Overlapping components

Abstract

The present invention provides a polymerizable composition which can be avoided from the generation of a polymerization product during the process for the production thereof and the like and which contains a 2-oxymethylacrylic acid. The present invention relates to a polymerizable composition comprising a 2-oxymethylacrylic acid (A) represented by formula (1) (wherein R represents a hydrogen atom or a saturated or unsaturated hydrocarbon group having 10 or less carbon atoms) and a carboxylic acid salt and / or water, the polymerizable composition being characterized by satisfying at least one of a requirement that the cation content ratio represented by calculation formula (I) is 0.01 or more and less than 1 and a requirement that the water content ratio represented by calculation formula (II) is 0.01 or more. (In the calculation formula (I), the total number of valencies of cations derived from the carboxylic acid salt is a total of [(the number of valencies of the cations derived from the carboxylic acid salt)×(the number of moles of the cations)]; and the total amount of 2-oxymethylacrylic acid moieties is a total of the number of moles of the 2-oxymethylacrylic acid (A) and the number of moles of 2-oxymethylacrylic acid ions derived from the 2-oxymethylacrylic acid (A).)

Description

[Technical Field]

[0001] The present invention relates to polymerizable compositions with improved stability. [Background technology]

[0002] It is known that α-substituted methyl acrylate esters undergo radical polymerization, and although the polymerization rate is slow, the termination rate is also low, so that polymers with a high degree of polymerization can sometimes be obtained (e.g., Non-Patent Document 1, Non-Patent Document 2). α-Allyloxymethyl acrylate esters, which have an α-substituted methyl acrylate ester type structure, are known to have cyclopolymerization properties and to exhibit radical polymerization activity similar to that of acrylate esters (e.g., Non-Patent Document 3, Patent Document 1). Furthermore, a method for inhibiting the radical polymerization of α-allyloxymethyl acrylate esters and improving their high-temperature stability and storage stability has also been disclosed (e.g., Patent Document 2). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2011-137123 [Patent Document 2] Japanese Patent Application Laid-Open No. 2014-31510 [Non-patent literature]

[0004] [Non-Patent Document 1] B. Yamada and S. Kobatake, Prog. Polym. Sci., 119, 1089 (1994) [Non-patent document 2] Yamada Bunichiro, Adhesion Technology, 14, 1 (1995) [Non-patent document 3] Michio Urushizaki, Toshiyuki Kodaira, Takeji Furuta, Yutaka Yamada, Shoji Oshitani, Macromolecules, 1999, Vol. 32, pp. 322-327 Summary of the Invention [Problem to be solved by the invention]

[0005] Although there are many cases in which the polymerizability of α-substituted methylacrylic acid esters has been investigated, there are few cases in which the polymerizability of α-substituted methylacrylic acid has been investigated. In particular, it was not known that when 2-hydroxymethylacrylic acid or 2-alkoxymethylacrylic acid (hereinafter, these may be simply referred to as 2-oxymethylacrylic acid) is handled, for example, during production, storage, transportation, composition preparation operations, etc., polymerization products are likely to be generated.

[0006] Therefore, an object of the present invention is to provide a polymerizable composition containing 2-oxymethylacrylic acid that can suppress the generation of polymerization products during the production process or the like. [Means for solving the problem]

[0007] The present inventors conducted extensive research to achieve the above-mentioned object and discovered that 2-oxymethylacrylic acid is prone to producing undesired polymerization products through a reaction believed to be cationic polymerization, and that this polymerization reaction does not occur with 2-oxymethylacrylic acid esters or 2-oxymethylacrylic acid salts, but is a reaction specific to 2-oxymethylacrylic acid. They then discovered that the production of the above-mentioned polymerization products can be effectively suppressed by preparing a composition in which 2-oxymethylacrylic acid is mixed with a carboxylate salt acting as a base or water so as to achieve a predetermined range of cation ratio or water ratio, thereby arriving at the present invention. Specifically, the present invention is described in the following items [1] to [8]. [1] Formula (1):

[0008] [ka]

[0009] (In the formula, R represents a hydrogen atom or a saturated or unsaturated hydrocarbon group having 10 or less carbon atoms.) A polymerizable composition comprising 2-oxymethylacrylic acid (A) represented by the formula: and a carboxylate and / or water, A polymerizable composition characterized by satisfying at least one of the following: a cation ratio represented by the following formula (I) being 0.01 or more and less than 1; or a water ratio represented by the following formula (II) being 0.01 or more.

[0010]

number

[0011] (In formula (I), the total valence of cations derived from carboxylate salts is the sum of [valence of cations derived from carboxylate salts × number of moles of cations]. The total amount of 2-oxymethylacrylic acid moieties is the sum of the number of moles of 2-oxymethylacrylic acid (A) and the number of moles of 2-oxymethylacrylic acid ions derived from 2-oxymethylacrylic acid (A).)

[0012]

number

[0013] [2] The polymerizable composition according to [1] above, wherein the cation derived from the carboxylate salt contains one or more cations selected from the group consisting of metal ions, metal oxide ions, and cations containing a non-metal atom of Group 15 of the periodic table. [3] The polymerizable composition according to [1] or [2] above, wherein the carboxylate salt comprises one or more carboxylate salts selected from the group consisting of salts of 2-oxymethylacrylic acid (A), salts of acrylic acid, and salts of methacrylic acid. [4] The polymerizable composition according to any one of [1] to [3] above, wherein the amount of 2-oxymethylacrylic acid ions contained in the carboxylate is 50 mol % or more and 100 mol % or less based on the total amount of carboxylate ions contained in the carboxylate. [5] The polymerizable composition according to any one of the above [1] to [4], wherein R in the general formula (1) is an allyl group or a methallyl group. [6] A polymer obtained by polymerizing the polymerizable composition according to any one of the above [1] to [5] under radical-generating conditions. [7] The following formula (1);

[0014] [ka]

[0015] (In the formula, R represents a hydrogen atom or a saturated or unsaturated hydrocarbon group having 10 or less carbon atoms.) A method for storing 2-oxymethylacrylic acid (A) represented by the formula: A method for storing 2-oxymethylacrylic acid (A), comprising storing the 2-oxymethylacrylic acid (A) in the presence of a carboxylate having a cation ratio represented by the following calculation formula (I) of 0.01 or more and less than 1, and / or in the presence of water having a water ratio represented by the following calculation formula (II) of 0.01 or more.

[0016]

number

[0017] (In formula (I), the total valence of cations derived from carboxylate salts is the sum of [valence of cations derived from carboxylate salts × number of moles of cations]. The total amount of 2-oxymethylacrylic acid moieties is the sum of the number of moles of 2-oxymethylacrylic acid (A) and the number of moles of 2-oxymethylacrylic acid ions derived from 2-oxymethylacrylic acid (A).)

[0018]

number

[0019] [ka]

[0020] (In the formula, R represents a hydrogen atom or a saturated or unsaturated hydrocarbon group having 10 or less carbon atoms.) A polymerization material comprising 2-oxymethylacrylic acid (A) represented by the formula: A polymeric material characterized by satisfying at least one of the following: a cation ratio represented by the following formula (I) being 0.01 or more and less than 1; or a water ratio represented by the following formula (II) being 0.01 or more.

[0021]

number

[0022] (In formula (I), the total valence of cations derived from carboxylate salts is the sum of [valence of cations derived from carboxylate salts × number of moles of cations]. The total amount of 2-oxymethylacrylic acid moieties is the sum of the number of moles of 2-oxymethylacrylic acid (A) and the number of moles of 2-oxymethylacrylic acid ions derived from 2-oxymethylacrylic acid (A).)

[0023]

number

[0024] According to the present disclosure, a polymerizable composition containing 2-oxymethylacrylic acid can be provided that exhibits good radical polymerizability during use while suppressing the generation of polymerization products due to reactions thought to be cationic polymerization. The polymerizable composition can be suitably used for various applications, such as a component of a curable composition used in various coatings, adhesives, sealings, and three-dimensional modeling, or as a copolymer raw material. DETAILED DESCRIPTION OF THE INVENTION

[0025] Preferred embodiments of the present disclosure will be specifically described below, but the present disclosure is not limited to the following description and can be appropriately modified and applied within the scope of the present disclosure. A combination of two or more of the preferred embodiments of the present disclosure described below also falls within the scope of the present disclosure. Furthermore, (meth)acrylic means acrylic or methacrylic. (Meth)allyl means allyl or methallyl.

[0026] The present disclosure provides a compound of formula (1):

[0027] [ka]

[0028] (In the formula, R represents a hydrogen atom or a saturated or unsaturated hydrocarbon group having 10 or less carbon atoms.) and a carboxylate and / or water, wherein the polymerizable composition satisfies at least one of the following: a cation ratio represented by the following formula (I) is 0.01 or more and less than 1; or a water ratio represented by the following formula (II) is 0.01 or more.

[0029]

number

[0030] (In formula (I), the total valence of cations derived from carboxylate salts is the sum of [valence of cations derived from carboxylate salts × number of moles of cations]. The total amount of 2-oxymethylacrylic acid moieties is the sum of the number of moles of 2-oxymethylacrylic acid (A) and the number of moles of 2-oxymethylacrylic acid ions derived from 2-oxymethylacrylic acid (A).)

[0031]

number

[0032] The polymerizable composition of the present disclosure, due to the above-described configuration, can suppress the generation of polymerization products and improve the stability of the polymerizable composition.

[0033] The inventors of the present invention have hypothesized that compounds with a structure such as 2-oxymethylacrylic acid (A) represented by the above formula (1) are likely to generate carbocations at the carbon bonded to the RO-CH2 group and carboxyl group due to the high electron-donating properties of the RO-CH2 group. Furthermore, the carboxyl group can also function as a catalyst or initiator for cationic polymerization, making cationic polymerization likely to occur without the addition of compounds typically used as cationic polymerization catalysts or initiators (e.g., sulfonic acid compounds or boron compounds). The inventors also hypothesized that the coexistence of a base would be sufficient to suppress the generation of carbocations or to deactivate any generated carbocations. Carboxylate salts and water can act as weak bases, as they are known to act as anionic polymerization initiators for vinyl compounds (e.g., 2-cyanoacrylates and methylene malonates) that have carbon atoms activated by electron-withdrawing groups. The configurations disclosed herein are believed to be able to suppress the generation of polymers that would otherwise result from the cationic polymerization mechanism of the above-mentioned 2-oxymethylacrylic acid (A). The reason for this is believed to be that the carboxylate salts and water act as bases, and when present in amounts exceeding a certain level, their inhibitory power exceeds the power to initiate and advance cationic polymerization.

[0034] The components constituting the polymerizable composition of the present disclosure will be described. <2-Oxymethylacrylic acid (A)> 2-Oxymethylacrylic acid (A) is represented by the following formula (1);

[0035] [ka]

[0036] (wherein R represents a hydrogen atom or a saturated or unsaturated hydrocarbon group having 10 or less carbon atoms).

[0037] The saturated or unsaturated hydrocarbon group having 10 or less carbon atoms in R may be linear or branched, or may be cyclic.

[0038] Specific examples of R include a hydrogen atom; linear or branched saturated hydrocarbon groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-amyl, sec-amyl, tert-amyl, neopentyl, n-hexyl, sec-hexyl, n-heptyl, n-octyl, sec-octyl, tert-octyl, 2-ethylhexyl, nonyl, and decyl; saturated hydrocarbon groups containing an alicyclic structure such as cyclopentyl, cyclopentylmethyl, cyclohexyl, cyclohexylmethyl, trimethylcyclohexyl, dicyclopentanyl, and isobornyl, and hydrocarbon groups containing an aromatic ring such as phenyl and benzyl; and hydrocarbon groups containing a non-conjugated unsaturated bond such as vinyl, allyl, methallyl, crotyl, butenyl, cyclohexenyl, and dicyclopentenyl; but are not limited to these examples, and two or more types may be combined.

[0039] From the viewpoint of achieving good radical polymerizability, the number of carbon atoms in the saturated or unsaturated hydrocarbon group represented by R is preferably 8 or less, more preferably 6 or less, and even more preferably 4 or less. The saturated or unsaturated hydrocarbon group is preferably a hydrocarbon group containing an unsaturated bond, and most preferably an allyl group or methallyl group, which have cyclopolymerizability and thereby exhibit polymerization activity similar to that of (meth)acrylates.

[0040] The methods for analyzing the content of 2-hydroxymethylacrylic acid (A) include gas chromatography; liquid chromatography based on various separation modes such as partition, adsorption, ion exchange, ion exclusion, size exclusion, and affinity; capillary electrophoresis; 1Spectroscopic techniques such as H-NMR and the like are included, but are not limited to these examples. From the viewpoint of being able to detect 2-oxymethylacrylic acid ions, ion chromatography and capillary electrophoresis are preferred, and from the viewpoint of being able to perform measurement in a short time, 1 H-NMR is preferred, and among these, capillary electrophoresis is preferred from the viewpoints of sensitivity and ease of maintenance of the equipment.

[0041] <Carboxylate> The carboxylate in the polymerizable composition of the present disclosure is not particularly limited as long as it is a compound having a carboxylate structure.

[0042] Specific examples of the carboxylate ion portion of the carboxylate salt include saturated monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, myristic acid, and stearic acid; saturated polycarboxylic acids such as oxalic acid, malonic acid, succinic acid, adipic acid, and cyclohexanetricarboxylic acid; aromatic carboxylic acids such as benzoic acid, phthalic acid, terephthalic acid, and trimellitic acid; carboxylic acids having a double bond conjugated with a carboxyl group, such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, and itaconic acid, which are not the 2-oxymethylacrylic acid (A) of the present disclosure; and 2-oxymethylacrylic acid (A) of the present disclosure, such as 2-hydroxymethylacrylic acid, 2-methoxymethylacrylic acid, 2-allyloxymethylacrylic acid, and 2-methallyloxymethylacrylic acid. However, the carboxylate ion portion of the carboxylate salt may be a combination of two or more types of carboxylate ions.

[0043] From the viewpoint of making the polymerizable composition of the present disclosure a composition with good radical polymerizability, the carboxylate ion portion of the carboxylate salt is preferably a carboxylate ion having a double bond conjugated with a carboxyl group, particularly preferably a carboxylate ion of acrylic acid, methacrylic acid, or the above-mentioned 2-oxymethylacrylic acid (A), with 2-oxymethylacrylic acid ion being more preferred. The carboxylate ion of 2-allyloxymethylacrylic acid or 2-methallyloxymethylacrylic acid is most preferred. Thus, the carboxylate salt preferably contains one or more carboxylate salts selected from the group consisting of salts of 2-oxymethylacrylic acid (A), salts of acrylic acid, and salts of methacrylic acid.

[0044] The amount of carboxylate ions having a double bond conjugated with a carboxyl group contained in the carboxylate salt is preferably 50 mol % or more and 100 mol % or less, more preferably 70 mol % or more and 100 mol % or less, and even more preferably 90 mol % or more and 100 mol % or less, based on the total amount of carboxylate ions in the carboxylate salt. The most preferred embodiment is one in which the amount of 2-oxymethylcarboxylate ions contained in the carboxylate salt is 50 mol % or more and 100 mol % or less, based on the total amount of carboxylate ions in the carboxylate salt.

[0045] The methods for analyzing the content of carboxylate ion moieties in carboxylate salts include 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 and the like are included, but are not limited to these examples. Ion chromatography and capillary electrophoresis are preferred from the viewpoint of being able to detect carboxylate ions, and from the viewpoint of being able to perform measurements in a short time. 1 H-NMR is preferred, and among these, capillary electrophoresis is preferred from the viewpoints of sensitivity and ease of maintenance of the equipment.

[0046] The cation that constitutes the carboxylate together with the carboxylate ion moiety may be an inorganic cation or an organic cation, and may be appropriately selected depending on the purpose and application.

[0047] Examples of inorganic cations include metal ions or metal oxide ions. Specific examples of the inorganic cations 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 inorganic cation moiety of the carboxylate salt is 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, preferred inorganic cation moieties of the carboxylate salt are ions of typical metal elements, metals belonging to Groups 3 and 4 of the periodic table, or metal oxides thereof. Taking into account availability and toxicity, lithium, sodium, potassium, magnesium, calcium, zinc, and aluminum are more preferred.

[0048] 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 nitrogen atoms are cationized (ammonium ions, protonated amines, and quaternary ammonium ions) and ions in which phosphorus atoms are cationized (phosphonium ions, protonated phosphines, and quaternary phosphonium ions). However, from the viewpoints of biological safety and availability, ions in which nitrogen atoms are cationized are preferred.

[0049] 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.

[0050] 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.

[0051] Thus, the cations derived from the carboxylate preferably contain one or more cations selected from the group consisting of metal ions, metal oxide ions, and cations containing non-metal atoms of Group 15 of the periodic table.

[0052] Methods for analyzing the content of the cationic moiety of a carboxylate include, but are not limited to, ICP emission spectroscopy, atomic absorption spectroscopy, X-ray fluorescence, ion chromatography, capillary electrophoresis, etc. From the viewpoints of being able to detect the cationic moiety and ease of maintenance of the equipment and pretreatment of the sample, ion chromatography and capillary electrophoresis are preferred, with capillary electrophoresis being particularly preferred.

[0053] <Water> The water used in the present disclosure is not particularly limited, and for example, deionized water (ion-exchanged water), pure water, ultrapure water, distilled water, etc. can be used. The water content in the polymerizable composition can be measured by the Karl Fischer method.

[0054] <Cation ratio, water ratio> The polymerizable composition of the present disclosure satisfies at least either that the cation ratio represented by the above formula (I) is 0.01 or more and less than 1, or that the water ratio represented by the above formula (II) is 0.01 or more. The polymerizable composition of the present disclosure preferably contains, together with the 2-oxymethylacrylic acid (A), a carboxylate salt such that the cation ratio represented by the above formula (I) is 0.01 or more and less than 1, or that the water ratio represented by the above formula (II) is 0.01 or more, and may contain the carboxylate salt and water in amounts within a predetermined range.

[0055] From the viewpoint of reducing the amount of carboxylate depending on the application, the cation ratio is more preferably 0.95 or less, even more preferably 0.9 or less, and particularly preferably 0.8 or less. From the viewpoint of suppressing the formation of polymers that are thought to occur through a cationic polymerization mechanism, the cation ratio must be 0.01 or more, preferably 0.02 or more, and more preferably 0.03 or more. That is, the cation ratio is preferably 0.01 or more and less than 1, more preferably 0.01 or more and 0.95 or less, even more preferably 0.02 or more and 0.9 or less, and particularly preferably 0.03 or more and 0.8 or less.

[0056] From the viewpoint of suppressing the formation of polymers, the water ratio is preferably 0.01 or more, more preferably 0.15 or more, and even more preferably 0.02 or more. From the viewpoint of suppressing the formation of polymers, there is no upper limit to the water ratio, but from the viewpoint of increasing the content of 2-oxymethylacrylic acid (A), it is preferably 50 or less, more preferably 40 or less, even more preferably 30 or less, and particularly preferably 20 or less. That is, the water ratio is preferably 0.01 or more and 50 or less, more preferably 0.01 or more and 40 or less, even more preferably 0.01 or more and 30 or less, and particularly preferably 0.01 or more and 20 or less.

[0057] Among these, the polymerizable composition of the present disclosure preferably includes the following first and second forms. (First form) A preferred first embodiment of the present disclosure is a polymerizable composition containing 2-oxymethylacrylic acid (A) represented by the above formula (1) and the above carboxylate, wherein the cation ratio represented by the above calculation formula (I) is 0.01 or more and less than 1. As long as the carboxylate is contained so as to achieve the above cation ratio, water may not be contained, but water may also be contained. When water is contained, the water ratio represented by the above calculation formula (II) is preferably 0.0005 or more, more preferably 0.001 or more. The preferred cation ratio in the first embodiment is as described above.

[0058] (Second form) A second preferred embodiment of the present disclosure is a polymerizable composition containing 2-oxymethylacrylic acid (A) represented by the above formula (1) and water, wherein the water ratio represented by the above calculation formula (II) is 0.01 or more. As long as the water content is sufficient to satisfy the above water ratio, the carboxylate may not be contained, but the carboxylate may also be contained. The preferred water ratio in the second embodiment is as described above.

[0059] <Other ingredients> The polymerizable composition of the present disclosure may contain components other than the 2-oxymethylacrylic acid (A), carboxylate, and water, depending on the intended use, application, etc. Examples of such components include radical polymerization inhibitors, radical polymerizable compounds, radical polymerization initiators, compounds having a reactive group other than radical polymerizable, organic solvents, thermoplastic resins, organic or inorganic fine particles, fillers, 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.

[0060] Among the other components, the main ones are specifically shown below, but the present disclosure is not limited to these examples.

[0061] [Radical polymerization inhibitors] From the viewpoint of suppressing undesired radical polymerization during various operations such as storage, transportation, and 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.

[0062] 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.

[0063] 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.

[0064] 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.

[0065] 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.

[0066] 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. 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.

[0067] 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.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.

[0068] 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.

[0069] 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.

[0070] 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.

[0071] The content 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, relative to 100 parts by mass of the total of the radically polymerizable components (monomer components), from the viewpoint of suppressing radical polymerization during various operations such as storage, transportation, composition preparation, and processing, while also ensuring radical polymerizability appropriate for the application. In this specification, the radically polymerizable component refers to, for example, the above-mentioned 2-oxymethylacrylic acid, the radically polymerizable carboxylate, and the radically polymerizable compound described below.

[0072] [Radical polymerizable compounds] The polymerizable composition of the present disclosure may contain a radically polymerizable compound other than the 2-oxymethylacrylic acid (A) of the present disclosure so that it can be used as, for example, a component of a curable composition used in various coatings or three-dimensional modeling, a copolymer raw material, or the like.

[0073] Radically polymerizable compounds 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.

[0074] [Monofunctional radically polymerizable monomer] Examples of the monofunctional radical polymerizable monomer (a) include (meth)acrylic acid esters, (meth)acrylamides, 2-(meth)allyloxymethylacrylic acid esters, unsaturated monocarboxylic acids, unsaturated polycarboxylic acids, unsaturated monocarboxylic acids in which the unsaturated group and the carboxyl group are chain-extended, unsaturated acid anhydrides, aromatic vinyls, N-substituted maleimides, conjugated dienes, vinyl esters, vinyl ethers, N-vinyl compounds, and unsaturated isocyanates, but the present disclosure is not limited to these examples. These monofunctional radical polymerizable monomers may be used alone or in combination of two or more.

[0075] Examples of the (meth)acrylic acid ester 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, and (meth)acrylate. Examples of the (meth)acrylic acid ester include tricyclodecanyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 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, methyl α-hydroxymethylacrylate, and ethyl α-hydroxymethylacrylate, 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.

[0076] 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.

[0077] 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.

[0078] Examples of unsaturated monocarboxylic acids include, but are not limited to, (meth)acrylic acid, crotonic acid, cinnamic acid, and vinylbenzoic acid. These unsaturated monocarboxylic acids may be used alone or in combination of two or more.

[0079] Examples of unsaturated polycarboxylic acids include, but are not limited to, maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid. These unsaturated polycarboxylic acids may be used alone or in combination of two or more.

[0080] Examples of unsaturated monocarboxylic acids in which the unsaturated group and the carboxyl group are chain-extended include mono(2-acryloyloxyethyl) succinate and mono(2-methacryloyloxyethyl) succinate, but the present disclosure is not limited to these examples. These unsaturated monocarboxylic acids in which the unsaturated group and the carboxyl group are chain-extended may be used alone or in combination of two or more.

[0081] Examples of unsaturated acid anhydrides include maleic anhydride and itaconic anhydride, but the present disclosure is not limited to these examples. These unsaturated acid anhydrides may be used alone or in combination of two or more.

[0082] Examples of aromatic vinyls include, but are not limited to, styrene, α-methylstyrene, vinyltoluene, and methoxystyrene. These aromatic vinyls may be used alone or in combination of two or more.

[0083] 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.

[0084] 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.

[0085] Examples of vinyl esters include, but are not limited to, vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl benzoate. These vinyl esters may be used alone or in combination of two or more.

[0086] 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.

[0087] Examples of N-vinyl compounds include, but are not limited to, N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylimidazole, N-vinylmorpholine, and N-vinylacetamide. These N-vinyl compounds may be used alone or in combination of two or more.

[0088] Examples of unsaturated isocyanates include, but are not limited to, isocyanatoethyl (meth)acrylate and allyl isocyanate. These unsaturated isocyanates may be used alone or in combination of two or more.

[0089] The content of the monofunctional radically polymerizable monomer (a) may be adjusted depending on the application or purpose, and it does not have to be included; however, when used, it is preferably 1 to 98 mass%, more preferably 2 to 95 mass%, and even more preferably 3 to 90 mass%, relative to 100 mass% of the total of the radically polymerizable components.

[0090] [Polyfunctional radically polymerizable compound] As described above, the polyfunctional radical polymerizable compound (b) is a compound having two or more radical polymerizable groups in the same molecule. The radical polymerizable group in the polyfunctional radical polymerizable compound is preferably a carbon-carbon double bond, more preferably a carbon-carbon double bond conjugated and activated by an adjacent functional group.

[0091] Examples of conjugated activated carbon-carbon double bonds include carbon-carbon double bonds in vicinal conjugation such as in a 1,3-butadiene structure, carbon-carbon double bonds in vicinal conjugation with a carbonyl group, carbon-carbon double bonds in vicinal conjugation with a cyano group, and carbon-carbon double bonds in vicinal conjugation with an aromatic ring, but the present disclosure is not limited to these examples. Among these conjugated activated carbon-carbon double bonds, from the viewpoint of enhancing polymerization activity, carbon-carbon double bonds in vicinal conjugation with a carbonyl group, carbon-carbon double bonds in vicinal conjugation with a cyano group, and carbon-carbon double bonds in vicinal conjugation with an aromatic ring are preferred, carbon-carbon double bonds in vicinal conjugation with a carbonyl group are more preferred, and a (meth)acryloyl group, a 2-(meth)allyloxymethylacryloyl group, and a maleimide group are even more preferred.

[0092] Therefore, among the polyfunctional radically polymerizable compounds, polyfunctional (meth)acrylic compounds having one or more (meth)acryloyl groups and other radically polymerizable groups, polyfunctional 2-(meth)allyloxymethylacrylic compounds having one or more 2-(meth)allyloxymethylacryloyl groups and other radically polymerizable groups, and polyfunctional maleimide compounds having one or more maleimide groups and other radically polymerizable groups are preferred, and polyfunctional (meth)acrylic compounds having two or more (meth)acryloyl groups, polyfunctional 2-(meth)allyloxymethylacrylic compounds having two or more 2-(meth)allyloxymethylacryloyl groups, and polyfunctional maleimide compounds having two or more maleimide groups are more preferred.

[0093] Examples of polyfunctional radically 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 radically polymerizable compounds may be used alone or in combination of two or more.

[0094] 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.

[0095] 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.

[0096] Examples of allyl group-containing (meth)acrylic acid esters include allyl (meth)acrylate, but the present disclosure is not limited to these examples.

[0097] 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.

[0098] 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.

[0099] 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.

[0100] 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.

[0101] 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.

[0102] 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.

[0103] Examples of polyfunctional aromatic vinyls include divinylbenzene, but the present disclosure is not limited to these examples.

[0104] 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.

[0105] 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.

[0106] 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.

[0107] 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.;

[0108] 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.;

[0109] 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;

[0110] 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;

[0111] 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.;

[0112] 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.

[0113] The content of the polyfunctional radical polymerizable compound (b) may be adjusted depending on the application or purpose, and it does not have to be included; however, when used, it is preferably 1 to 98 mass%, more preferably 2 to 95 mass%, and even more preferably 3 to 90 mass%, relative to 100 mass% of the total of the radical polymerizable components.

[0114] The content of the radical polymerizable compound (i.e., the total content of the monofunctional radical polymerizable monomer (a) and the polyfunctional radical polymerizable compound (b)) may be adjusted depending on the application or purpose, and may not be included; however, when used, it is preferably 1 to 98 mass%, more preferably 2 to 95 mass%, and even more preferably 3 to 90 mass%, relative to 100 mass% of the total of the radical polymerizable components.

[0115] [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.

[0116] Examples of photoradical initiators include alkylphenone compounds, benzophenone compounds, benzoin compounds, ketal compounds, anthraquinone compounds, phosphine oxide compounds, thioxanthone compounds, halomethylated triazine compounds, halomethylated oxadiazole compounds, biimidazole compounds, oxime ester compounds, titanocene compounds, benzoic acid ester compounds, and acridine compounds, but the present disclosure is not limited to these examples. These photoradical initiators may be used alone or in combination of two or more.

[0117] Specific examples include acetophenone, 1,1-dichloroacetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butadiene. Alkylphenone compounds such as benzophenone, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone; benzophenone compounds such as benzophenone, 4,4'-bis(dimethylamino)benzophenone, 2-carboxybenzophenone, and 4-benzoyl-4'-methyldiphenyl sulfide; benzoin compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; ketal compounds such as acetophenone dimethyl ketal and benzil dimethyl ketal; anthraquinone compounds such as 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-chloroanthraquinone, and 2-amylanthraquinone;

[0118] Phosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, [3-(3,4-dimethyl-9-oxothioxanthone] Thioxanthone compounds such as [santen-2-yl]oxy-2-hydroxypropyl]-trimethylazanium chloride; 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-sec-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-sec-triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-sec-triazine, 2-(4-ethoxycarboxynylnaphthyl)-4,6-bis(trichloromethyl)-sec-triazine, etc. halomethylated triazine compounds; halomethylated oxadiazole compounds such as 2-trichloromethyl-5-[β-(2'-benzofuryl)vinyl]-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-(6''-benzofuryl)vinyl)]-1,3,4-oxadiazole, and 2-trichloromethyl-5-furyl-1,3,4-oxadiazole; 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4 -dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole and other biimidazole compounds; 1-[4-(phenylthio)-,2-(O-benzoyloxime)]-1,2-octanedione, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime)ethanone and other oxime ester compounds;Examples of suitable compounds include titanocene compounds such as bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium; acylphosphine oxide compounds such as bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide; benzoic acid ester compounds such as p-dimethylaminobenzoic acid and p-diethylaminobenzoic acid; and acridine compounds such as 9-phenylacridine, but the present disclosure is not limited to these examples.

[0119] As the thermal radical initiator, an organic peroxide initiator or an azo initiator is suitable, and specific examples thereof include the following.

[0120] 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.

[0121] 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- 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].

[0122] These may be used alone or in combination of two or more.

[0123] The content of the radical polymerization initiator is not particularly limited, but 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 radical polymerizable components.

[0124] [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.

[0125] 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 the like.

[0126] 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.

[0127] [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.

[0128] 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.

[0129] 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.

[0130] Furthermore, the content of other components other than the above-mentioned components may be adjusted depending on the application or purpose, and may not 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, relative to 100 parts by mass of the total of the radical polymerizable components.

[0131] <Polymer of the present disclosure> The present disclosure also relates to a polymer obtained by polymerizing the polymerizable composition of the present disclosure under radical-generating conditions.

[0132] 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 combined simultaneously, or may be combined 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.

[0133] 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.

[0134] 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.

[0135] As described above, the polymerizable composition of the present disclosure has good radical polymerizability, and therefore can be suitably used for various industrial or medical applications that undergo radical polymerization by heating or irradiation with active energy rays, such as coating materials, adhesives, sealants, pressure-sensitive adhesives, primers, sealants, 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, and water-absorbent resins, for electric and electronic components, optical components, and medical applications.

[0136] <How to save> The present disclosure also provides a method for storing 2-oxymethylacrylic acid (A) represented by the above formula (1), which comprises storing the 2-oxymethylacrylic acid (A) in the presence of a carboxylate having a cation ratio represented by the above calculation formula (I) of 0.01 or more and less than 1, and / or in the presence of water having a water ratio represented by the above calculation formula (II) of 0.01 or more.

[0137] The storage method of the present disclosure can suppress the generation of polymerization products due to cationic polymerization of 2-oxymethylacrylic acid (A) represented by the above formula (1), and provides excellent storage stability of 2-oxymethylacrylic acid (A).

[0138] The 2-oxymethylacrylic acid (A), carboxylate, and water used in the preservation method of the present disclosure are the same as those described above, and the cation ratio and water ratio are also the same as those described above.

[0139] The storage method is not particularly limited, and the 2-oxymethylacrylic acid (A) can be stored by a known method, such as by placing the 2-oxymethylacrylic acid (A) in a container or the like and leaving it to stand in the presence of a carboxylate having a cation ratio within a predetermined range and / or in the presence of water having a water ratio within a predetermined range.

[0140] The storage temperature is preferably 0 to 50°C, more preferably 5 to 40°C, from the viewpoint of suppressing radical polymerization and enabling easy temperature control.

[0141] The storage period is not particularly limited, but is, for example, 1 day to 2 years, preferably 1 day to 1 year. During this period, the 2-oxymethylacrylic acid (A) can be stored stably.

[0142] <Polymer materials> The present disclosure also provides a polymerization material comprising 2-oxymethylacrylic acid (A) represented by the above formula (1), a carboxylate and / or water, and a radical polymerization initiator, wherein the polymerization material satisfies at least one of the following: a cation ratio represented by the above formula (I) is 0.01 or more and less than 1; or a water ratio represented by the above formula (II) is 0.01 or more.

[0143] The polymer material of the present disclosure can suppress the generation of polymerization products due to cationic polymerization of the 2-oxymethylacrylic acid (A), and can provide a polymer with excellent storage stability and desired properties.

[0144] The 2-oxymethylacrylic acid (A), carboxylate, water, and radical polymerization initiator contained in the polymerization material of the present disclosure are the same as those described above, and the cation ratio and water ratio are also the same as those described above.

[0145] The polymerizable material of the present disclosure can be mixed with other components to form a polymerizable composition. Examples of the other components include those similar to those used in the polymerizable compositions described above. The polymerizable composition thus obtained is suitable for use in the production of various industrial or medical products. [Example]

[0146] 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."

[0147] <Carboxylate 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: 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 0.1N sodium hydroxide aqueous solution and ultrapure water to prepare measurement samples.

[0148] <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

[0149] <2-Oxymethylacrylic acid (A) and carboxylates> 2-Methoxymethylacrylic acid: 2-Methoxymethylacrylic acid with a purity of 97.3% (2-methoxymethylacrylic acid concentration of 8.38 mmol / g) containing 0.05% (based on the total volume of the liquid) hydroquinone monomethyl ether as a radical polymerization inhibitor was prepared. The purity was measured using a capillary electrophoresis system.

[0150] 2-Allyloxymethylacrylic acid: 2-Allyloxymethylacrylic acid with a purity of 96.7% (2-allyloxymethylacrylic acid concentration of 6.80 mmol / g) was prepared, containing 0.04% (based on the total volume of the solution) of hydroquinone monomethyl ether and 0.06% (based on the total volume of the solution) of 2,2'-(ethylenedithio)diethanol as radical polymerization inhibitors. The purity was measured using a capillary electrophoresis system.

[0151] 50% aqueous solution of sodium 2-allyloxymethylacrylate: An equivalent amount (equivalent to 100% neutralization) of 2-allyloxymethylacrylic acid was added to a 10% aqueous solution of sodium carbonate to neutralize it, then concentrated and an appropriate amount of water was added again to prepare an aqueous solution of sodium 2-allyloxymethylacrylate with a concentration of 50% (3.05 mmol / g).The solution contained 0.02% (based on the total volume of the solution) of hydroquinone monomethyl ether and 0.03% (based on the total volume of the solution) of 2,2'-(ethylenedithio)diethanol as radical polymerization inhibitors.The concentration of sodium 2-allyloxymethylacrylate was measured using a capillary electrophoresis system, and this concentration was used as the sodium 2-allyloxymethylacrylate concentration.

[0152] [Comparative Example 1] 3.25 g of 2-methoxymethylacrylic acid and 0.75 g of ultrapure water were placed in a 50 ml test tube with a stir bar and stirred to homogenize. Next, non-thermal desolvation and dehydration were carried out according to the following procedure. 4.0 g of diisopropyl ether and 3.0 g of acetone were added and stirred to homogenize. The test tube was connected to a vacuum line, and the degree of vacuum was gradually increased while keeping the temperature at room temperature, while taking care to avoid bumping. After the pressure reached 0.2 kPa, the pressure was maintained for 30 minutes. After the dehydration operation was completed, the pressure was returned to normal and the stirring was stopped. The stirrer was removed and the contents were checked, finding that they were cloudy. The cloudy contents were left to stand overnight, resulting in the deposition of a white precipitate. The liquid was removed from the test tube by decantation. 1.0 g of methanol was added to the test tube and dissolved, and the solution was added dropwise to a mixed solvent of acetone / hexane = 1 / 1 (weight ratio) to cause reprecipitation. The precipitate was removed by suction filtration and further dried in a vacuum at room temperature. The resulting solid was dissolved in heavy water with a sodium carbonate concentration of 2% and measured by 1H-NMR, which confirmed that it was a polymer. The molecular weight of the resulting solid was measured using an APC system and found to be 99,000.

[0153] [Example 1] A 50 ml test tube with a rim and a stir bar was charged with 0.15 g (1.4 mmol) of sodium carbonate and 0.75 g of ultrapure water, and the mixture was stirred to dissolve the sodium carbonate. Then, 3.25 g (27.2 mmol) of 2-methoxymethylacrylic acid was added and stirred to homogenize the mixture. 10 mol % of the 2-methoxymethylacrylic acid was converted to sodium salt, producing polymerizable composition (1) of the present disclosure. Here, the total amount of 2-methoxymethylacrylic acid moieties in polymerizable composition (1) was 27.2 mmol, the valence of the sodium ion derived from sodium 2-methoxymethylacrylate was 1, and the number of moles was 2.8 mmol. Therefore, the cation ratio based on the following calculation formula (I) was 0.10.

[0154]

number

[0155] (In formula (I), the total valence of cations derived from carboxylate salts is the sum of (valence of cations derived from carboxylate salts × number of moles of cations). The total amount of 2-oxymethylacrylic acid moieties is the number of moles of 2-oxymethylacrylic acid (A) + number of moles of 2-oxymethylacrylic acid ions derived from salts of 2-oxymethylacrylic acid (A).) Next, non-heating desolvation and dehydration operations were carried out in the same manner as in Comparative Example 1, and after completion of the operations, the state of the contents of the test tube was checked. The contents were transparent.

[0156] Comparative Example 2 3.40 g of 2-allyloxymethylacrylic acid and 0.60 g of ultrapure water were placed in a 50 ml test tube with a stir bar and stirred to homogenize. Next, non-heating desolvation and dehydration operations were carried out in the same manner as in Comparative Example 1, and after the operations were completed, the state of the contents of the test tube was checked and found to be cloudy. The cloudy contents were reprecipitated and dried in the same manner as in Comparative Example 1, and the resulting solid 1 H-NMR analysis confirmed that the product was a polymer. The molecular weight of the solid obtained was measured using an APC system and found to be 142,000.

[0157] [Example 2] 3.10 g (21.1 mmol) of 2-allyloxymethylacrylic acid, 0.77 g (2.3 mmol) of a 50% aqueous solution of sodium 2-allyloxymethylacrylate, and 0.23 g of ultrapure water were placed in a 50 ml test tube with a stir bar and stirred to homogenize, yielding polymerizable composition (2) of the present disclosure. Here, the total amount of 2-allyloxymethylacrylic acid moieties in polymerizable composition (2) was 23.4 mmol, the valence of the sodium ion derived from sodium 2-allyloxymethylacrylate was 1, and the number of moles was 2.3 mmol, resulting in a cation ratio of 0.10. Next, non-heating desolvation and dehydration operations were carried out in the same manner as in Comparative Example 1, and after completion of the operations, the state of the contents of the test tube was checked. The contents were transparent.

[0158] [Example 3] 3.30 g (22.4 mmol) of 2-allyloxymethylacrylic acid, 0.23 g (0.7 mmol) of a 50% aqueous solution of sodium 2-allyloxymethylacrylate, and 0.49 g of ultrapure water were placed in a 50 ml test tube with a stirring bar and stirred to homogenize, yielding polymerizable composition (3) of the present disclosure. Here, the total amount of 2-allyloxymethylacrylic acid moieties in polymerizable composition (3) was 23.1 mmol, the valence of the sodium ion derived from sodium 2-allyloxymethylacrylate was 1, and the number of moles was 0.7 mmol, resulting in a cation ratio of 0.03. Next, non-heating desolvation and dehydration operations were carried out in the same manner as in Comparative Example 1, and after completion of the operations, the state of the contents of the test tube was checked. The contents were transparent.

[0159] [Example 4] A 50 ml test tube with a rim and a stir bar was charged with 3.40 g (23.1 mmol) of 2-allyloxymethylacrylic acid, 0.14 g (3.5 mmol) of magnesium oxide powder, and 0.60 g of ultrapure water, and the mixture was stirred at 45° C. 15 mol % of the 2-allyloxymethylacrylic acid was converted into magnesium salt to produce polymerizable composition (4) of the present disclosure. Here, the total amount of 2-allyloxymethylacrylic acid moieties in polymerizable composition (4) was 23.1 mmol, and the valence of the magnesium ions derived from magnesium 2-allyloxymethylacrylate was 2, with a molar number of 3.5 mmol, resulting in a cation ratio of 0.30. Next, non-heating desolvation and dehydration operations were carried out in the same manner as in Comparative Example 1, and after completion of the operations, the state of the contents of the test tube was checked. The contents were transparent.

[0160] [Example 5] 3.40 g (23.1 mmol) of 2-allyloxymethylacrylic acid, 0.56 g (6.9 mmol) of zinc oxide powder, and 0.60 g of ultrapure water were placed in a 50 ml test tube with a stir bar and stirred at 45°C, and 60 mol% of the 2-allyloxymethylacrylic acid was converted to zinc chloride to produce polymerizable composition (5) of the present disclosure. Here, the total amount of 2-allyloxymethylacrylic acid moieties in polymerizable composition (5) was 23.1 mmol, and the valence of the zinc ions derived from zinc 2-allyloxymethylacrylate was 2, with a molar number of 6.9 mmol, resulting in a cation ratio of 0.60. Next, non-heating desolvation and dehydration operations were carried out in the same manner as in Comparative Example 1, and after completion of the operations, the state of the contents of the test tube was checked. The contents were transparent.

[0161] [Example 6] A 50 ml test tube with a rim and a stir bar was charged with 3.40 g (23.1 mmol) of 2-allyloxymethylacrylic acid, 0.51 g (3.4 mmol) of N,N'-bis(2-hydroxyethyl)ethylenediamine, and 0.60 g of ultrapure water, and the mixture was stirred at 45°C to convert 30 mol% of the 2-allyloxymethylacrylic acid into an amine salt, producing polymerizable composition (6) of the present disclosure. Here, the total amount of 2-allyloxymethylacrylic acid moieties in polymerizable composition (6) was 23.1 mmol, and the amine constituting the amine salt of 2-allyloxymethylacrylic acid had a valence of 2 and a molar number of 3.4 mmol, resulting in a cation ratio of 0.30. Next, non-heating desolvation and dehydration operations were carried out in the same manner as in Comparative Example 1, and after completion of the operations, the state of the contents of the test tube was checked. The contents were transparent.

[0162] [Example 7] The water content of 2-allyloxymethylacrylic acid was measured with a Karl Fischer moisture meter and found to be 1.25%, which means that the water ratio based on the following formula (II) is 0.013.

[0163]

number

[0164] This was poured into a 1.5 ml glass vial up to 70% of the capacity and stored in the refrigerator (approximately 4°C). Checks were carried out every 3 months, and no polymerization occurred even after 18 months of storage.

[0165] Comparative Example 3 10.0 g of the prepared 2-allyloxymethylacrylic acid and 5.0 g of ethyl acetate were placed in a 50 ml rubbed recovery flask equipped with a stirrer. The flask was heated to 60°C while gradually reducing the pressure to perform azeotropic dehydration. The pressure was finally reduced to 0.5 kPa, and after reaching 0.5 kPa, the pressure was maintained for 20 minutes before being released. The filter holder of the suction filtration apparatus was filled with 1 g of silica gel (Wakogel C-200, Fujifilm Wako Pure Chemical Industries, Ltd.) as a filter aid, and the dehydrated 2-allyloxymethylacrylic acid was subjected to suction filtration. The moisture content after filtration was measured using a Karl Fischer moisture meter and found to be 0.07%. Therefore, the moisture ratio based on the above formula (II) was 0.0007. This was filled to 70% of a 1.5 ml glass vial and stored in the refrigerator (approximately 4°C). When checked every 3 months, it had solidified in the 15th month.

[0166] [Example 8] 1.0 g of the content obtained in Example 5 after the non-heating solvent removal and dehydration operation (a mixture of 2-allyloxymethylacrylic acid and zinc 2-allyloxymethylacrylate), 2.0 g of 2-ethylhexyl acrylate, and 0.09 g of 1-hydroxycyclohexyl phenyl ketone were mixed and stirred to obtain a homogeneous solution. The obtained solution was applied to a heat-resistant acrylic film (a 140 μm-thick film made by melt-extruding pellets obtained by the method described in Production Example 7 of JP 2019-179124 A) using a bar coater No. 2, and then the film was heated in a belt conveyor-type UV irradiation device (illuminance 500 mW / cm 2 , cumulative light intensity 5J / 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.

[0167] The results of Examples 1 to 6 revealed that the polymerizable composition of the present disclosure suppresses the generation of polymerization products during non-heating desolvation and dehydration operations. Furthermore, the results of Example 7 revealed that the generation of polymerization products during low-temperature storage is suppressed. Furthermore, the results of Example 8 revealed that the polymerizable composition of the present disclosure has good photoradical polymerizability.

Claims

1. The following formula (1): 【number】 (In the formula, R represents a hydrogen atom or a saturated or unsaturated hydrocarbon group having 10 or less carbon atoms.) A polymerizable composition comprising 2-oxymethylacrylic acid (A) represented by the formula: and a carboxylate salt, A polymerizable composition characterized in that the cation ratio represented by the following formula (I) is 0.01 or more and less than 1: [Equation 1] (In formula (I), the total valence of cations derived from carboxylate salts is the sum of [valence of cations derived from carboxylate salts × number of moles of cations]. The total amount of 2-oxymethylacrylic acid moieties is the sum of the number of moles of 2-oxymethylacrylic acid (A) and the number of moles of 2-oxymethylacrylic acid ions derived from 2-oxymethylacrylic acid (A).)

2. 2. The polymerizable composition according to claim 1, wherein the cation derived from the carboxylate comprises one or more cations selected from the group consisting of a metal ion, a metal oxide ion, and a cation containing a nonmetal atom of Group 15 of the periodic table.

3. 3. The polymerizable composition according to claim 1, wherein the carboxylate comprises one or more carboxylates selected from the group consisting of a salt of 2-oxymethylacrylic acid (A), a salt of acrylic acid, and a salt of methacrylic acid.

4. 3. The polymerizable composition according to claim 1, wherein the amount of 2-oxymethylacrylic acid ions contained in the carboxylate is 50 mol % or more and 100 mol % or less of the total amount of carboxylate ions contained in the carboxylate.

5. 3. The polymerizable composition according to claim 1, wherein R in the general formula (1) is an allyl group or a methallyl group.

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

7. The following formula (1): 【number】 (In the formula, R represents a hydrogen atom or a saturated or unsaturated hydrocarbon group having 10 or less carbon atoms.) A method for storing 2-oxymethylacrylic acid (A) represented by the formula: The method for storing 2-oxymethylacrylic acid (A) comprises storing the 2-oxymethylacrylic acid (A) in the presence of a carboxylate having a cation ratio represented by the following calculation formula (I) of 0.01 or more and less than 1: [Equation 2] (In formula (I), the total valence of cations derived from carboxylate salts is the sum of [valence of cations derived from carboxylate salts × number of moles of cations]. The total amount of 2-oxymethylacrylic acid moieties is the sum of the number of moles of 2-oxymethylacrylic acid (A) and the number of moles of 2-oxymethylacrylic acid ions derived from 2-oxymethylacrylic acid (A).)

8. The following formula (1): 【number】 (In the formula, R represents a hydrogen atom or a saturated or unsaturated hydrocarbon group having 10 or less carbon atoms.) A polymerization material comprising 2-oxymethylacrylic acid (A) represented by the formula: A polymeric material characterized in that the cation ratio represented by the following formula (I) is 0.01 or more and less than 1. [Equation 3] (In formula (I), the total valence of cations derived from carboxylate salts is the sum of [valence of cations derived from carboxylate salts × number of moles of cations]. The total amount of 2-oxymethylacrylic acid moieties is the sum of the number of moles of 2-oxymethylacrylic acid (A) and the number of moles of 2-oxymethylacrylic acid ions derived from 2-oxymethylacrylic acid (A).)

Images