-2,5-bis(m-toluylperoxy)hexane, t-hexyl peroxybenzoate, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane, t-butylperoxyallyl monocarbonate, t-butyltrimethylsilyl peroxide, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, and 2,3-dimethyl-2,3-diphenylbutane.

[0111] 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, 1-[(1-cyano-1-methylethyl)azo]formamide, 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2-azobis(2-methylbutyronitrile), 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile), 2,2'-azobis(2-methylpropionamidine) dihydrochloride, 2,2'-azobis(2-methyl 2,2'-Azobis[N-(4-chlorophenyl)-2-methylpropionamidine]dihydrochloride, 2,2'-Azobis[N-(4-hydrophenyl)-2-methylpropionamidine]dihydrochloride, 2,2'-Azobis[2-methyl-N-(phenylmethyl)propionamidine]dihydrochloride, 2,2'-Azobis[2-methyl-N-(2-propenyl)propionamidine]dihydrochloride, 2,2'-Azobis[N-(2-hydroxyethyl)- 2-Methylpropionamidine]dihydrochloride, 2,2'-azobis[2-(5-methyl-2-imidazolin-2-yl)propane]dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride, 2,2'-azobis[2-(4,5,6,7-tetrahydro-1H-1,3-diazepin-2-yl)propane]dihydrochloride, 2,2'-azobis[2-(3,4,5,6-tetrahydropyrimidin-2-yl)propane]dihydrochloride, 2,2'-azobis[2-(5-methyl-2-imidazolin-2-yl)propane]dihydrochloride 2,2'-Azobis{2-[1-(2-hydroxyethyl)-2-imidazolin-2-yl]propane}dihydrochloride, 2,2'-Azobis[2-(2-imidazolin-2-yl)propane], 2,2'-Azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide}, 2,2'-Azobis{2-methyl-N-[1,1-bis(hydroxymethyl)ethyl]propionamide}, 2,Azo initiators such as 2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], 2,2'-azobis(2-methylpropionamide), 2,2'-azobis(2,4,4-trimethylpentane), 2,2'-azobis(2-methylpropane), dimethyl-2,2-azobis(2-methylpropionate), 4,4'-azobis(4-cyanopentanoic acid), and 2,2'-azobis[2-(hydroxymethyl)propionitrile]. These may be used alone or in combination of two or more.

[0112] The content of the radical polymerization initiator is preferably 0.05 to 10.0 parts by mass, more preferably 0.1 to 7.0 parts by mass, and even more preferably 0.2 to 5.0 parts by mass, relative to 100 parts by mass of the total of the radically polymerizable components.

[0113] [Compounds having reactive groups other than radical polymerizable groups] Depending on the application, a low molecular weight compound, oligomer, or polymer compound having a reactive group other than radical polymerizable groups may be used to improve various properties such as heat resistance and adhesion. Examples of such compounds include compounds having a cationically polymerizable group such as an epoxy group, an oxetanyl group, or a vinyl ether group; compounds having a functional group that reacts with a carboxyl group such as an epoxy group, an oxazoline group, a carbodiimide group, or an aziridine group; compounds having an isocyanate group, compounds having a functional group that reacts with a hydroxyl group such as an amino resin; and compounds having a silane coupling group.

[0114] The content of the compound having a reactive group other than radical polymerizable groups may be adjusted depending on the application or purpose, and it does not have to be included; however, when used, the content is preferably 1 to 300 parts by mass, more preferably 2 to 200 parts by mass, and even more preferably 3 to 100 parts by mass per 100 parts by mass of the total of the radical polymerizable components.

[0115] [Organic solvents] An appropriate amount of organic solvent may be contained from the viewpoint of adjusting viscosity, adjusting the thickness of the coating film, dissolving the resin in the composition, and the like. Examples of organic solvents include monoalcohols such as methanol, ethanol, isopropanol, n-butanol, and sec-butanol; glycols such as ethylene glycol and propylene glycol; cyclic ethers such as tetrahydrofuran and dioxane; glycol monoethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, and 3-methoxybutanol; glycol ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol dimethyl ether, and propylene glycol diethyl ether; ethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol mono Esters of glycol monoethers such as dipropylene glycol monobutyl ether acetate, dipropylene glycol monobutyl ether acetate, and 3-methoxybutyl acetate; alkyl esters such as methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl lactate, ethyl lactate, butyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl acetoacetate, and ethyl acetoacetate;Examples of suitable organic solvents include, but are not limited to, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; aromatic hydrocarbon compounds such as benzene, toluene, xylene, and ethylbenzene; aliphatic hydrocarbon compounds such as hexane, cyclohexane, and octane; and amides such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. These organic solvents may be used alone or in combination of two or more.

[0116] The content of the organic solvent may be adjusted depending on the application or purpose, and it does not have to be included; however, when used, the content is preferably 1 to 1,000 parts by mass, more preferably 2 to 700 parts by mass, and even more preferably 3 to 500 parts by mass, per 100 parts by mass of the total of the radically polymerizable components.

[0117] Furthermore, the content of other components other than the above-mentioned components may be adjusted depending on the application or purpose, and they do not necessarily need to be included; however, when used, the content is preferably 1 to 300 parts by mass, more preferably 2 to 200 parts by mass, and even more preferably 3 to 100 parts by mass, per 100 parts by mass of the total of the radical polymerizable components.

[0118] <Method for producing polymerizable composition of the present disclosure> Next, a method for producing the polymerizable composition of the present disclosure will be described. The method for producing the polymerizable composition of the present disclosure includes a step of hydrolyzing a 2-allyloxymethyl acrylic acid ester to produce a cyclopolymerizable carboxylic acid compound (A) (hereinafter, sometimes simply referred to as a hydrolysis step), and a step of combining the cyclopolymerizable carboxylic acid compound (A) with a radically polymerizable compound (C) (hereinafter, sometimes simply referred to as a combining step).

[0119] The hydrolysis step is a step including a step of hydrolyzing 2-allyloxymethyl acrylate with a strong acid or a medium to strong base, and from the viewpoint of suppressing polymerization during the hydrolysis reaction, a method of hydrolysis with a medium to strong base is preferred.

[0120] The combining step is a step of uniformly mixing the cyclopolymerizable carboxylic acid compound (A) and the radically polymerizable compound (C) in the composition.

[0121] The hydrolysis step and the combining step can be carried out either integrally or independently. Either the hydrolysis step or the combining step can be carried out first. The integrated method can be broadly divided into two types. One is a method in which a portion of the 2-allyloxymethyl acrylic acid ester is hydrolyzed. In this case, at least the starting material 2-allyloxymethyl acrylic acid ester is contained as the radical polymerizable compound (C) along with the cyclopolymerizable carboxylic acid compound (A) produced via hydrolysis. The other is a method including a step of hydrolyzing the 2-allyloxymethyl acrylic acid ester in the presence of a radical polymerizable compound (C) other than the 2-allyloxymethyl acrylic acid ester. In this case, it is preferable to select a compound that is less likely to undergo structural change under hydrolysis conditions as the radical polymerizable compound (C). The independent method refers to a method in which the radical polymerizable compound (C) is added after the hydrolysis step. From the viewpoint of efficiency, the hydrolysis step and the combining step are preferably carried out integrally. However, from the viewpoint of being able to use various compounds as the radical polymerizable compound (C), it is preferable to carry them out independently.

[0122] Furthermore, to achieve the desired composition, steps other than the hydrolysis step and the conjugation step (hereinafter sometimes referred to as "other steps") may be included. Examples of other steps include a step of adding a strong acid to convert a salt of 2-allyloxymethylacrylic acid into 2-allyloxymethylacrylic acid (strong acid treatment), a step of adding a strong acid salt of another metal species to an aqueous solution of the salt of 2-allyloxymethylacrylic acid to perform cation exchange (metaserosity treatment), a step of extracting the cyclopolymerizable carboxylic acid compound (A) with an organic solvent that separates into two layers from water, a step of removing water-soluble inorganic salts and by-products by washing with water, a step of distilling off water and the organic solvent, and a step of removing the polymerized product. The other steps may be performed simultaneously with or after the hydrolysis step, and may be performed before, simultaneously with, or after the conjugation step. Two or more of the other steps may be combined, and two or more may be performed simultaneously or independently, in any order, and may be repeated two or more times.

[0123] The polymerizable composition of the present disclosure is characterized by a reduced amount of the β-hydroxycarboxylic acid compound (B), and the following describes in detail the steps and operations that have a significant impact on reducing the amount of the β-hydroxycarboxylic acid compound (B). The following also describes in detail the steps and operations that have a significant impact on suppressing the generation of undesired polymers (by-products).

[0124] <Hydrolysis process> 2-Allyloxymethyl acrylate can be hydrolyzed with a strong acid or a medium- to strong-base. From the viewpoint of inhibiting polymerization during hydrolysis, hydrolysis with a medium- to strong-base solution that exhibits a pH of 9.5 or higher when dissolved in water is preferred. Inorganic bases are preferred to avoid introducing excess organic components. Considering the ability to achieve colorlessness, the metal component (which may be two or more) of the inorganic base is preferably a typical metal element or a metal belonging to Group 3 or Group 4 of the periodic table. Considering toxicity, lithium, sodium, potassium, magnesium, calcium, zinc, or aluminum is more preferred. Considering the solubility and availability of the inorganic base in water, lithium, sodium, or potassium is even more preferred. Specific examples of such inorganic bases include lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, trisodium phosphate, tripotassium phosphate, sodium aluminate, and potassium aluminate. Considering ease of post-treatment and wastewater treatment, sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate are particularly preferred, but the inorganic base is not limited to these examples.

[0125] As the 2-allyloxymethyl acrylic acid ester, from the viewpoints of availability and the fact that hydrolysis occurs under mild conditions, a lower ester having a small number of carbon atoms is preferred, an ester of a saturated hydrocarbon having 4 or less carbon atoms is more preferred, and methyl 2-allyloxymethylacrylate and ethyl 2-allyloxymethylacrylate are particularly preferred.

[0126] When 2-allyloxymethylacrylic ester is hydrolyzed with an inorganic base, the main reaction is hydrolysis of the ester moiety, and the important products are the inorganic salt of 2-allyloxymethylacrylic acid and alcohol. For example, when the 2-allyloxymethylacrylic ester is methyl 2-allyloxymethylacrylate and the inorganic base is sodium hydroxide, the main reaction is the production of sodium 2-allyloxymethylacrylate and methanol (see the reaction scheme below).

[0127] [ka]

[0128] On the other hand, it is speculated that the main side reaction is the Michael addition of hydroxide ions derived from water or alkoxide ions derived from the alcohol produced in the main reaction to the double bond conjugated with the carbonyl group, followed by hydrogen abstraction, elimination, and hydrolysis of the ester moiety to produce the β-hydroxycarboxylic acid compound (B).The main side reaction and by-products are specifically shown below when the 2-allyloxymethyl acrylic ester is methyl 2-allyloxymethylacrylate and the inorganic base is sodium hydroxide.

[0129] [ka]

[0130] Therefore, in order to reduce the amount of the β-hydroxycarboxylic acid compound (B), one or both of the following two methods may be carried out: suppression of the Michael addition reaction; and purification treatment after hydrolysis.

[0131] Methods for suppressing the Michael addition include, but are not limited to, using an aqueous solution of a low concentration inorganic base, lowering the reaction temperature, removing the alcohol produced by hydrolysis of the ester moiety during the reaction from the reaction system (by distillation, etc.), using a moderate inorganic base, and partially hydrolyzing the 2-allyloxymethyl acrylic acid ester (by stopping the reaction midway, using a base in an amount less than the chemical equivalent, etc.). Two or more of these methods for suppressing the Michael addition may be combined, or two or more may be carried out simultaneously or independently, in any order, and may be repeated two or more times.

[0132] As particularly preferred examples of the method for suppressing the Michael addition, methods (1) to (3) are exemplified below. A method of combining two or more of methods (1) to (3) is more preferred. Furthermore, by combining methods (1) to (3) with the water washing treatment described below as a purification treatment after hydrolysis, the β-hydroxycarboxylic acid compound (B) can be reduced more effectively.

[0133] (1) Method using a low-concentration strong alkaline solution This method uses a low-concentration strong alkaline aqueous solution to hydrolyze substantially all of the raw material 2-allyloxymethyl acrylate.

[0134] As the strong alkali, hydroxides of metals of Group 1 or 2 of the periodic table are preferred, among which lithium hydroxide, sodium hydroxide and potassium hydroxide are preferred, and sodium hydroxide and potassium hydroxide are particularly preferred.

[0135] In the hydrolysis, it is preferable to mix and stir only the strong alkaline aqueous solution and the 2-allyloxymethyl acrylate without using an organic solvent. The 2-allyloxymethyl acrylate to be used is preferably methyl 2-allyloxymethylacrylate or ethyl 2-allyloxymethylacrylate.

[0136] The concentration of the strong alkaline aqueous solution is preferably 0.1 to 1.6 mmol / g, more preferably 0.2 to 1.3 mmol / g, and even more preferably 0.3 to 1.0 mmol / g.

[0137] The reaction temperature is preferably 0 to 60°C, more preferably 0 to 50°C, even more preferably 0 to 40°C, and most preferably 0 to 35°C.

[0138] It is preferable to hydrolyze substantially all of the raw material 2-allyloxymethyl acrylic acid ester, and the molar ratio of strong alkali / 2-allyloxymethyl acrylic acid ester used for this purpose is preferably 0.98 to 1.10, more preferably 0.99 to 1.09, and even more preferably 1.0 to 1.08.

[0139] (2) A method using a medium strength aqueous solution of alkali This method uses an aqueous alkaline solution of moderate strength to hydrolyze substantially the entire amount of the starting material, 2-allyloxymethyl acrylate. As the alkali of medium strength, carbonates of Group 1 of the periodic table are preferred, and among these, sodium carbonate and potassium carbonate are preferred.

[0140] In the hydrolysis, it is preferable to mix and stir only the above-mentioned aqueous alkaline solution of moderate strength and the 2-allyloxymethyl acrylate without using an organic solvent. The 2-allyloxymethyl acrylate to be used is preferably methyl 2-allyloxymethylacrylate or ethyl 2-allyloxymethylacrylate.

[0141] The concentration of the aqueous carbonate solution is preferably 5 to 30% by mass, more preferably 7 to 25% by mass, and more preferably 9 to 20% by mass.

[0142] The reaction temperature is preferably 50 to 100°C, more preferably 60 to 95°C, and even more preferably 65 to 90°C.

[0143] It is preferable to hydrolyze substantially all of the raw material 2-allyloxymethyl acrylate, and the molar ratio of carbonate / 2-allyloxymethyl acrylate used for this purpose is preferably 0.8 to 2.0, more preferably 0.9 to 1.6, and even more preferably 0.95 to 1.2.

[0144] (3) Partial hydrolysis of 2-allyloxymethyl acrylate The Michael addition can also be suppressed by partially hydrolyzing the 2-allyloxymethyl acrylate ester instead of completely hydrolyzing it.

[0145] The consumption rate of the raw material 2-allyloxymethyl acrylic acid ester is preferably 10 to 80%, more preferably 20 to 70%, and even more preferably 30 to 60%.

[0146] In the hydrolysis, it is preferable to mix and stir only the aqueous solution of inorganic alkali and the 2-allyloxymethyl acrylic acid ester without using an organic solvent. The inorganic alkali used is preferably the aforementioned strong alkali or medium alkali. The 2-allyloxymethyl acrylic acid ester used is preferably methyl 2-allyloxymethyl acrylate or ethyl 2-allyloxymethyl acrylate.

[0147] The amount of inorganic alkali used is preferably 0.1 to 0.8, more preferably 0.2 to 0.7, and even more preferably 0.3 to 0.6, in terms of the molar ratio of inorganic alkali / 2-allyloxymethyl acrylic acid ester.

[0148] The concentration of the aqueous inorganic alkali solution can be a high concentration aqueous solution even if the alkali used is a strong alkali, and is preferably 5 to 30 mass %, more preferably 7 to 25 mass %, and more preferably 9 to 20 mass %.

[0149] The reaction temperature may be set depending on the type of alkali used, and in the case of a strong alkali, it is preferably 0 to 60°C, more preferably 0 to 50°C, even more preferably 0 to 40°C, and most preferably 0 to 35°C. In the case of a medium-strength alkali, it is preferably 50 to 100°C, more preferably 60 to 95°C, and even more preferably 65 to 90°C.

[0150] When 2-allyloxymethyl acrylate is hydrolyzed, particularly when the reaction is carried out under heat or reduced pressure, polymers may be generated through a radical polymerization mechanism. One way to prevent this is to carry out the hydrolysis in the presence of the aforementioned primary antioxidant and / or secondary antioxidant. Phenols are preferred among primary antioxidants, and thioethers are preferred among secondary antioxidants, as they are more likely to exhibit polymerization-inhibiting effects even under hydrolysis conditions and are less likely to cause coloration.

[0151] <Purification process after hydrolysis> The purification treatment after hydrolysis is preferably carried out after converting all carboxylates present in the reaction system into carboxylic acids by treatment with a strong acid, or after the metathesis treatment described below. Specific reduction procedures include distillation and removal of the aqueous layer containing the β-hydroxycarboxylic acid compound (B) (water washing treatment). Water washing treatment is preferred from the viewpoint of suppressing the generation of polymers due to the radical polymerization mechanism.

[0152] <Strong acid treatment and water washing treatment> The strong acid treatment is a treatment in which a carboxylate salt is carboxylated by adding an acid having a stronger acid strength than the carboxylic acid. Examples of such acids include, but are not limited to, inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid; and organic acids such as methanesulfonic acid, p-toluenesulfonic acid, and trifluoroacetic acid. From the viewpoints of the solubility of the salt produced by the strong acid treatment in water and ease of wastewater treatment, hydrochloric acid and sulfuric acid are preferred. The equivalence relationship between the strong acid and the carboxylic acid salt may be either an excess or an equivalent amount, and may be appropriately selected depending on the purpose.

[0153] When treated with a strong acid, 2-allyloxymethylacrylic acid is generated in an amount proportional to the amount of strong acid added. However, even when treated at low temperatures in the presence of a radical polymerization inhibitor, polymers may still form. This is thought to be because the strong acid acts as an initiator or catalyst, causing the 2-allyloxymethylacrylic acid to polymerize via a cationic polymerization mechanism. Methods for suppressing the formation of such polymers include, for example, reducing the concentration of the strong acid added or adding the strong acid slowly over time.

[0154] Furthermore, 2-allyloxymethylacrylic acid itself is relatively lipophilic, and when mixed with water it separates into two layers. Therefore, strong acid treatment often results in separation into two layers: an organic layer containing primarily 2-allyloxymethylacrylic acid and an aqueous layer containing primarily a salt of the strong acid. Furthermore, since many β-hydroxycarboxylic acid compounds (B) are miscible with water, the β-hydroxycarboxylic acid compound (B) can be reduced by separating the organic layer containing primarily 2-allyloxymethylacrylic acid and the aqueous layer, and then removing the aqueous layer. This corresponds to the water washing treatment mentioned above. From the viewpoint of efficient two-layer separation, it is preferable to use an organic liquid that separates into two layers together with water, which may be added before, simultaneously with, or after the addition of the strong acid. Such an organic liquid may be an organic solvent or a radical polymerizable compound (C) that separates into two layers together with water, and the amount used may be appropriately selected depending on the purpose.

[0155] The water washing treatment may be repeated. That is, washing water is added to the extracted organic layer containing 2-allyloxymethylacrylic acid, and the mixture is stirred, then allowed to stand to separate into two layers, and the aqueous layer is discarded, thereby removing a larger amount of the β-hydroxycarboxylic acid compound (B). The washing water may consist of water alone, or may contain additives. Examples of additives include, but are not limited to, water-soluble inorganic salts (sodium sulfate, potassium sulfate, sodium chloride, potassium chloride, etc.) for increasing the specific gravity of the aqueous layer. Such water washing treatment may be performed two or more times.

[0156] <Metalysis treatment and water washing treatment> Metathesis treatment involves adding a strong acid salt of another metal species to an aqueous solution of a salt of 2-allyloxymethylacrylic acid to perform cation exchange. The aqueous solution of the salt of 2-allyloxymethylacrylic acid before metathesis treatment is preferably an aqueous solution of an alkali metal salt, with sodium or potassium salts being particularly preferred. From the perspective of efficient cation exchange, the strong acid salt of the metal species to be added is preferably an inorganic salt of a polyvalent ion of a metal or metal oxide and a strong inorganic acid. Examples of metals or metal oxides that constitute such inorganic salts include metals or metal oxides belonging to Groups 2 to 15 of the periodic table. From the perspective of achieving colorlessness, metals or metal oxides belonging to Groups 2, 3, 4, 12, 13, 14, and 15 of the periodic table are preferred. Taking into account toxicity and availability, magnesium, calcium, zirconium oxide, zinc, and aluminum are preferred. Examples of strong acids that constitute inorganic salts include hydrochloric acid, sulfuric acid, and nitric acid.

[0157] Salts of 2-allyloxymethylacrylic acid with metals or metal oxides belonging to Groups 2 to 15 of the periodic table are relatively lipophilic, and if an organic liquid that separates into two layers from water is added in advance, separation into two layers is often achieved: an organic layer mainly containing salts of 2-allyloxymethylacrylic acid with metals or metal oxides belonging to Groups 2 to 15 of the periodic table, and an aqueous layer mainly containing alkali metal salts of strong acids. Furthermore, since many β-hydroxycarboxylic acid compounds (B) are miscible with water, the β-hydroxycarboxylic acid compound (B) can be reduced by separating the organic layer mainly containing salts of 2-allyloxymethylacrylic acid with metals or metal oxides belonging to Groups 2 to 15 of the periodic table and the aqueous layer, and then removing the aqueous layer. This corresponds to the water washing treatment described above.

[0158] The organic liquid that separates into two layers from water may be any organic solvent that separates into two layers from water or a radical polymerizable compound (C), and the amount used may be selected appropriately depending on the purpose. For example, if styrene is added to an aqueous solution of sodium 2-allyloxymethylacrylate and then zinc sulfate is added to the solution, a styrene solution containing mainly zinc 2-allyloxymethylacrylate as the cyclopolymerizable carboxylic acid compound (A) is obtained.

[0159] The water washing treatment may be repeated. That is, washing water is further added to the extracted organic layer containing a salt of a metal or metal oxide belonging to Groups 2 to 15 of the periodic table and 2-allyloxymethylacrylic acid, and the mixture is stirred and then allowed to stand to separate into two layers. The aqueous layer is then discarded, thereby enabling a greater reduction in the amount of β-hydroxycarboxylic acid compound (B). The washing water may consist of water alone, or may contain additives. Examples of additives include, but are not limited to, water-soluble inorganic salts (sodium sulfate, potassium sulfate, sodium chloride, potassium chloride, etc.) used to increase the specific gravity of the aqueous layer. Such water washing treatment may be performed two or more times.

[0160] <Removal of water and organic solvents> Depending on the purpose, water and / or the organic solvent may be distilled off from a mixture containing the cyclopolymerizable carboxylic acid compound (A) and water and / or an organic solvent by heating and / or reducing the pressure. In this case, polymers may be generated through a radical polymerization mechanism. One way to suppress this is to add the aforementioned primary antioxidants and / or secondary antioxidants. Phenols are preferred among primary antioxidants, and thioethers are preferred among secondary antioxidants, as they are more likely to exhibit polymerization inhibition effects even in aqueous systems and are less likely to cause coloration.

[0161] When water or solvent is distilled off from a mixture containing a large amount of 2-allyloxymethylacrylic acid, polymers may be generated even if a radical polymerization inhibitor is added. This is believed to be due to a cationic polymerization mechanism. A preferred method for suppressing the generation of such polymers is to allow a carboxylate to coexist, with 2-allyloxymethylacrylic acid salt being particularly preferred. The amount of carboxylate added is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more, relative to the 2-allyloxymethylacrylic acid.

[0162] <Removal of polymers> Polymers may be generated in various processes and operations. Polymers containing a large amount of carboxylate-type structures are water-soluble, but those containing a large amount of carboxylic acid-type structures tend to be poorly soluble in water and in organic solvents other than alcohols. Therefore, the generated polymers can be removed by filtering or centrifuging the polymers to a state where they contain a large amount of carboxylic acid-type structures. Filtration is preferred because it can be performed using a simple device, and the use of a filter aid or adsorbent can improve work efficiency.

[0163] The present disclosure also relates to a polymer obtained by polymerizing the polymerizable composition of the present disclosure under radical-generating conditions.

[0164] Examples of radical generation methods include heating the polymerizable composition of the present disclosure and / or irradiating the polymerizable composition of the present disclosure with active energy rays. Heating or irradiating with active energy rays may be performed in one step or in two or more separate steps. Heating and irradiating with active energy rays may be combined, may be performed simultaneously, or may be performed separately. When heating or irradiating with active energy rays, it is more preferable that the polymerizable composition of the present disclosure contains the above-mentioned radical polymerization initiator.

[0165] The heating temperature may be appropriately selected depending on the presence or absence, type, content, and application of a radical polymerization initiator. When a thermal radical initiator is used, the heating temperature is 40°C or higher, more preferably 50°C or higher, and even more preferably 60°C or higher.

[0166] The active energy rays can be those that are commonly used, including electromagnetic waves such as gamma rays, X-rays, ultraviolet rays, visible light, and infrared rays, and particle rays such as electron beams, neutron beams, and proton beams. Among these, in terms of energy intensity, energy ray generator, etc., gamma rays, X-rays, ultraviolet rays, visible light, and electron beams are preferred, ultraviolet rays, visible light, and electron beams are more preferred, and ultraviolet rays are most preferred. When a photoradical initiator is not used, it is preferable to use active energy rays with high energy such as gamma rays, X-rays, and electron beams, and when a photoradical initiator is used, it is preferable to use active energy rays such as ultraviolet rays and visible light, which have relatively low energy but are easy to generate and economical.

[0167] <Uses of the polymerizable composition of the present disclosure> As described above, the polymerizable composition of the present disclosure has good radical polymerizability, and therefore can be suitably used in a variety of applications that undergo radical polymerization by heating or irradiation with active energy rays, such as coating materials, adhesives, sealants, pressure-sensitive adhesives, primers, paints, inks, resists, dental materials, lenses, molding materials, various types of three-dimensional modeling (inkjet, SLA, DLP), intermediate layers in optical films, resins for negative resists, water-absorbent resins, compositions for quantum dot inks, compositions for EUV resists, materials for electronic components (prepregs, pressure-sensitive adhesives for electrical materials, adhesives for electrical materials, etc.), fiber treatment agents, and compositions for surface treatment agents. [Example]

[0168] The present disclosure will be described in more detail below with reference to examples, but the present disclosure is not limited to these examples. Unless otherwise specified, "parts" means "parts by mass" and "%" means "% by mass."

[0169] <Measurement of carboxylate ions> Measuring equipment Capillary electrophoresis system Agilent 7100 (Agilent Technologies, Inc.) Measurement conditions The measurement was carried out by the indirect absorption method using a background absorber. Capillary: Bubble self-fused silica capillary (inner diameter 75 μm x total length 80.5 cm) Running buffer: Running buffer for anion analysis (pH = 8.2) Applied voltage: -20kV ○Quantitative method Quantitation was carried out by the internal standard method based on the area ratio (internal standard: sodium propionate). Preparation of standard sample: Dissolve sodium propionate and the substance to be quantified (sodium salt of carboxylic acid ion) in heavy water. 1 The molar ratio was determined by H-NMR, and then the solution was diluted with ultrapure water to prepare a standard sample for creating a calibration curve. Preparation of measurement samples: The sodium propionate aqueous solution and the test sample were weighed and diluted with 1% sodium bicarbonate aqueous solution and ultrapure water to prepare measurement samples.

[0170] <Metal ion measurement> Measuring equipment Capillary electrophoresis system Agilent 7100 (Agilent Technologies, Inc.) Measurement conditions The measurement was carried out by the indirect absorption method using a background absorber. Capillary: Standard fused silica capillary (inner diameter 75 μm x total length 80.5 cm) Running buffer: Running buffer for cation analysis (pH = 3.9) Applied voltage: 20 kV ○Quantitative method Quantitation was carried out by the internal standard method (internal standard: magnesium sulfate) based on the area ratio. Preparation of standard samples: Magnesium sulfate, sodium sulfate, and zinc sulfate heptahydrate were diluted with ultrapure water to prepare standard samples for preparing a calibration curve. Preparation of measurement samples: Magnesium sulfate and the test sample were weighed and diluted with 1.0% sulfuric acid and ultrapure water to prepare measurement samples.

[0171] <Molecular weight measurement> Measuring equipment ACQUITY APC (Advanced Polymer Chromatography) System (Nihon Waters Co., Ltd.) Measurement conditions Separation columns: ACQUITY APC XT columns, 450Å pore size x 1, 125Å pore size x 1, 45Å pore size x 1 Elution solvent: tetrahydrofuran / methanol = 2 / 1 (weight ratio) mixture, phosphoric acid concentration 1.0% Molecular weight standard: Polymethyl methacrylate

[0172] <Preparation of Polymerizable Composition> [Example 1] A 50 ml recovery flask containing a stirrer was charged with 5.0 g of methyl 2-allyloxymethylacrylate (containing 0.03% p-methoxyphenol and 0.06% dimethyl 3,3'-thiodipropionate) and 32.0 g of 4% aqueous sodium hydroxide (equivalent to the amount of methyl 2-allyloxymethylacrylate used) and stirred at room temperature for 1 hour. The flask was heated while bubbling oxygen / nitrogen gas (oxygen concentration 7%). Once the internal temperature reached 60°C, the pressure was gradually reduced to distill off water and low-boiling components. When the distillate reached 19.2 g, the pressure was released and the flask was cooled to room temperature. While cooling with water, 1.6 g of sulfuric acid (equivalent to the amount of sodium hydroxide used) was slowly added dropwise, followed by the addition of 4.5 g of styrene. Stirring was continued for an additional 5 minutes, and the organic components were extracted with styrene. The stirring was stopped, and the contents were transferred to a separatory funnel. After standing for 30 minutes, the aqueous layer (lower layer) was discarded, and 9.0 g of the organic layer was removed to obtain a polymerizable composition (1) of the present disclosure (a styrene solution containing 2-allyloxymethylacrylic acid). The polymerizable composition was analyzed by a capillary electrophoresis system to measure the amounts of the partial structure (1) and the partial structures (2) to (4) as carboxylate ions. The results are shown in Table 1.

[0173] [Comparative Example 1] A 50 ml recovery flask equipped with a stirrer was charged with 5.0 g of methyl 2-allyloxymethylacrylate (containing 0.03% p-methoxyphenol and 0.06% dimethyl 3,3'-thiodipropionate) and 6.4 g of 20% aqueous sodium hydroxide (equivalent to the amount of methyl 2-allyloxymethylacrylate used). The mixture was stirred at room temperature for 1 hour. 6.4 g of ultrapure water was added, and then 1.6 g of sulfuric acid (equivalent to the amount of sodium hydroxide used) was slowly added dropwise while cooling with water. 4.5 g of styrene was then added and stirring was continued for another 5 minutes to extract the organic matter with styrene. The stirring was stopped, and the contents were transferred to a separatory funnel. After allowing to stand for 30 minutes, the aqueous layer (lower layer) was discarded, and 9.0 g of the organic layer was removed to obtain comparative polymerizable composition (1) (a styrene solution containing 2-allyloxymethylacrylic acid). The polymerizable composition was analyzed by a capillary electrophoresis system to measure the amounts of the partial structure (1) and the partial structures (2) to (4) as carboxylate ions. The results are shown in Table 1.

[0174] Comparative Example 2 A 50 ml recovery flask equipped with a stirrer was charged with 5.0 g of methyl 2-allyloxymethylacrylate (containing 0.03% p-methoxyphenol and 0.06% dimethyl 3,3'-thiodipropionate) and 12.8 g of 10% aqueous sodium hydroxide (equivalent to the amount of methyl 2-allyloxymethylacrylate used). The mixture was stirred at room temperature for 1 hour. While cooling with water, 1.6 g of sulfuric acid (equivalent to the amount of sodium hydroxide used) was slowly added dropwise, followed by the addition of 4.5 g of styrene. Stirring was continued for an additional 5 minutes, and the organic fraction was extracted with styrene. The stirring was stopped, and the contents were transferred to a separatory funnel. After allowing to stand for 30 minutes, the aqueous layer (lower layer) was discarded, and 9.0 g of the organic layer was removed to obtain comparative polymerizable composition (2) (a styrene solution containing 2-allyloxymethylacrylic acid). The polymerizable composition was analyzed using a capillary electrophoresis system to measure the amounts of the partial structure (1) (a1) and the partial structures (2) to (4) (b1 to b6) as carboxylate ions. The results are shown in Table 1.

[0175] [Example 2] A 100 ml recovery flask was equipped with a stirrer and connected to a condenser and distillate receiver via a thermometer, gas inlet, and a side tube. The recovery flask was charged with 2.9 g of potassium hydroxide, 7.1 g of potassium carbonate, and 60.0 g of ultrapure water, and stirred to form a homogeneous solution. 20.0 g of methyl 2-allyloxymethylacrylate (containing 0.03% p-methoxyphenol and 0.06% dimethyl 3,3'-thiodipropionate) was then added to the recovery flask. The recovery flask was then connected to a vacuum line, and the pressure was reduced to 60 kPa while bubbling an oxygen / nitrogen mixed gas (oxygen concentration 7%). After reaching 60 kPa, heating was initiated and the internal temperature was adjusted to maintain a temperature of 66–69°C. After 4 hours, the pressure was released and the flask was cooled to room temperature. 10.8 g of 15% aqueous potassium hydroxide solution was added, and the pressure was reduced to 60 kPa again. After the pressure reached 60 kPa, heating was initiated and the heating was adjusted to maintain the internal temperature at 66-69°C. Four hours after the internal temperature reached 66°C, the pressure was gradually reduced to 20 kPa, and water and low-boiling fractions were distilled off. After the total distillate reached 30 g, the pressure was released and the contents were cooled to room temperature. 20.0 g of diisopropyl ether was added, and 9.0 g of sulfuric acid was slowly added dropwise while cooling with water. The stirring was stopped, and the contents were transferred to a separatory funnel. After standing for 30 minutes, the aqueous layer (lower layer) was discarded. 20 g of 5% potassium sulfate aqueous solution was added to the separatory funnel, followed by shaking and mixing. After standing for 30 minutes, the aqueous layer (lower layer) was discarded. 20 g of ultrapure water was added to the separatory funnel, followed by shaking and mixing. After standing for 30 minutes, the aqueous layer (lower layer) was discarded, and the organic layer was transferred to a recovery flask. The recovery flask was connected to a vacuum line, and the pressure was reduced while stirring, and the diisopropyl ether was distilled off. After silica gel was spread on a filter paper, the residual liquid after distillation was filtered under suction. 3.0 g of the filtrate was mixed with 3.0 g of methyl acrylate to obtain a polymerizable composition (2) (a methyl acrylate solution containing 2-allyloxymethylacrylic acid) of the present disclosure. The polymerizable composition was analyzed by a capillary electrophoresis system to measure the amounts of the partial structure (1) and the partial structures (2) to (4) as carboxylate ions. The results are shown in Table 1.

[0176] [Example 3] A 50 ml recovery flask containing a stirrer was charged with 5.0 g of methyl 2-allyloxymethylacrylate (containing 0.03% p-methoxyphenol and 0.06% dimethyl 3,3'-thiodipropionate) and 32.0 g of 4% aqueous sodium hydroxide (equivalent to the amount of 2-allyloxymethylacrylate used). The mixture was stirred at room temperature for 1 hour. The mixture was heated while bubbling oxygen / nitrogen gas (7% oxygen concentration). Once the internal temperature reached 60°C, the pressure was gradually reduced to distill off water and low-boiling fractions. After the distillate reached 19.2 g, the pressure was released and the mixture was cooled to room temperature. 10.0 g of diisopropyl ether was added, and 1.6 g of sulfuric acid (equivalent to the amount of sodium hydroxide used) was slowly added dropwise while cooling with water. The stirring was stopped, the contents were transferred to a separatory funnel, and after 30 minutes of settling, the aqueous layer (lower layer) was discarded and the organic layer was transferred to the recovery flask. The recovery flask was connected to a vacuum line, and the pressure was reduced while stirring to distill off the diisopropyl ether. Silica gel was placed on filter paper, and the remaining liquid after distillation was filtered under suction. 3.0 g of the filtrate was mixed with 3.0 g of methyl acrylate to obtain polymerizable composition (3) of the present disclosure (a methyl acrylate solution containing 2-allyloxymethylacrylic acid). The polymerizable composition was analyzed by a capillary electrophoresis system to measure the amounts of the partial structure (1) and the partial structures (2) to (4) as carboxylate ions. The results are shown in Table 1.

[0177] Comparative Example 3 A 50 ml recovery flask containing a stirrer was charged with 5.0 g of methyl 2-allyloxymethylacrylate (containing 0.03% p-methoxyphenol and 0.06% dimethyl 3,3'-thiodipropionate) and 6.4 g of 20% aqueous sodium hydroxide (equivalent to the amount of methyl 2-allyloxymethylacrylate used). The mixture was stirred at room temperature for 1 hour. 6.4 g of ultrapure water and 10.0 g of diisopropyl ether were then added, followed by the slow dropwise addition of 1.6 g of sulfuric acid (equivalent to the amount of sodium hydroxide used) while cooling with water. The stirring was stopped, and the contents were transferred to a separatory funnel. After allowing to stand for 30 minutes, the aqueous layer (lower layer) was discarded, and the organic layer was transferred to the recovery flask. The recovery flask was connected to a vacuum line and the pressure was reduced while stirring, allowing the diisopropyl ether to be distilled off. Silica gel was placed on a filter paper, and the remaining liquid after distillation was filtered under suction. A 3.0 g portion of the filtrate was mixed with 3.0 g of methyl acrylate to obtain a comparative polymerizable composition (3) (a methyl acrylate solution containing 2-allyloxymethylacrylic acid). The polymerizable composition was analyzed using a capillary electrophoresis system to measure the amounts of partial structure (1) and partial structures (2) to (4) as carboxylate ions. The results are shown in Table 1, and the electropherogram is shown in Figure 1.

[0178] [Example 4] A 50 ml recovery flask equipped with a stirrer was charged with 5.0 g of methyl 2-allyloxymethylacrylate (containing 0.03% p-methoxyphenol and 0.06% dimethyl 3,3'-thiodipropionate) and 6.4 g of 10% aqueous sodium hydroxide (0.5 equivalents relative to the amount of methyl 2-allyloxymethylacrylate used). The mixture was stirred at room temperature for 1 hour. 2.3 g of zinc sulfate heptahydrate was added and the mixture was stirred for 30 minutes. After stirring, the mixture was stopped and the contents were transferred to a separatory funnel and allowed to stand for 30 minutes. The aqueous layer (lower layer) was discarded, and 5.0 g of the organic layer was removed to obtain polymerizable composition (4) of the present disclosure (a methyl 2-allyloxymethylacrylate solution containing zinc 2-allyloxymethylacrylate and sodium 2-allyloxymethylacrylate). The polymerizable composition was analyzed using a capillary electrophoresis system to measure the amounts of partial structure (1) and partial structures (2) to (4) as carboxylate ions. Zinc and sodium were also quantified. The results are shown in Table 1.

[0179] [Table 1]

[0180] [ka]

[0181] <Radical polymerization of polymerizable composition> [Example 5] A 50 ml test tube containing a stirrer was charged with 4.0 g of the polymerizable composition (2) obtained in Example 2, 6.0 g of ethanol, and 0.04 g of 2,2'-azobis(2,4-dimethylvaleronitrile), and heating was initiated with stirring. Stirring was continued for 4 hours while adjusting the heating so that the internal temperature remained at 66°C ± 1°C, followed by cooling to room temperature. The contents were mixed with 30 g of tetrahydrofuran and then added dropwise to 100 g of n-hexane with stirring. Stirring was continued for 30 minutes, and the precipitate was removed by decantation. The precipitate was placed in a 50 ml recovery flask (pre-weighed) and vacuum-dried at 80°C for 1 hour to obtain a polymer. The weight of the resulting polymer, including the recovery flask, was precisely weighed, and the yield of the polymer relative to the weight of the polymerizable composition added was calculated to be 95.9%. The weight-average molecular weight of the polymer purified by pre-precipitation using an APC system was measured to be 50,000.

[0182] [Example 6] A polymer was obtained in the same manner as in Example 5, except that the polymerizable composition obtained in Example 3 was used as the polymerizable composition. The yield was 92.9%, and the weight-average molecular weight was 46,000.

[0183] Comparative Example 4 A polymer was obtained in the same manner as in Example 5, except that the polymerizable composition obtained in Comparative Example 3 was used as the polymerizable composition. The yield was 75.9%, and the weight-average molecular weight was 32,000. Both the yield and the molecular weight were lower than those in Examples 5 and 6.

[0184] [Example 7] 3.0 g of the polymerizable composition obtained in Example 4, 0.09 g of 1-hydroxycyclohexyl phenyl ketone, and 0.09 g of 1-[4-(2-hydroxyethoxyl)-phenyl]-2-hydroxymethylpropanone were mixed and stirred to obtain a homogeneous solution. Using a bar coater No. 2, the obtained solution was applied to a cycloolefin polymer film (ZEONOR (registered trademark) 1410R / manufactured by Nippon Zeon Co., Ltd., which was formed into a 100 μm thick film using a small press), and then the applied solution was applied to a belt conveyor-type UV irradiation device (illuminance 200 mW / cm). 2 , cumulative light intensity 400mJ / cm 2 ) was used for polymerization. The adhesion of the polymer layer was evaluated in accordance with JIS K 5600-5-6 (cross-cut method). That is, the number of squares remaining without peeling or damage out of all squares (10 × 10 squares = 100 squares) was evaluated, and the result was 100.

[0185] [Example 8] An isobornyl acrylate solution containing 2-allyloxymethylacrylic acid was prepared in the same manner as in Example 3, except that 8.0 g of isobornyl acrylate was used instead of 3.0 g of methyl acrylate. Next, 0.86 g of zinc oxide powder was added and the mixture was stirred at 60°C for approximately 3 hours until transparent. After confirming that the mixture had become transparent, 1.56 g of N,N'-bis(2-hydroxyethyl)ethylenediamine was added and the mixture was stirred for approximately 30 minutes until transparent, yielding an isobornyl acrylate solution of 2-allyloxymethylacrylic acid, in which 50 mol% of the 2-allyloxymethylacrylic acid was neutralized with zinc and 50 mol% with N,N'-bis(2-hydroxyethyl)ethylenediamine. After allowing the mixture to cool to room temperature, 0.4 g of 1-hydroxycyclohexyl phenyl ketone was added and the mixture was stirred to obtain a uniform solution, which was used as a UV-curable composition. This polymerizable composition was analyzed using a capillary electrophoresis system, and the amounts of partial structure (1) and partial structures (2) to (4) were measured as carboxylate ions. The molar ratios of the partial structures (a1, b1 to b6) were the same as in Example 3.

[0186] Two glass plates (15 cm x 7 cm) with 2 mm thick polypropylene plates attached were placed facing each other with the polypropylene plates facing inwards, and a 0.5 mm thick U-shaped silicone sheet was sandwiched between them as a spacer and secured with clips to form a casting mold. The polymerizable composition was then poured into the casting mold using a belt conveyor-type UV irradiation device (high-pressure mercury lamp, illuminance 200 mW / cm). 2 ) belt speed, the cumulative light intensity per pass is 1 J / cm 2After adjusting the temperature to the desired value, one side of the mold into which the polymerizable composition had been poured was irradiated with UV light from above, then the mold was turned upside down and irradiated with UV light again. The plate and silicone sheet were removed, and the resulting very hard sheet, approximately 13 cm x 5 cm x 0.5 mm thick, was punched into a dumbbell-shaped No. 3 shape using a heated sample cutter at a heating temperature of 110°C. Using a tensile tester equipped with an oven, the specimen was stretched at a gripper distance of 60 mm, a pulling rate of 60 mm / min, and an oven temperature of 150°C. The tension was stopped when the specimen reached 100% elongation (i.e., 2x stretch), the oven was removed, and the specimen was returned to room temperature and then removed from the gripper. The resulting specimen was solidified at 100% elongation and was transparent.

[0187] The results in Table 1 reveal that the polymerizable composition of the present invention is hydrophilic, water-soluble, and has a reduced content of β-hydroxycarboxylic acid compound (B) having partial structures (2) to (4) that have an adverse effect on radical polymerization.

[0188] Furthermore, the results of Examples 5 and 6 revealed that the polymerizable composition of the present disclosure has better solution radical polymerizability than a polymerizable composition containing a large amount of the β-hydroxycarboxylic acid compound (B) having the partial structures (2) to (4). Furthermore, the results of Examples 7 and 8 revealed that the polymerizable composition of the present disclosure has better UV curability.

Claims

1. The following formula (1): 【Chemical 1】 a cyclopolymerizable carboxylic acid and / or a salt thereof (A) having a partial structure represented by the following formula: The following formulas (2) to (4): 【Chemistry 2】 (wherein R and R' each independently represent a hydrogen atom or a saturated hydrocarbon group having 4 or less carbon atoms), and / or a salt thereof (B), a polymerizable composition comprising (A) the cyclopolymerizable carboxylic acid and / or its salt and (C) a radical polymerizable compound other than (B) the β-hydroxycarboxylic acid and / or its salt, A polymerizable composition, wherein the molar ratio of the partial structure represented by any one of formulas (2) to (4) that is contained in the polymerizable composition in the largest molar amount is 1.5 or less relative to 100 molar amounts of the partial structure represented by formula (1).

2. 2. The polymerizable composition according to claim 1, wherein the radical polymerizable compound (C) is one or more compounds selected from the group consisting of compounds having a (meth)acryloyl group, compounds having a 2-(meth)allyloxymethylacryloyl group other than the cyclopolymerizable carboxylic acid and / or salt thereof (A), N-vinyl amides, (meth)acrylonitrile, aromatic vinyls, vinyl ethers, and vinyl esters.

3. 3. The polymerizable composition according to claim 1, wherein R and R' in the formulas (2) to (4) each independently represent a hydrogen atom, a methyl group, or an ethyl group.

4. 3. The polymerizable composition according to claim 1, wherein the total molar amount of the partial structures represented by any one of formulas (2) to (4) is 4 or less per 100 molar amount of the partial structure represented by formula (1).

5. A polymer obtained by polymerizing the polymerizable composition according to claim 1 or 2 under radical-generating conditions.

Images