TW202346488A - Polymerizable composition - Google Patents

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

polymeric composition

The present invention relates to a polymerizable composition with improved stability.

It is known that α-substituted methacrylate undergoes radical polymerization, and it is known that although the polymerization speed is low, the termination speed is also low, so polymers with a high degree of polymerization can sometimes be obtained (for example, Non-Patent Document 1, Non-Patent Document 2 ). It is known that α-allyloxy methacrylates with an α-substituted methacrylate structure have cyclopolymerizability and exhibit radical polymerization activity close to that of acrylates (for example, Non-patent Document 3, Patent Document 1) . Furthermore, a method of inhibiting radical polymerization of α-allyloxy methacrylates to improve high-temperature stability and storage stability has also been disclosed (for example, Patent Document 2). [Prior technical literature] [Patent Document]

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

[Non-patent document 1] B. Yamada and S. Kobatake, Prog. Polym. Sci., 119, 1089 (1994) [Non-patent document 2] Yamada Bunichiro, Subsequent Technology, 14, 1 (1995) [Non-patent document 3] Michio Urushizaki, Toshiyuki Kodaira, Takeji Furuta, Yutaka Yamada, Shoji Oshitani, Macromolecules, 1999, Volume 32, Pages 322-327

[Problem to be solved by the invention]

There are abundant research examples related to the polymerizability of α-substituted methacrylates, but there are few research examples related to the polymerizability of α-substituted methacrylic acid. In particular, it has not been known that 2-hydroxymethacrylic acid or 2-alkane When oxymethacrylic acid (hereinafter, these may be simply referred to as 2-oxymethacrylic acid) is processed, polymerization products are likely to be generated during, for example, manufacturing, storage, transportation, composition preparation operations, and the like.

Therefore, an object of the present invention is to provide a polymerizable composition containing 2-oxymethacrylic acid that can suppress the generation of polymerization products in manufacturing steps and the like. [Technical means to solve the problem]

The inventors of the present invention have conducted various studies in order to achieve the above object. As a result, they have found that 2-oxymethacrylic acid is considered to be a cationic polymerization reaction and easily generates unwanted polymerization products. Furthermore, this polymerization reaction does not occur with 2-oxymethacrylic acid. It is produced from oxymethacrylate or 2-oxymethacrylate, but is a reaction unique to 2-oxymethacrylic acid. Furthermore, it was found that by preparing a composition in which a carboxylic acid salt or water functioning as a base is contained in 2-oxymethacrylic acid so that the cation ratio or the water ratio falls within a predetermined range, it can be effectively suppressed. The present invention was conceived from the production of the above-mentioned polymer products. That is, the present invention is described in the following [1] to [8]. [1] A polymerizable composition containing the following formula (1):

(In the formula, R represents a hydrogen atom or a saturated or unsaturated hydrocarbon group with less than 10 carbon atoms) The 2-oxymethacrylic acid (A), carboxylate and/or water represented are characterized by satisfying The cation ratio represented by the following calculation formula (I) is 0.01 or more and less than 1, or The moisture ratio expressed by the following calculation formula (II) is 0.01 or more At least any one of them.

(In the calculation formula (I), the total valence of the cations derived from the carboxylate is the sum of [the valence of the cations derived from the carboxylate × the molar number of the cation]; the 2-oxymethacrylic acid moiety The total amount is the sum of the moles of 2-oxymethacrylic acid (A) and the moles of 2-oxymethacrylate ions derived from 2-oxymethacrylic acid (A)).

[2] The polymerizable composition according to the above [1], wherein the cation derived from the carboxylate contains a cation selected from the group consisting of metal ions, metal oxide ions, and non-metal atoms of Group 15 of the periodic table. A group of more than one cation. [3] The polymerizable composition according to the above [1] or [2], wherein the carboxylate salt contains a salt selected from the group consisting of a salt of 2-oxymethacrylic acid (A), a salt of acrylic acid, and methacrylic acid. One or more carboxylates in a group of salts. [4] The polymerizable composition according to any one of the above [1] to [3], characterized in that the amount of 2-oxymethacrylate ions contained in the carboxylic acid salt is relative to the amount of the carboxylic acid. The total amount of carboxylate ions contained in the salt is 50 mol% or more and 100 mol% or less. [5] The polymerizable composition according to any one of the above [1] to [4], characterized in that R in the above general formula (1) is allyl or metallyl. [6] A polymer obtained by polymerizing the polymerizable composition of any one of the above [1] to [5] under free radical generation conditions. [7] A method for preserving 2-oxymethacrylic acid (A), wherein the 2-oxymethacrylic acid (A) is represented by the following formula (1):

(In the formula, R represents a hydrogen atom or a saturated or unsaturated hydrocarbon group with less than 10 carbon atoms) The 2-oxymethacrylic acid (A) is stored in the presence of a carboxylate with a cation ratio of 0.01 or more and less than 1 represented by the following calculation formula (I), and/or in the presence of the following calculation formula (II) The 2-oxymethacrylic acid (A) is stored in the presence of water with a moisture ratio of 0.01 or more.

(In the calculation formula (I), the total valence of the cations derived from the carboxylate is the sum of [the valence of the cations derived from the carboxylate × the molar number of the cation]; the 2-oxymethacrylic acid moiety The total amount is the sum of the moles of 2-oxymethacrylic acid (A) and the moles of 2-oxymethacrylate ions derived from 2-oxymethacrylic acid (A)).

[8] A polymeric material containing the following formula (1):

(In the formula, R represents a hydrogen atom or a saturated or unsaturated hydrocarbon group with less than 10 carbon atoms) The represented 2-oxymethacrylic acid (A), carboxylate and/or water, and radical polymerization initiator, and is characterized by satisfying The cation ratio represented by the following calculation formula (I) is 0.01 or more and less than 1, or The moisture ratio expressed by the following calculation formula (II) is 0.01 or more At least any one of them.

(In the calculation formula (I), the total valence of the cations derived from the carboxylate is the sum of [the valence of the cations derived from the carboxylate × the molar number of the cation]; the 2-oxymethacrylic acid moiety The total amount is the sum of the moles of 2-oxymethacrylic acid (A) and the moles of 2-oxymethacrylate ions derived from 2-oxymethacrylic acid (A)).

[Effects of the invention]

According to the present invention, it is possible to provide a polymerizable composition containing 2-oxymethacrylic acid that suppresses the generation of a polymerization product due to a reaction considered to be cationic polymerization and exhibits good radical polymerizability when used. The above-mentioned polymerizable composition can be preferably used for various purposes, such as a component of a curable composition used for various coatings, bonding, sealing, or three-dimensional molding, and a copolymer raw material.

Hereinafter, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to the following description, and may be appropriately modified and applied within the scope that does not change the gist of the present invention. Furthermore, a combination of two or more of each of the preferred aspects of the invention described below also belongs to the preferred aspects of the invention. Moreover, (meth)acrylic acid means acrylic acid or methacrylic acid. (Meth)allyl means allyl or metallyl.

The present invention is a polymerizable composition containing the following formula (1):

(In the formula, R represents a hydrogen atom or a saturated or unsaturated hydrocarbon group with less than 10 carbon atoms) The represented 2-oxymethacrylic acid (A), carboxylate and/or water is characterized by satisfying The cation ratio represented by the following calculation formula (I) is 0.01 or more and less than 1, or The moisture ratio expressed by the following calculation formula (II) is 0.01 or more At least any one of them.

(In the calculation formula (I), the total valence of the cations derived from the carboxylate is the sum of [the valence of the cations derived from the carboxylate × the molar number of the cation]; the 2-oxymethacrylic acid moiety The total amount is the sum of the moles of 2-oxymethacrylic acid (A) and the moles of 2-oxymethacrylate ions derived from 2-oxymethacrylic acid (A)).

The polymerizable composition of the present invention has the above structure, which can suppress the generation of polymerization products, thereby improving the stability of the polymerizable composition.

The inventors believe that the compound having the structure of 2-oxymethacrylic acid (A) represented by the above formula (1) has a high electron-donating property of the RO-CH ₂ group, so it is easy to combine with the RO-CH ₂ group and Carbocations are generated on the carbon to which the carboxyl group is bonded, and the carboxyl group will also become a catalyst or initiator for cationic polymerization. Therefore, even if compounds commonly used as catalysts or initiators for cationic polymerization (such as sulfonic acid compounds or Boron compounds) are also prone to cationic polymerization. Furthermore, it is considered that in order to suppress the generation of carbocation or to deactivate the carbocation even if it is generated, it is considered that a base only needs to coexist. Carboxylic acid salts or water are known to function as anionic polymerization initiators for vinyl compounds (2-cyanoacrylate, methylenemalonate, etc.) having carbon activated with electron-withdrawing groups. A weak base comes into play. It is speculated that the reason why the formation of the polymer thought to be generated in the cationic polymerization mechanism of the above-mentioned 2-oxymethacrylic acid (A) can be suppressed by the constitution of the present invention is that carboxylate or water acts as a base, and as long as it contains a fixed If the amount is above the amount, its inhibitory power will exceed the power to initiate and proceed cationic polymerization.

The components constituting the polymerizable composition of the present invention will be described. ＜2-oxymethacrylic acid (A)＞ 2-Oxymethacrylic acid (A) is a compound represented by the following formula (1):

(In the formula, R represents a hydrogen atom or a saturated or unsaturated hydrocarbon group with a carbon number of 10 or less).

The saturated or unsaturated hydrocarbon group with a carbon number of 10 or less in the above-mentioned R may be linear, branched, or cyclic.

Specific examples of R include: a hydrogen atom; a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a second butyl group, an isobutyl group, a third butyl group, an n-pentyl group, a third Dipentyl, third pentyl, neopentyl, n-hexyl, second hexyl, n-heptyl, n-octyl, second octyl, third octyl, 2-ethylhexyl, nonyl, decyl, etc. Straight-chain or branched saturated hydrocarbon groups; cyclopentyl, cyclopentylmethyl, cyclohexyl, cyclohexylmethyl, trimethylcyclohexyl, dicyclopentyl, isobornyl and other saturated hydrocarbon groups containing alicyclic structures , phenyl, benzyl and other hydrocarbon groups containing aromatic rings; vinyl, allyl, methylallyl, crotyl, butenyl, cyclohexenyl, dicyclopentenyl and other non-conjugated hydrocarbon groups containing unconjugated Hydrocarbon groups with saturated bonds, etc. are not limited to these examples, and two or more types may be combined.

From the viewpoint of improving 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 still more preferably 4 or less. The above-mentioned saturated or unsaturated hydrocarbon group is preferably a hydrocarbon group containing an unsaturated bond, and most preferably is an allyl group or a methallyl group that exhibits polymerization activity close to that of (meth)acrylate due to its cyclopolymerizability.

Examples of methods for analyzing the content of 2-oxymethacrylic acid (A) include: gas chromatography; various methods based on distribution, adsorption, ion exchange, ion exclusion, particle size screening, affinity chromatography, etc. Separation mode liquid chromatography; capillary electrophoresis; ¹ H-NMR and other spectroscopic optical methods; however, it is not limited to this example. From the viewpoint that it can be detected as 2-oxymethacrylate ions, ion chromatography and capillary electrophoresis are preferred, and from the viewpoint that measurement can be performed in a short time, ¹ H-NMR is preferred. . Among them, capillary electrophoresis is preferred from the viewpoint of sensitivity and maintainability of the device.

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

If the compound name of carboxylic acid specifically represents the carboxylate ion part of the carboxylate, for example, monovalent saturated carboxylic acid such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, myristic acid, stearic acid, etc. Acids; oxalic acid, malonic acid, succinic acid, adipic acid, cyclohexanetricarboxylic acid and other polyvalent saturated carboxylic acids; benzoic acid, phthalic acid, terephthalic acid, 1,2,4-benzenetricarboxylic acid, etc. Aromatic carboxylic acids; acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, etc. have a double bond conjugated with a carboxyl group and are not 2-oxymethacrylic acid (A) of the present invention Carboxylic acid; 2-hydroxymethylacrylic acid, 2-methoxymethacrylic acid, 2-allyloxymethacrylic acid, 2-methylallyloxymethacrylic acid and other 2-oxymethacrylates of the present invention acrylic acid (A), etc.; however, it is not limited to this example, and the carboxylate ion part of the carboxylate may be a combination of two or more carboxylate ions.

From the viewpoint of making the polymerizable composition of the present invention a composition with good radical polymerizability, the carboxylate ion part of the carboxylate is preferably a carboxylate ion having a double bond conjugated with a carboxyl group, and particularly preferably Acrylic acid, methacrylic acid, and the carboxylate ion of the above-mentioned 2-oxymethacrylic acid (A) are more preferably 2-oxymethacrylate ions. The most preferred ones are carboxylate ions of 2-allyloxymethacrylic acid and 2-methylallyloxymethacrylic acid. Thus, the carboxylate preferably contains one or more carboxylates selected from the group consisting of salts of 2-oxymethacrylic acid (A), salts of acrylic acid, and salts of methacrylic acid.

The amount of carboxylate ions having a double bond conjugated with a carboxyl group contained in the carboxylate is preferably 50 mol% or more and 100 mol% or less relative to the total amount of carboxylate ions in the carboxylate. More preferably, it is 70 mol% or more and 100 mol% or less, and still more preferably, it is 90 mol% or more and 100 mol% or less. The optimal form is one in which the amount of 2-oxymethylcarboxylate ions contained in the carboxylate is 50 mol% or more and 100 mol% or less relative to the total amount of carboxylate ions in the carboxylate.

Examples of methods for analyzing the content of the carboxylate ion portion of carboxylates include: liquid chromatography based on various separation modes such as distribution, adsorption, ion exchange, ion exclusion, particle size screening, and affinity; capillary tube Electrophoresis; ¹ H-NMR and other optical methods; however, the method is not limited to this example. From the viewpoint that it can be detected as carboxylate ions, ion chromatography and capillary electrophoresis are preferred, and from the viewpoint that measurement can be performed in a short time, ¹ H-NMR is preferred. Among them, capillary electrophoresis is preferred from the viewpoint of sensitivity and maintainability of the device.

The cation constituting the carboxylate together with the carboxylate ion moiety may be an inorganic cation or an organic cation, and may be appropriately selected according to the purpose and use.

Examples of inorganic cations include metal ions or metal oxide ions. When specifically expressed by element names or metal oxide names, examples include Group 1 elements of the periodic table such as lithium, sodium, and potassium; magnesium, calcium, Elements from Group 2 of the periodic table such as barium; transition metal elements or transition metal oxides such as lanthanum, zirconium oxide, iron, cobalt, nickel, copper, etc.; elements from Groups 12 to 15 of the periodic table such as zinc, aluminum, tin, lead, bismuth, etc. Typical metal elements, etc.; however, it is not limited to this example, and may also be a combination of two or more metals or metal oxide ions. From the viewpoint of making the polymerizable composition of the present invention colorless, the inorganic cation part of the carboxylate is preferably a typical metal element, a metal belonging to Group 3 and Group 4 of the periodic table, or a metal oxide. If the ions are taken into account in terms of availability and toxicity, then lithium, sodium, potassium, magnesium, calcium, zinc, and aluminum are more preferred.

Examples of organic cations include cations containing non-metallic elements of Group 15 of the periodic table. Examples of non-metallic elements in Group 15 of the periodic table include nitrogen, phosphorus, and arsenic. Preferable examples include ions formed by cationization of nitrogen atoms (ammonium ions, protonated amines, quaternary ammonium ions), and ions formed by cationization of phosphorus atoms (phosphonium ions, protonated phosphine, quaternary ammonium ions). phosphonium ion), from the viewpoint of biological safety and accessibility, ions in which nitrogen atoms are cationized are preferred.

When the protonated amine is specifically expressed by the name of the amine before protonation, examples include: methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, etc. amine, ethanolamine, diethanolamine, triethanolamine, tris(2-aminoethyl)amine, hexamethylenediamine, iminobispropylamine, methyliminobispropylamine, 3,6 ,9,12-tetraoxa-tetradecane-1,14diamine (3,6,9,12-tetraoxa-tetradecane-1,14-diamine), N,N'-bis(2-hydroxyethyl) )Ethylenediamine, 1,3-bisaminomethylcyclohexane, 1,4-bisaminomethylcyclohexane, 3-aminomethyl-3,5,6-trimethylcyclohexylamine , Isophorone diamine, 2,5(or 2,6)-bis(aminomethyl)bicyclo[2,2,1]heptane, 2,6(or 2,7)-bis(amine methyl)bicyclo[3,2,1]octane, 2,5(or 2,6)-bis(aminomethyl)-7-dimethylbicyclo[2,2,1]heptane , 2,6-bis(aminomethyl)adamantane, m-phenylenediamine, p-phenylenediamine, bis(4-aminophenyl)methane, 1,4 (or 2,6 or 2,7) -Bis(aminomethyl)naphthalene, piperazine , aminoethyl piperazine , Bisaminopropylpiper ,2,4,6-triamino-1,3,5-tri , polyethylenimine and other amines whose nitrogen atom part has a structure of primary to tertiary, and the valence of the amine is monovalent or divalent or higher; however, the present invention is not limited to this example.

Specific examples of quaternary ammonium ions include tetramethylammonium ion, tetraethylammonium ion, tetrabutylammonium ion, benzyltrimethylammonium ion, hexadecyltrimethylammonium ion, and the like. However, the present invention is not limited to this example.

Thus, the cation derived from the carboxylate preferably contains 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.

Examples of methods for analyzing the content of the cationic part of the carboxylate include, but are not limited to, ICP emission spectroscopy, atomic absorption, fluorescent X-ray, ion chromatography, and capillary electrophoresis. From the viewpoints of detection in the form of cations, ease of maintenance of the device, and ease of sample pretreatment, ion chromatography and capillary electrophoresis are preferred, and capillary electrophoresis is particularly preferred.

＜Water＞ The water used in the present invention is not particularly limited, and for example, deionized water (ion exchange water), pure water, ultrapure water, distilled water, etc. can be used. The water content in the above-mentioned polymerizable composition can be measured by the Karnofsky method.

＜Cation ratio, moisture ratio＞ The polymerizable composition of the present invention satisfies at least one of the cation ratio represented by the above calculation formula (I) being 0.01 or more and less than 1 or the moisture ratio represented by the above calculation formula (II) being 0.01 or more. The polymerizable composition of the present invention preferably contains the above-mentioned 2-oxymethacrylic acid (A) and at least a carboxylate so that the cation ratio represented by the above-mentioned calculation formula (I) is 0.01 or more and less than 1. Alternatively, water may be contained so that the moisture ratio represented by the above calculation formula (II) becomes 0.01 or more, or carboxylic acid salt and water may be contained in predetermined range amounts.

From the viewpoint of reducing the amount of carboxylic acid salt according to the use, the cation ratio is more preferably 0.95 or less, further preferably 0.9 or less, and particularly preferably 0.8 or less. From the viewpoint of suppressing the formation of a polymer thought to be generated in 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, further preferably 0.02 or more and 0.9 or less, particularly preferably 0.03 or more and 0.8 or less.

From the viewpoint of suppressing the formation of polymer, the moisture ratio is preferably 0.01 or more, more preferably 0.15 or more, and still more preferably 0.02 or more. From the viewpoint of suppressing the formation of the polymer, there is no upper limit to the moisture ratio. From the viewpoint of increasing the content of 2-oxymethacrylic acid (A), it is preferably 50 or less, more preferably 40 or less, and further preferably The best value is below 30, and the best value is below 20. That is, the moisture content is preferably 0.01 or more and 50 or less, more preferably 0.01 or more and 40 or less, further preferably 0.01 or more and 30 or less, particularly preferably 0.01 or more and 20 or less.

Among these, preferred examples of the polymerizable composition of the present invention include the following first and second aspects. (1st form) A preferred first aspect of the present invention is a polymerizable composition containing 2-oxymethacrylic acid (A) represented by the above formula (1) and the above carboxylate salt, and the above calculation formula (I) is The cation ratio expressed is 0.01 or more and less than 1. As long as the carboxylic acid salt is contained so as to achieve the above-mentioned cation ratio, water may not be contained, but water may be further contained. When the above-mentioned water is contained, the moisture ratio represented by the above-mentioned calculation formula (II) is preferably 0.0005 or more, more preferably 0.001 or more. Preferable cationic ratios in the first form are as described above.

(2nd form) A preferred second aspect of the present invention is a polymerizable composition containing 2-oxymethacrylic acid (A) represented by the above formula (1) and water, and the moisture content represented by the above calculated formula (II) The ratio is above 0.01. As long as water is contained so as to achieve the above-mentioned moisture ratio, the above-mentioned carboxylic acid salt may not be contained, but the above-mentioned carboxylic acid salt may be further contained. The preferred moisture ratio in the second form is as above.

＜Other ingredients＞ The polymerizable composition of the present invention may contain components other than the above-mentioned 2-oxymethacrylic acid (A), carboxylate, and water depending on the purpose of use, use, etc. Examples of such components include radical polymerization inhibitors, radical polymerizable compounds, radical polymerization initiators, compounds having reactive groups other than radical polymerizability, organic solvents, thermoplastic resins, and organic or inorganic fine particles. , fillers, dyes, pigments, dispersants, ultraviolet absorbers, leveling agents, surface conditioners, antistatic agents, adhesion improvers, coupling agents, release agents, viscosity adjusters, etc., but the invention is not limited to Wait.

Main components among other components are specifically shown below, but the present invention is not limited to this illustration.

[Radical polymerization inhibitor] From the viewpoint of suppressing unwanted radical polymerization in various operations such as storage, transportation, preparation and handling of the composition, an appropriate amount of primary polymer having anti-radical chain reaction properties may be used in the polymerizable composition of the present invention. Antioxidants and/or secondary antioxidants with peroxide decomposability.

Examples of primary antioxidants include hydroquinones, benzoquinones, phenols, aromatic amines, and thiophenes. compounds, metal dithiocarbamates, nitroso compounds, etc., but the present invention is not limited to these examples. Examples of secondary antioxidants include phosphorus-based compounds such as phosphines and phosphites, sulfur-based compounds such as thioethers, mercaptobenzimidazole, and thiourea, but the present invention is not limited to these examples. The primary antioxidant and the secondary antioxidant can be used individually, but it is more preferable to use them in combination.

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

Examples of phenols include monoetherified hydroquinones, hindered phenols and their polymers (including dimers) or derivatives of polymers, semi-hindered phenols and their polymers (including Dimer) or polymer derivatives, etc., but the present invention is not limited only to these examples. These phenols may be used individually, or 2 or more types may be used together.

Examples of monoetherified hydroquinones include hydroquinone monomethyl ether, hydroquinone mono-n-butyl ether, hydroquinone monobenzyl ether, hydroquinone monocyclohexyl ether, and 4- Methoxy-1-naphthol, etc., but the present invention is not limited only to these examples. These monoetherified hydroquinones may be used individually, or two or more types may be used in combination.

Examples of hindered phenols include 2,6-bis(tert-butyl)-4-methylphenol and 3-(3,5-di-tert-butyl-4-hydroxyphenyl)octadecylpropionate. Ester, 3-(3,5-di-tert-butyl-4-hydroxyphenyl) isooctyl propionate, 2,4-bis-(n-octylthio)-6-(4-hydroxy-3, 5-Di-tert-butylanilino)-1,3,5-tri , 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid-diethyl ester, etc., but the present invention is not limited only to these examples. Examples of polymers or derivatives of polymers of hindered phenols include pentaerythrityl and tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylene Bis(3,5-di-tert-butyl-4-hydroxy-hydrocinamide), 1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxybenzene) ethyl)propionate], tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-isocyanurate, 1,3,5-trimethyl-2,4,6- Tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, etc., but the present invention is not limited only to this example. Hindered phenols and their polymers (including dimers) or derivatives of the polymers may be used individually, or two or more types may be used in combination.

Examples of semi-hindered phenols include 6-tert-butyl-o-cresol, 6-tert-butyl-2,4-xylenol, and 2,4,8,10-tetra-tert-butyl -6-[3-(3-methyl-4-hydroxy-5-tert-butylphenyl)propoxy]dibenzo[d,f][1,3,2]dioxaphosphorus heterocycle Heptane (dioxaphosphepin), 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-tertiary butylphenol, 2-tertiary amylphenol, 2,4-di-tertiary butylphenol Amylphenol, etc., but the present invention is not limited only to these examples. Examples of polymers or derivatives of polymers of semi-hindered phenols include methylenebis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionic acid ester], 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, terephthalyl-bis(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'-butylenebis(6-tert-butyl-3-methyl phenol), 4,4'-thiobis(6-tert-butyl-3-methylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butyl) Phenyl)butane, 2,2'-methylenebis(4-methyl-6-tertbutylphenol), 2,2'-methylenebis(4-ethyl-6-tertbutylphenol) phenol), 2,2'-thiobis(4-methyl-6-tert-butylphenol), acrylic acid 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl) Ethyl]-4,6-di-tert-pentylphenyl ester, 2-tert-butyl acrylate-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methyl phenyl ester, etc., but the present invention is not limited only to these examples. Semi-hindered phenols and their polymers (including dimers) or derivatives of the polymers may be used individually, or two or more types may be used in combination.

Examples of the phosphine include triethylphosphine, tributylphosphine, tris(2-ethylhexyl)phosphine, triphenylphosphine, etc., but the present invention is not limited only to these examples. These phosphines may be used individually or in combination of 2 or more types.

Examples of the phosphite include diethyl hydrogen phosphite, bis(2-ethylhexyl) hydrogen phosphite, dilauryl hydrogen phosphite, dioleyl hydrogen phosphite, and diphenyl hydrogen phosphite. , triethyl phosphite, tributyl phosphite, tris(2-ethylhexyl) phosphite, triisodecyl phosphite, trilauryl phosphite, tridecyl phosphite, phosphorous acid Trioleyl ester, tristearyl phosphite, diisodecyl phenyl phosphite, diphenyl methyl phosphite, 2-ethylhexyl diphenyl phosphite, isodecyl diphenyl phosphite, Tridecyl diphenyl phosphate, bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite, triphenyl phosphite, tricresyl phosphite, tris(nonyl) phosphite Phenyl) ester, tris(2,4-di-tert-butylphenyl) phosphite, bis(isodecyl)neopenterythritol diphosphite, bis(tridedecyl)neopenterythritol diphosphite Phosphite, bis (stearyl) neopentyl erythritol diphosphite, bis (nonylphenyl) neopentyl erythritol diphosphite, bis (2,4-di-tert-butylphenyl) neon Pentaerythritol diphosphite, bis(2,6-di-tert-butyl-6-methylphenyl)neopentaerythritol diphosphite, 4,4'-butylene bis(3-methyl phosphite) 6-tert-butylphenyl diisotridecyl) ester, tetraphenyl dipropylene glycol diphosphite, tetraphenyl tetrakis(tridecalyl)neopenterythritol tetraphosphite, tetrakis(tridecyl)phosphite C12~C15-yl)-4,4'-isopropylidene diphenyl ester, tetrakis(tridecayl)-1,1,3-tris(2-methyl-5-tert-butyl-4-hydroxybenzene) hydroxy)butane diphosphite, 2,4,8,10-tetra-tert-butyl-6-[3-(3-methyl-4-hydroxy-5-tert-butylphenyl)propoxy base]dibenzo[d,f][1,3,2]dioxaphosphorane, phosphorous acid 2,2-methylenebis(4,6-tert-butylphenyl)-2 - Ethylhexyl, trilauryl trithiophosphite, etc., but the present invention is not limited to these examples. These phosphites may be used individually or in combination of 2 or more types.

Examples of thioethers include: 2,2'-thiodiglycolic acid, (ethylidenedithio)diacetic acid, 2,2'-(ethylidenedithio)diethanol, 3,3 '-Thiodipropionic acid, 3,3'-dimethyl thiodipropionate, 3-laurylthiopropionic acid, methyl 3-laurylthiopropionate, (3-octylthiopropionate Acid) neopenterythritol tetraester, (3-decylthiopropionic acid) neopenterythritol tetraester, (3-laurylthiopropionic acid) neopenterythritol tetraester, (3-oleylthiopropionic acid) Propionic acid) neopenterythritol tetraester, (3-stearylthiopropionic acid) neopenterythritol tetraester, (3-laurylthiopropionic acid)-4,4'-thiobis(3- Methyl-5-tert-butyl-4-phenol) ester, dioctylthiodipropionate, didecylthiodipropionate, dilaurylthiodipropionate, 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, 2,4-bis(dodecyl sulfide) (thiomethyl)-o-cresol, etc., but the present invention is not limited only to these examples. These thioethers may be used individually, or two or more types may be used in combination.

From the viewpoint of inhibiting radical polymerization during various operations in storage, transportation, composition preparation and handling, etc. and ensuring radical polymerizability according to the use, the content of the radical polymerization inhibitor is relative to the radical polymerizable component. (monomer components), the total amount is preferably 0.005 to 2 parts by mass, more preferably 0.01 to 1 part by mass, and still more preferably 0.02 to 0.5 parts by mass. In addition, in this specification, a radically polymerizable component means, for example, the above-mentioned 2-oxymethacrylic acid, a radically polymerizable carboxylate, and the following radically polymerizable compound.

[Radically polymerizable compound] The polymerizable composition of the present invention may also contain radically polymerizable compounds other than the 2-oxymethacrylic acid (A) of the present invention, so as to be components applicable to curable compositions used for various coatings or three-dimensional modeling, for example. , copolymer raw materials, etc.

Radically polymerizable compounds can be classified into compounds having one radical polymerizable group in the same molecule, that is, monofunctional radical polymerizable monomers, and compounds having two or more radical polymerizable groups in the same molecule, that is, monofunctional radical polymerizable monomers. Multifunctional free radical polymerizable compound.

[Monofunctional radical polymerizable monomer] Examples of the monofunctional radical polymerizable monomer (a) include (meth)acrylate, (meth)acrylamide, 2-(meth)allyloxy methacrylate, and unsaturated monomer. Carboxylic acid, unsaturated polycarboxylic acid, unsaturated monocarboxylic acid with chain extension between unsaturated group and carboxyl group, unsaturated acid anhydride, aromatic vinyl, N-substituted maleimide, conjugated Diene, vinyl ester, vinyl ether, N-vinyl compound, unsaturated isocyanate, etc., but the present invention is not limited only to these examples. These monofunctional radical polymerizable monomers may be used individually, or two or more types may be used in combination.

Examples of the (meth)acrylate include: (meth)acrylic acid methyl ester, (meth)ethyl acrylate, (meth)acrylic acid n-propyl ester, (meth)acrylic acid isopropyl ester, (meth)acrylic acid isopropyl ester, and (meth)acrylic acid ethyl ester. ) n-butyl acrylate, 2-butyl (meth)acrylate, 3-butyl (meth)acrylate, n-pentyl (meth)acrylate, 2-pentyl (meth)acrylate, (meth)acrylic acid Third amyl ester, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, tridecyl (meth)acrylate, cyclohexyl (meth)acrylate Ester, cyclohexylmethyl (meth)acrylate, octyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, benzyl (meth)acrylate, (meth)acrylic acid Phenyl ester, isocamphenyl (meth)acrylate, adamantyl (meth)acrylate, tricyclodecanyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, (meth)acrylate 2-hydroxypropyl acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxy(meth)acrylate Butyl ester, 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, (meth)acrylic acid (3,4-epoxy) Cyclohexyl)methyl ester, N,N-dimethylaminoethyl (meth)acrylate, α-hydroxymethylmethyl acrylate, α-hydroxymethylethyl acrylate, etc., but the present invention is not limited only to these examples. . These (meth)acrylates may be used individually, or two or more types may be used in combination.

Examples of (meth)acrylamide include N,N-dimethyl(meth)acrylamide, N-hydroxymethyl(meth)acrylamide, acrylomorpholine, and the like. The present invention is not limited only to this example. These (meth)acrylamides may be used individually or in combination of 2 or more types.

Examples of 2-(meth)allyloxy methacrylate include methyl 2-(meth)allyloxy methacrylate and ethyl 2-(meth)allyloxy methacrylate. Ester, 2-(meth)allyloxy methacrylate n-propyl ester, 2-(meth)allyloxy methacrylate isopropyl ester, 2-(meth)allyloxy methacrylate n-propyl ester Butyl ester, 2-(meth)allyloxy methacrylate 2-butyl ester, 2-(meth)allyloxy methacrylate 3-butyl ester, 2-(meth)allyloxymethacrylate n-pentyl acrylate, 2-(meth)allyloxy methacrylate second pentyl ester, 2-(meth)allyloxy methacrylate third pentyl ester, 2-(meth)allyl Neopentyl oxymethacrylate, n-hexyl 2-(meth)allyloxy methacrylate, second hexyl 2-(meth)allyloxy methacrylate, 2-(meth)ene n-heptyl propoxy methacrylate, 2-(meth)allyloxy n-octyl methacrylate, 2-octyl 2-(meth)allyloxy methacrylate, 2-(methyl ) tert-octyl allyloxy methacrylate, 2-ethylhexyl 2-(meth)allyloxy methacrylate, 2-(meth)allyloxy octyl methacrylate, 2 -(Meth)allyloxy nonyl methacrylate, 2-(meth)allyloxy decyl methacrylate, 2-(meth)allyloxy undecyl methacrylate, 2- (Meth)allyloxy lauryl methacrylate, 2-(meth)allyloxy tridecyl methacrylate, 2-(meth)allyloxy myristyl methacrylate, 2- Pentadecyl (meth)allyloxy methacrylate, cetyl 2-(meth)allyloxy methacrylate, heptadecyl 2-(meth)allyloxy methacrylate, 2 -(Meth)allyloxy stearyl methacrylate, 2-(meth)allyloxy nonadenic acid methacrylate, 2-(meth)allyloxy methacrylic acid eicosyl ester, 2-(Meth)allyloxy methacrylate wax ester, 2-(meth)allyloxy methacrylate wax ester, 2-(meth)allyloxy methacrylate wax ester, 2 -(Meth)allyloxy methacrylate 1,1-dimethyl-2-propenyl ester, 2-(meth)allyloxy methacrylate 2-methylbutenyl ester, 2-(methyl) 3-methyl-2-butenyl)allyloxy methacrylate, 3-methyl-3-butenyl 2-(meth)allyloxy methacrylate, 2-(methyl) 2-Methyl-3-butenyl allyloxy methacrylate, 2-(meth)allyloxy oleyl methacrylate, 2-(meth)allyloxy linoleyl methacrylate , 2-(meth)allyloxy linoleyl methacrylate, 2-(meth)allyloxy cyclopentyl methacrylate, 2-(meth)allyloxy methacrylic acid cyclopentyl ester Pentyl methyl ester, 2-(meth)allyloxycyclohexyl methacrylate, 2-(meth)allyloxycyclohexyl methacrylate, 2-(meth)allyloxy 4-Methylcyclohexyl methacrylate, 4-tert-butylcyclohexyl methacrylate, 2-(meth)allyloxy methacrylate tricyclodecane Ester, 2-(meth)allyloxyisocamphenyl methacrylate, 2-(meth)allyloxydiamantyl methacrylate, 2-(meth)allyloxymethacrylic acid bicyclo Pentyl ester, 2-(meth)allyloxydicyclopentenyl methacrylate, 2-(meth)allyloxyphenyl methacrylate, 2-(meth)allyloxymethyl Methylphenyl acrylate, 2-(meth)allyloxydimethylphenyl methacrylate, 2-(meth)allyloxytrimethylphenyl methacrylate, 2-(methyl) 4-tert-butylphenyl allyloxy methacrylate, 2-(meth)allyloxy benzyl methacrylate, 2-(meth)allyloxy diphenyl methyl methacrylate , 2-(Meth)allyloxy diphenylethyl methacrylate, 2-(meth)allyloxy triphenylmethyl methacrylate, 2-(meth)allyloxymethyl Phenylyl acrylate, 2-(meth)allyloxy naphthyl methacrylate, 2-(meth)allyloxy anthracene methacrylate, 2-(meth)allyloxymethyl Methoxyethoxyethyl acrylate, 2-(meth)allyloxymethoxyethoxyethyl methacrylate, 2-(meth)allyloxymethoxyethoxyethyl methacrylate Oxyethyl ester, 3-methoxybutyl 2-(meth)allyloxy methacrylate, 2-(meth)allyloxyethoxyethyl methacrylate, 2-(methyl )allyloxyethoxyethoxyethyl methacrylate, 2-(meth)allyloxycyclopentoxyethyl methacrylate, 2-(meth)allyloxymethacrylic acid Cyclohexoxyethyl ester, 2-(meth)allyloxy methacrylate cyclopentoxyethoxyethyl ester, 2-(meth)allyloxy methacrylate cyclohexyloxyethoxy Ethyl ester, 2-(meth)allyloxydicyclopentenoxyethyl methacrylate, 2-(meth)allyloxyphenoxyethyl methacrylate, 2-(methyl) Allyloxyphenoxyethoxyethyl methacrylate, 2-(meth)allyloxyglycidyl methacrylate, 2-(meth)allyloxymethacrylic acid β-methyl 2-ethyl glycidyl ester, 2-(meth)allyloxy methacrylate β-ethyl glycidyl ester, 2-(meth)allyloxy methacrylic acid 3,4-epoxycyclohexylmethyl Ester, 2-(meth)allyloxy methacrylate 2-oxetane methyl ester, 2-(meth) allyloxy methacrylate 3-methyl-3-oxetane methyl ester , 2-(Meth)allyloxy methacrylate 3-ethyl-3-oxocyclobutane methyl ester, 2-(meth)allyloxy methacrylate tetrahydrofuran ester, 2-(methyl) Allyloxytetrahydrofuran methyl methacrylate, 2-(meth)allyloxytetrahydropyranyl methacrylate, 2-(meth)allyloxymethacrylate dioxolane, 2-(Meth)allyloxydioxanyl methacrylate, etc., but the present invention is not limited only to these examples. These 2-(meth)allyloxy methacrylates may be used individually, or two or more types may be used in combination.

Examples of unsaturated monocarboxylic acids include (meth)acrylic acid, crotonic acid, cinnamic acid, vinyl benzoic acid, and the like, but the present invention is not limited to these examples. These unsaturated monocarboxylic acids may be used individually, or two or more types may be used in combination.

Examples of the unsaturated polycarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, etc., but the present invention is not limited only to these examples. These unsaturated polycarboxylic acids may be used individually, or two or more types may be used in combination.

Examples of the unsaturated monocarboxylic acid with a chain extended relationship between an unsaturated group and a carboxyl group include succinic acid mono(2-acryloxyethyl) ester and succinic acid mono(2-methacryloxyethyl). esters, etc., but the present invention is not limited only to these examples. The unsaturated monocarboxylic acids with chain extension between the unsaturated group and the carboxyl group can be used individually, or two or more types can be used in combination.

Examples of the unsaturated acid anhydride include maleic anhydride, itaconic anhydride, and the like, but the present invention is not limited to these examples. These unsaturated acid anhydrides may be used individually, or two or more types may be used in combination.

Examples of the aromatic vinyl include styrene, α-methylstyrene, vinyltoluene, methoxystyrene, etc., but the present invention is not limited only to these examples. These aromatic vinyls may be used individually, or two or more types may be used in combination.

Examples of N-substituted maleimide include methylmaleimide, ethylmaleimide, isopropylmaleimide, and cyclohexylmaleimide. Examples include enediimide, phenylmaleimide, benzylmaleimide, naphthylmaleimide, etc., but the present invention is not limited only to these examples. These N-substituted maleic imines may be used individually, or two or more types may be used in combination.

Examples of conjugated dienes include 1,3-butadiene, isoprene, chloroprene, and the like, but the present invention is not limited to these examples. These conjugated dienes may be used individually, or 2 or more types may be used in combination.

Examples of the vinyl ester include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, and the like, but the present invention is not limited to these examples. These vinyl esters may be used individually, or two or more types may be used in combination.

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, and cyclohexyl vinyl ether. Ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, methoxyethoxyethyl vinyl ether, methoxy polyethylene glycol vinyl ether, 2-hydroxyethyl vinyl ether, 4-hydroxy butyl vinyl ether, etc., but the present invention is not limited only to these examples. These vinyl ethers may be used individually, or two or more types may be used in combination.

Examples of N-vinyl compounds include N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylimidazole, N-vinyl pholine, N-vinyl acetamide, etc., but the present invention is not limited only to these examples. These N-vinyl compounds may be used individually, or two or more types may be used in combination.

Examples of the unsaturated isocyanate include isocyanatoethyl (meth)acrylate, allyl isocyanate, and the like, but the present invention is not limited to these examples. These unsaturated isocyanates may be used individually, or two or more types may be used in combination.

The content of the monofunctional radical polymerizable monomer (a) can be adjusted according to the use and purpose. The monofunctional radical polymerizable monomer (a) may not be included. When using the monofunctional radical polymerizable monomer (a) In the case of , it is preferably 1 to 98 mass%, more preferably 2 to 95 mass%, and still more preferably 3 to 90 mass%, based on 100 mass% of the total radically polymerizable components.

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

Examples of the conjugated activated carbon-carbon double bonds include adjacently conjugated carbon-carbon double bonds such as a 1,3-butadiene structure, and adjacently conjugated carbon-carbon double bonds with carbonyl groups. Double bonds, adjacently conjugated carbon-carbon double bonds of cyano groups, adjacently conjugated carbon-carbon double bonds of aromatic rings, etc., but the present invention is not limited only to these examples. Among these conjugated activated carbon-carbon double bonds, from the viewpoint of improving polymerization activity, the carbon-carbon double bonds with adjacent conjugated carbonyl groups and the carbon-carbon double bonds with adjacent conjugated cyano groups are preferred. and aromatic rings with adjacent conjugated carbon-carbon double bonds, more preferably carbonyl groups with adjacent conjugated carbon-carbon double bonds, further preferably (meth)acrylyl, 2-(meth)allyloxy Methacrylic acid group, maleic acid imide group.

Therefore, among the polyfunctional radically polymerizable compounds, polyfunctional (meth)acrylic compounds having one or more (meth)acrylyl groups and other radically polymerizable groups, and polyfunctional (meth)acrylic compounds having one or more 2 -Polyfunctional 2-(meth)allyloxymethacrylic acid-based compounds with (meth)allyloxymethacrylyl groups and other radically polymerizable groups, and compounds with one or more maleic dibutene groups A polyfunctional maleimide compound having an acyl imine group and other radically polymerizable groups, more preferably a polyfunctional (meth)acrylic acid compound having two or more (meth)acrylyl groups, Polyfunctional 2-(meth)allyloxymethacrylic acid-based compounds having two or more 2-(meth)allyloxymethacrylyl groups, and polyfunctional 2-(meth)allyloxymethacrylic acid-based compounds having two or more maleic acid groups It is a polyfunctional maleic imine compound with an imine group.

Examples of the polyfunctional radically polymerizable compound include polyfunctional (meth)acrylates, vinyl ether group-containing (meth)acrylates, allyl group-containing (meth)acrylates, polyfunctional (meth)acrylates, Polyfunctional (meth)acrylic compounds such as (meth)acrylyl isocyanate and polyfunctional urethane (meth)acrylate; multifunctional 2-(meth)allyloxy methyl methacrylate; polyfunctional maleimide compound; polyfunctional vinyl ether; polyfunctional allyl compound; polyfunctional aromatic vinyl, etc.; however, the present invention is not limited to these examples. These polyfunctional radically polymerizable compounds may be used individually, or two or more types may be used in combination.

Examples of polyfunctional (meth)acrylates include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, and propylene glycol. Di(meth)acrylate, butylene glycol di(meth)acrylate, hexylene glycol di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, bisphenol A alkylene oxide ( alkylene oxide) di(meth)acrylate, bisphenol F alkylene oxide di(meth)acrylate, trimethylolpropane tri(meth)acrylate, di-trimethylolpropane tetra(meth)acrylate Acrylate, glyceryl tri(meth)acrylate, neopenterythritol tetra(meth)acrylate, dineopenterythritol penta(meth)acrylate, dineopenterythritol hexa(meth)acrylate, Addition of ethylene oxide to trimethylolpropane tri(meth)acrylate, addition of ethylene oxide to di-trimethylolpropane tetra(meth)acrylate, addition of ethylene oxide to neopentylerythritol Tetra(meth)acrylate, ethylene oxide addition, dineopenterythritol hexa(meth)acrylate, propylene oxide addition, trimethylolpropane tri(meth)acrylate, propylene oxide addition Di-trimethylolpropane tetra(meth)acrylate, propylene oxide added to neopentaerythritol tetra(meth)acrylate, propylene oxide added to dineopenterythritol hexa(meth)acrylate, Addition of ε-caprolactone to trimethylolpropane tri(meth)acrylate, addition of ε-caprolactone to di-trimethylolpropane tetra(meth)acrylate, addition of ε-caprolactone to new Pentaerythritol tetra(meth)acrylate, ε-caprolactone addition dipenterythritol hexa(meth)acrylate, etc., but the present invention is not limited only to these examples. These polyfunctional (meth)acrylates may be used individually, or two or more types may be used in combination.

Examples of the vinyl ether group-containing (meth)acrylate include 2-vinyloxyethyl (meth)acrylate, 3-vinyloxypropyl (meth)acrylate, and 1-vinyloxypropyl (meth)acrylate. Methyl-2-vinyloxyethyl ester, 2-vinyloxypropyl (meth)acrylate, 4-vinyloxybutyl (meth)acrylate, 4-vinyloxycyclohexyl (meth)acrylate , 5-vinyloxypentyl (meth)acrylate, 6-vinyloxyhexyl (meth)acrylate, 4-vinyloxymethylcyclohexylmethyl (meth)acrylate, (meth)acrylic acid Ethyleneoxymethylphenyl methyl ester, 2-(ethyleneoxyethoxy)ethyl (meth)acrylate, 2-(ethyleneoxyethoxyethoxyethoxy)ethyl (meth)acrylate ester, etc., but the present invention is not limited only to these examples. These vinyl ether group-containing (meth)acrylates may be used individually, or two or more types may be used in combination.

Examples of the allyl group-containing (meth)acrylate include allyl (meth)acrylate, but the present invention is not limited to this example.

Examples of the polyfunctional (meth)acrylyl group-containing isocyanate include tris(acryloxyethyl)isocyanurate and tris(methacryloxyethyl)isocyanurate. Oxyethyl) ester, alkylene oxide addition to tris(acryloxyethyl)isocyanurate, alkylene oxide addition to tris(methacryloyloxyethyl)isocyanurate etc., but the present invention is not limited only to this example. These polyfunctional (meth)acrylyl group-containing isocyanurates can be used individually, or two or more types can be used in combination.

Examples of the polyfunctional urethane (meth)acrylate include the use of polyfunctional isocyanates such as toluene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, and 2-hydroxyethyl (meth)acrylate. polyfunctional urethane (meth)acrylate, etc. obtained by the reaction of hydroxyl-containing (meth)acrylate such as 2-hydroxypropyl (meth)acrylate, etc., but the present invention is not limited only to this Example.

Examples of the polyfunctional 2-(meth)allyloxy methacrylate include the polyfunctional 2-(meth)allyloxy methacrylate described in Japanese Patent No. 05689628. However, The present invention is not limited only to this example. These polyfunctional 2-(meth)allyloxy methacrylates may be used individually, or two or more types may be used in combination.

Examples of polyfunctional maleimide compounds include 4,4'-diphenylmethane bismaleimide, m-phenylene bismaleimide, and bisphenol A. Diphenyl ether bis-maleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bis-maleimide, 4-methyl Base-1,3-phenyl bis-maleyl imide, 1,6-bis-maleyl imide-(2,2,4-trimethyl)hexane, phenylmethane butyl enediimide oligomers, etc., but the present invention is not limited only to these examples. These polyfunctional maleimide compounds may be used individually, or two or more types may be used in combination.

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, and hexylene glycol divinyl ether. Ether, bisphenol A alkylene oxide divinyl ether, bisphenol F alkylene oxide divinyl ether, trimethylolpropane triethylene ether, di-trimethylolpropane tetraethylene ether, glyceryl triethylene ether, neopentyl ether Alcohol tetraethylene ether, dipenterythritol pentaethylene ether, dipenterythritol hexaethylene ether, ethylene oxide added to trimethylolpropane triethylene ether, ethylene oxide added to di-trimethylol Propane tetraethylene ether, ethylene oxide added to neopentyritol tetraethylene ether, ethylene oxide added to dineopenterythritol hexaethylene ether, etc., but the present invention is not limited to these examples. These polyfunctional vinyl ethers may be used individually, or two or more types may be used in combination.

Examples of the polyfunctional allyl compound include ethylene glycol diallyl ether, diethylene glycol diallyl ether, polyethylene glycol diallyl ether, propylene glycol diallyl ether, and butylene glycol diallyl ether. Allyl ether, hexylene glycol diallyl ether, bisphenol A alkylene oxide diallyl ether, bisphenol F alkylene oxide diallyl ether, trimethylolpropane triallyl ether, di-trimethylol Propane tetraallyl ether, glycerol triallyl ether, neopentylerythritol tetraallyl ether, dineopenterythritol pentaallyl ether, dineopenterythritol hexaallyl ether, ethylene oxide plus trimethylol Triallyl ether of propane, addition of ethylene oxide to di-trimethylolpropane tetraallyl ether, addition of ethylene oxide to neopentyl glycol tetraallyl ether, addition of ethylene oxide to dineopenterythritol Polyfunctional allyl ethers such as alcohol hexaallyl ether; isocyanurates containing multifunctional allyl groups such as triallyl isocyanate; diallyl phthalate, biphenyl dicarboxylate Polyfunctional allyl esters such as allyl ester; bisallyl nadimide compounds, etc.; however, the present invention is not limited to these examples. These polyfunctional allyl compounds may be used individually, or two or more types may be used in combination.

Examples of the polyfunctional aromatic vinyl include divinylbenzene, but the present invention is not limited to this example.

The polyfunctional radical polymerizable compound may be an oligomer or a polymer in which the skeleton part other than the radical polymerizable group has a repeating unit based on a monomer. When the molecular weight of the polyfunctional radical polymerizable compound is less than 1,000, it can be classified into an oligomer, and when the molecular weight is 1,000 or more, it can be classified into a polymer.

Examples of the skeleton of the oligomer or polymer of the polyfunctional radical polymerizable compound include a polyester skeleton, a polyether skeleton, a polyurethane skeleton, polybutadiene, or polyisoprene. Conjugated diene polymer skeleton such as olefin, poly(meth)acrylate skeleton, phenol resin skeleton, aniline resin skeleton, polyolefin skeleton, polyamide skeleton, cyclic olefin polymer skeleton, polysiloxane Alkane-based skeleton, etc., but the present invention is not limited to these examples. Among these skeletons, preferred are polyester skeletons, polyether skeletons, polyurethane skeletons, conjugated diene polymer skeletons, poly(meth)acrylate skeletons, phenolic resin skeletons, and Aniline resin skeleton. The skeleton part and the radically polymerizable group only need to be bonded through a covalent bond, and preferably they are bonded through an ester bond and/or a urethane bond.

Examples of oligomers or polymers of polyfunctional radical polymerizable compounds include urethane (meth)acrylic acid in which a (meth)acrylyl group is bonded to a skeleton moiety via a urethane bond. Ester-based polymerizable oligomer, a urethane (meth)acrylate-based polymer in which a (meth)acrylyl group is bonded to a skeleton part via a urethane bond, having the ability to make (meth)acrylic acid Epoxy (meth)acrylate polymerizable oligomer added to the structure of epoxy resin (oligomer or polymer having an epoxy group), capable of adding (meth)acrylic acid to epoxy resin Epoxy (meth)acrylate polymer (oligomer or polymer with epoxy group) structure, polyester (meth)acrylate (meth)acrylate group bonded to the polyester skeleton via ester bond (meth)acrylate polymerizable oligomer, a (meth)acrylate polymer in which a (meth)acryl group is bonded to a polyester skeleton via an ester bond, and a (meth)acrylate group is bonded to a polyester skeleton via an ester bond. Phenylmethane (meth)acrylate polymerizable oligomer bonded to the phenol resin skeleton, phenylmethane (meth)acrylate whose (meth)acrylyl group is bonded to the phenol resin skeleton via an ester bond It is a phenylmethane maleimide polymeric oligomer in which the maleimide group is directly bonded to the aniline resin skeleton. The maleimide group is directly bonded to aniline. However, the present invention is not limited only to these examples.

Polyfunctional radically polymerizable compounds are readily commercially available. Examples of polyfunctional radical polymerizable compounds that are easily commercially available include: Trade names: Light Acrylate 3EG-A, Light Acrylate 4EG-A, Light Acrylate 9EG- manufactured by Kyeisha Chemical Co., Ltd. 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.;

Manufactured by SARTOMER Company, 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, SR 480, CD540 , SR541, CD542, SR603, SR644, SR740, SR9036, SR351S, SR368, SR415, SR444, SR454, SR492, SR499, CD501, SR502, SR9020, 9021, SR9035, SR350, SR9009, SR9011, SR295, SR355, SR 494、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, CN982E75, CN982P90, CN983, CN985B88, CN989, CN991 , CN996, CN9001, CN9002, CN9004, CN9005, CN9006, CN9007 , CN9008, CN9009, CN9010, CN9011, CN9014, CN9178, CN9788, CN9893, CN902J75, CN970A60, CN970E60, CN970H75, CN971, CN971A80, CN972, CN973, CN973A80, CN973H85, CN97 3J75, CN975, CN977C70, CN978, CN992, CN994, CN997 , CN999, CN9165, CN9782, CN9783, CN1963, CN2901, CN2902, CN2920, CN2921, CN3210, CN3211, CN104, CN104A80, CN104B80, CN104D80, CN111US, CN112C60, CN113D70, CN115, CN 116, CN117, CN118, CN119, CN120, CN120A75 , CN120B60, CN120B80, CN120C60, CN120C80, CN120D80, CN120E50, CN120M50, CN121, CN132, CN133, CN136, CN137, CN151, CN152, CNUVE151, CNUVE150/80, CN160, CN2100, CN21 01. CN2102E, CN292, CN293, CN394, CN296 , CN299, CN2200, CN2203, CN2250, CN2251, CN2252, CN2253, CN2254, CN2255, CN2256, CN2257, CN2258, CN2259, CN2260, CN2261, CN2262, CN2270, CN2271E, CN2272, CN2273, CN2 276, 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 wait;

Manufactured by 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, etc.;

Manufactured by Japan Synthetic Chemical Industry Co., Ltd., trade names: Purple UV-1700B, Purple UV-6300B, Purple UV-7550B, Purple UV-7600B, Purple UV-7605B, Purple UV-7610B, Purple UV-7620EA, Purple UV- 7630B, Purple UV-7640B, Purple UV-7650B, Purple UV-6630B, Purple UV-7000B, Purple UV-7510B, Purple UV-7461TE, Purple UV-2000B, Purple UV-2750B, Purple UV-3000B, Purple UV- 3200B, Purple UV-3210EA, Purple UV-3300B, Purple UV-3310B, Purple UV-3500BA, Purple UV-3520TL, Purple UV-3700B, Purple UV-6640B, etc.;

Manufactured by Toa Gosei 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.;

Manufactured by Nippon Shokubai Co., Ltd., product names: VEEA, VEEM, etc.; manufactured by Kuraray Co., Ltd., product number: UC-203; manufactured by Daiwa Chemical Industry Co., Ltd., product number: BMI-1000, BMI-2000, BMI- 2300, BMI-3000, BMI-4000, BMI-5100, BMI-7000, BMI-TMH, etc.; manufactured by Maruzen Petrochemical Co., Ltd., product number: BANI-X, BANI-M, etc.; however, the present invention is not limited to This example. These polyfunctional radically polymerizable compounds may be used individually, or two or more types may be used in combination.

The content of the polyfunctional radical polymerizable compound (b) may be adjusted according to the use and purpose, and the polyfunctional radical polymerizable compound (b) may not be included in the case where the polyfunctional radical polymerizable compound (b) is used. , relative to the total of 100 mass% of radically polymerizable components, preferably 1 to 98 mass%, more preferably 2 to 95 mass%, and still more preferably 3 to 90 mass%.

The content of the radically polymerizable compound (that is, the total content of the monofunctional radically polymerizable monomer (a) and the polyfunctional radically polymerizable compound (b)) can be adjusted according to the use and purpose, and it does not need to contain radical polymerization. When a radically polymerizable compound is used, it is preferably 1 to 98% by mass, more preferably 2 to 95% by mass, and still more preferably 3%, based on 100% by mass of the total number of radically polymerizable components. ~90% by mass.

[Radical polymerization initiator] Radical polymerization initiators can be classified into optical radical initiators that generate free radicals by irradiation of active energy rays, and thermal radical initiators that generate free radicals by heating. You can choose according to the use and purpose. , it is also possible to use a photo radical initiator and a thermal radical initiator together.

Examples of the photoradical initiator include alkylphenone compounds, benzophenone compounds, benzoin compounds, ketal compounds, anthraquinone compounds, phosphine oxide compounds, 9- oxygen sulfur Series compounds, halomethyl trichloride series compounds, halomethylation Oxidazole-based compounds, biimidazole-based compounds, oxime ester-based compounds, titanocene-based compounds, benzoate-based compounds, acridine-based compounds, etc., but the present invention is not limited only to these examples. . These photoradical initiators may be used individually, or two or more types may be used in combination.

Specific examples include: acetophenone, 1,1-dichloroacetophenone, 2,2-diethoxyacetophenone, and 2,2-dimethoxy-2-phenylphenethyl Ketone, 2,2-diethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenylketone, 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- Methylpropanyl)benzyl]phenyl}-2-methylpropan-1-one, 2-methyl-1-(4-methylthiophenyl)-2- Phinylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4- Phylinophenyl)-1-butanone, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4- Phylyl)phenyl]-1-butanone and other alkylbenzophenone compounds; benzophenone, 4,4'-bis(dimethylamino)benzophenone, 2-carboxybenzophenone, Benzophenone compounds such as 4-benzoyl-4'-methyldiphenyl sulfide; benzoin compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; acetophenone dimethyl ketal compounds such as benzil dimethyl ketal; 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-chloroanthraquinone, 2-pentanthraquinone Anthraquinone compounds such as anthraquinone;

2,4,6-Trimethylbenzoyldiphenylphosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, Phosphine oxide compounds such as bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; 9-oxosulfide , 2-ethyl-9-oxosulfide , 2-isopropyl-9-oxosulfide , 2-Chloro-9-oxosulfide , 2,4-dimethyl-9-oxosulfide , 2,4-diethyl-9-oxosulfide , [3-(3,4-dimethyl-9-side oxysulfide -2-yl)oxy-2-hydroxypropyl]-trimethylammonium chloride and other 9-oxosulfides System compound; 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-second-third , 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-second-three , 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-second-three , 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)-second-three Isohalomethylated tris Compound; 2-trichloromethyl-5-[β-(2'-benzofuranyl)vinyl]-1,3,4- Oxidazole, 2-trichloromethyl-5-[β-(2'-(6''-benzofuranyl)vinyl)]-1,3,4- Oxidazole, 2-trichloromethyl-5-furyl-1,3,4- Halomethylation of diazoles etc. Diazole compounds; 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, 2,2'-bis(2,4,6-trichlorophenyl)-4 ,4',5,5'-tetraphenyl-1,2'-biimidazole and other biimidazole compounds; 1-[4-(phenylthio)-,2-(O-benzoyl oxime)] -1,2-octanedione, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(O-acetyl oxime ) Oxime ester compounds such as ethanone; bis(eta5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-benzene Titanium-based compounds such as titanium; bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl oxide Phosphines and other phosphine oxide compounds; benzoate compounds such as p-dimethylaminobenzoic acid and p-diethylaminobenzoic acid; acridine compounds such as 9-phenylacridine; but the present invention It is not limited to the above examples.

The thermal radical initiator is preferably an organic peroxide-based initiator or an azo-based initiator. Specific examples thereof include the following initiators.

Methyl ethyl ketone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide, methyl peroxyacetyl acetate, 1,1-bis(tert-hexylperoxy) )-3,3,5-trimethylcyclohexane, 1,1-bis(tert-hexylperoxy)cyclohexane, 1,1-bis(tert-butylperoxy)-3,3 ,5-trimethylcyclohexane, 1,1-bis(tert-butylperoxy)-2-methylcyclohexane, 1,1-bis(tert-butylperoxy)cyclohexane , 1,1-bis(tert-butylperoxy)cyclododecane, 1,1-bis(tert-butylperoxy)butane, 2,2-bis(4,4-di- Tributylperoxycyclohexyl)propane, p-menthane hydroperoxide, dicumyl hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide , tert-hexyl hydroperoxide, tert-butyl hydroperoxide, α,α'-bis(tert-butylperoxy)diisopropylbenzene, dicumyl peroxide, 2,5-diisopropylbenzene Methyl-2,5-bis(tert-butylperoxy)hexane, tert-butylcumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2, 5-Bis(tert-butylperoxy)hexyne-3, isobutyl peroxide, 3,5,5-trimethylhexyl peroxide, octyl peroxide, lauryl peroxide, hard peroxide Fatty acid, peroxysuccinic acid, m-toluyl benzyl peroxide, benzoyl peroxide, di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, peroxide Bis(4-tert-butylcyclohexyl)dicarbonate, di-2-ethoxyethyl peroxydicarbonate, di-2-ethoxyhexyl peroxydicarbonate, di-3-peroxydicarbonate -Methoxybutyl ester, di-butyl peroxydicarbonate, di(3-methyl-3-methoxybutyl)peroxydicarbonate, α,α'-bis(neodecyl) Peroxy) (neodecanoyl peroxy) diisopropylbenzene, cumyl peroxyneodecanoate (Cumyl peroxyneodecanoate), neodecanoic acid 1,1,3,3-tetramethylbutyl peroxide, peroxide 1-cyclohexyl-1-methylethyl neodecanoate, tert-hexyl peroxyneodecanoate, tert-butyl peroxyneodecanoate, t-hexyl peroxy pivalate ), tert-butyl peroxypivalate, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis(2 -Ethylhexylperoxy)hexanoate, 1-cyclohexyl-1-methylethyl peroxy-2-ethylhexanoate, tert-hexyl peroxy-2-ethylhexanoate, peroxy-2-ethylhexanoate tert-butyl 2-ethylhexanoate, tert-butyl peroxyisopropyl monocarbonate, tert-butyl peroxyisobutyrate, tert-butyl peroxymalate, peroxy-3,5 , tert-butyl 5-trimethylhexanoate, tert-butyl peroxylaurate, tert-butyl peroxyisopropyl monocarbonate, tert-butyl peroxy-2-ethylhexyl monocarbonate, peroxy tert-butyl acetate, tert-butyl peroxy-m-toluyl benzoate, tert-butyl peroxybenzoate, di-tert-butyl peroxyisophthalate, 2,5-dimethyl -2,5-bis(m-toluylperoxy)hexane, tert-hexyl peroxybenzoate, 2,5-dimethyl-2,5-bis(benzylperoxy) Hexane, tert-butyl peroxyallyl monocarbonate, tert-butyltrimethylsilyl peroxide, 3,3',4,4'-tetrakis(tert-butylperoxycarbonyl)diphenyl Organic peroxide-based initiators such as methanone and 2,3-dimethyl-2,3-diphenylbutane.

2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, 1-[(1-cyano-1-methylethyl)azo]methamide, 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'-Azo Bis(2-methylpropionamidine) dihydrochloride, 2,2'-Azobis(2-methyl-N-phenylpropionamidine) dihydrochloride, 2,2'- Azobis[N-(4-chlorophenyl)-2-methylpropionamidine]dihydrochloride, 2,2'-azobis[N-(4-hydroxyphenyl)-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-imidazoline) -2-yl)propane]dihydrochloride, 2,2'-azobis[2-(4,5,6,7-tetrahydro-1H-1,3-diazazo-2-yl)propane ]Dihydrochloride, 2,2'-azobis[2-(3,4,5,6-tetrahydropyrimidine (tetrahydropyrimidine)-2-yl)propane]dihydrochloride, 2,2'- Azobis[2-(5-hydroxy-3,4,5,6-tetrahydropyrimidin-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]propanamide}, 2,2'-azobis{2-methyl-N- [1,1-bis(hydroxymethyl)ethyl]propionamide}, 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], 2,2 '-Azobis(2-methylpropylamide), 2,2'-Azobis(2,4,4-trimethylpentane), 2,2'-Azobis(2-methyl Propane), dimethyl-2,2-azobis(2-propionic acid methyl ester), 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis[2 -(hydroxymethyl)propionitrile] and other azo starters.

These may be used individually by 1 type, and may be used in combination of 2 or more types.

The content of the radical polymerization initiator is not particularly limited, but it is preferably 0.05 to 10.0 parts by mass, more preferably 0.1 to 7.0 parts by mass, and still more preferably 100 parts by mass in total of the radical polymerizable components. 0.2～5.0 parts by mass.

[Compounds having reactive groups other than radical polymerizability] Low-molecular compounds, oligomers, or polymer compounds having reactive groups other than radical polymerizability can also be used to improve various properties such as heat resistance and adhesion depending on the application.

Examples of such compounds include compounds having a cationic polymerizable group such as an epoxy group, an oxetanyl group, and a vinyl ether group; compounds having an epoxy group, Compounds with functional groups that react with carboxyl groups, such as oxazoline groups, carbodiimide groups, and aziridyl groups; compounds with isocyanate groups, amine resins, and other compounds with functional groups that react with hydroxyl groups, etc.

The content of the compound having reactive groups other than radical polymerizability can be adjusted according to the use and purpose. The compound having reactive groups other than radical polymerizability may not be contained. When using the compound having reactivity other than radical polymerizability, In the case of a radical compound, the amount is preferably 1 to 300 parts by mass, more preferably 2 to 200 parts by mass, and still more preferably 3 to 100 parts by mass based on 100 parts by mass of the radically polymerizable components in total.

[organic solvent] An appropriate amount of organic solvent may also be included from the viewpoints of adjusting the viscosity, adjusting the thickness of the coating film, and dissolving the resin in the composition.

Examples of the organic solvent include: monoalcohols such as methanol, ethanol, isopropyl alcohol, n-butanol, and dibutanol; diols such as ethylene glycol and propylene glycol; tetrahydrofuran, diol, etc. Alkanes and other cyclic ethers; 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, 3-methoxybutanol and other glycol monoethers; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol ethyl methyl ether, diethylene glycol Glycol ethers such as glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether ethyl Acid ester, 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 Acid ester, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, 3-methoxy acetate Esters of glycol monoethers such as butyl ester; 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, acetyl Alkyl esters such as methyl acetate and ethyl acetate; 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; amides such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone; however, the present invention is not limited to these examples. . These organic solvents may be used individually, or two or more types may be used in combination.

The content of the organic solvent may be adjusted according to the use and purpose, and the organic solvent may not be included. When an organic solvent is used, it is preferably 1 to 1,000 parts by mass relative to 100 parts by mass of the radically polymerizable components in total. More preferably, it is 2-700 parts by mass, and still more preferably 3-500 parts by mass.

In addition, the content of other components other than the above-mentioned components may be adjusted according to the use and purpose, and the content of other components other than the above-mentioned components may not be contained. When other components other than the above-mentioned components are used, relative to the total of 100 radically polymerizable components Parts by mass are preferably 1 to 300 parts by mass, more preferably 2 to 200 parts by mass, and still more preferably 3 to 100 parts by mass.

<Polymer of the present invention> Furthermore, the present invention is also a polymer obtained by polymerizing the above-mentioned polymerizable composition of the present invention under radical generating conditions.

Examples of the free radical generation method include a method of heating the polymerizable composition of the present invention, and/or a method of irradiating the polymerizable composition of the present invention with active energy rays. Heating or irradiation of active energy rays can be performed in one stage or divided into two or more stages. Heating and irradiation with active energy rays can also be combined, either simultaneously or separately. When heating or active energy ray irradiation is performed, the polymerizable composition of the present invention is preferably in a state containing the above-mentioned radical polymerization initiator.

The heating temperature can be appropriately selected according to the presence, type, content, and use of the radical polymerization initiator. When a thermal radical initiator is used, it is 40°C or higher, more preferably 50°C or higher, and still more preferably Above 60℃.

As the active energy rays, those commonly used can be used, and examples thereof include electromagnetic waves such as gamma rays, X-rays, ultraviolet rays, visible rays, and infrared rays, and particle beams such as electron beams, neutron beams, and proton beams. Among them, in terms of energy intensity, energy ray generating device, etc., gamma rays, X-rays, ultraviolet rays, visible rays, and electron beams are preferred, and ultraviolet rays, visible rays, and electron beams are more preferred. for ultraviolet light. When a photo-radical initiator is not used, it is better to use active energy rays with stronger energy such as gamma rays, X-rays, electron beams, etc. When a photo-radical initiator is used, it is better to use Use ultraviolet, visible light and other active energy rays that are relatively weak but easy to produce and affordable.

The polymerizable composition of the present invention has good radical polymerizability as described above, and therefore can be preferably used in, for example, coating materials, adhesives, sealants, adhesives, primers, sealants, coatings, inks, and resists. Agents, dental materials, lenses, molding materials, various methods of three-dimensional molding (inkjet, SLA, DLP), interlayers of optical films, resins for negative resists, water-absorbent resins and other motors, electronic parts, optical parts It is used for various industrial products or medical purposes such as free radical polymerization by heating or irradiation of active energy rays.

＜How to save＞ Furthermore, the present invention is a method for preserving 2-oxymethacrylic acid (A), wherein the 2-oxymethacrylic acid (A) is represented by the above formula (1), and the above 2-oxymethyl The method of preserving acrylic acid (A) includes storing the above-mentioned 2-oxymethacrylic acid (A) in the presence of a carboxylate with a cation ratio represented by the above-mentioned calculation formula (I) of 0.01 or more and less than 1, and/or Store in the presence of water with a moisture ratio expressed by the above calculation formula (II) of 0.01 or more.

The storage method of the present invention can suppress the generation of polymerization products due to cationic polymerization of 2-oxymethacrylic acid (A) represented by the above formula (1), thereby making the storage stability of 2-oxymethacrylic acid (A) excellent. .

The 2-oxymethacrylic acid (A), carboxylate, and water used in the preservation method of the present invention are the same as described above. In addition, the cation ratio and the moisture ratio are also the same as above.

The storage method is not particularly limited, but the above-mentioned 2-oxymethacrylic acid (A) can be stored in the presence of a carboxylate having a cation ratio that satisfies a specified range, and/or in water that satisfies a moisture ratio that satisfies a specified range. Preserve by known methods such as placing it in a container and letting it stand in the presence of the liquid.

As a storage temperature, from the viewpoint of suppressing radical polymerization and enabling easy control of the temperature, 0 to 50°C is preferred, and 5 to 40°C is more preferred.

The storage period is not particularly limited, but is, for example, 1 day to 2 years, preferably 1 day to 1 year. The above-mentioned 2-oxymethacrylic acid (A) can be stably stored during this period.

＜Polymer materials＞ Furthermore, the present invention is a polymer material containing 2-oxymethacrylic acid (A) represented by the above formula (1), a carboxylate and/or water, and a radical polymerization initiator, and is characterized in that it satisfies The cation ratio represented by the above calculation formula (I) is at least 0.01 and less than 1, or the moisture ratio represented by the above calculation formula (II) is at least either one of 0.01 or more.

The polymer material of the present invention can suppress the generation of polymerization products due to cationic polymerization of the above-mentioned 2-oxymethacrylic acid (A), thereby providing a polymer with excellent storage stability and desired characteristics.

The 2-oxymethacrylic acid (A), carboxylate, water, and radical polymerization initiator contained in the polymer material of the present invention are the same as above. In addition, the cation ratio and the moisture ratio are also the same as above.

The polymeric material of the present invention can be mixed with other ingredients to form a polymeric composition. Examples of the other components described above include the same components as those used in the polymerizable composition. The polymerizable composition obtained in the above manner can be preferably used in the manufacture of various industrial products or medical products. [Example]

The following examples will be disclosed to describe the present invention in more detail, but the present invention is not limited only to these examples. In addition, unless otherwise specified, "part" means "mass part" and "%" means "mass %".

<Measurement of carboxylate ions> ○Measurement device capillary electrophoresis system Agilent 7100 (Agilent Technologies Co., Ltd.) ○Measurement conditions are based on the indirect absorption method between background absorbers. Capillary: Bubble Cell Fused Silica Capillary (inner diameter 75 μm × total length 80.5 cm) Electrophoresis solution: Electrophoresis solution for anion analysis (pH = 8.2) Applied voltage: -20 kV ○The quantitative method is an internal standard method based on area ratio (internal standard Substance: sodium propionate) for quantitation. Preparation of standard sample: Dissolve sodium propionate and the substance to be quantified (sodium salt of carboxylate ion) in heavy water, quantify the molar ratio using ¹ H-NMR, and then dilute it with ultrapure water. As a standard sample for making calibration curve. Preparation of the sample for measurement: Weigh the sodium propionate aqueous solution and the test sample, and dilute it with a 0.1 normal sodium hydroxide aqueous solution and ultrapure water as the sample for measurement.

＜Measurement of molecular weight＞ ○Measuring device ACQUITY APC (Advanced Polymer Chromatography) System (Japan Waters Co., Ltd.) ○Measurement conditions Separation column: ACQUITY APC XT column, pore diameter 450 Å × 1 column, pore diameter 125 Å × 1 column, pore diameter 45 Å × 1 column Dissolution solvent: tetrahydrofuran/methanol = 2/1 (weight ratio) mixture, phosphoric acid concentration 1.0% Molecular weight standard material: polymethyl methacrylate

＜2-Oxymethacrylic acid (A) and carboxylate＞ ○2-Methoxymethacrylic acid: Prepare 2 containing 0.05% (relative to the total volume of the solution) hydroquinone monomethyl ether as a free radical polymerization inhibitor with a purity of 97.3% (8.38 mmol/g based on the concentration of 2-methoxymethacrylic acid) -Methoxymethacrylic acid. Furthermore, purity was determined using a capillary electrophoresis system.

○2-allyloxymethacrylic acid: Prepare hydroquinone monomethyl ether containing 0.04% (relative to the total amount of the solution) and 0.06% (relative to the total amount of the solution) 2,2'-(ethyldithio)diethanol as free radical polymerization inhibitors. 2-allyloxymethacrylic acid with a purity of 96.7% (based on 2-allyloxymethacrylic acid concentration of 6.80 mmol/g). Furthermore, purity was determined using a capillary electrophoresis system.

○2-Allyloxysodium methacrylate 50% aqueous solution: Add an equivalent amount (equivalent to 100% neutralization) of 2-allyloxymethacrylic acid to the 10% sodium carbonate aqueous solution for neutralization, then add concentrated and appropriate amount of water to prepare a content of 0.02% (relative to the total solution) Hydroquinone monomethyl ether and 0.03% (relative to the total amount of solution) 2,2'-(ethyldithio)diethanol are used as free radical polymerization inhibitors and 2-allyloxy methacrylic acid An aqueous solution of sodium 2-allyloxymethacrylate with a sodium concentration of 50% (3.05 mmol/g). In addition, the 2-allyloxysodium methacrylate concentration was determined by measuring 2-allyloxymethacrylate ions using a capillary electrophoresis system, and the concentration was defined as the 2-allyloxysodium methacrylate concentration.

[Comparative Example 1] Add 3.25 g of 2-methoxymethacrylic acid and 0.75 g of ultrapure water to a 50 ml frosted test tube equipped with a stirring rod, and stir evenly. Then, non-heating solvent removal and dehydration operations are performed in the following order. Add 4.0 g of diisopropyl ether and 3.0 g of acetone and stir evenly. Connect the test tube to the vacuum line and keep it at room temperature while paying attention to the boiling while slowly increasing the degree of decompression. After the pressure reaches 0.2 kPa, maintain this state for 30 minutes. After the dehydration operation is completed and normal pressure is restored, stop stirring, take out the stirring rod, and confirm the condition of the contents. The result is white turbidity. Let the turbid contents stand overnight, and a white precipitate will settle. Use decantation to remove the liquid from the test tube. Add 1.0 g of methanol to the test tube to dissolve, and add the dissolved result dropwise to a mixed solvent of acetone/hexane = 1/1 (weight ratio) for reprecipitation. The precipitate was removed by suction filtration and then vacuum dried at room temperature. The obtained solid was dissolved in heavy water with a sodium carbonate concentration of 2%, and ¹ H-NMR was measured. As a result, it was confirmed that a polymer was found. The molecular weight of the obtained solid was measured using the APC system, and the result was that the molecular weight was 99,000.

[Example 1] Add 0.15 g (1.4 mmol) of sodium carbonate and 0.75 g of ultrapure water to a 50 ml frosted test tube with a stirring rod and stir to dissolve the sodium carbonate. Then add 3.25 g (27.2 mmol) of 2-methoxymethacrylic acid. ) and stir evenly to make 10 mol% sodium salt of 2-methoxymethacrylic acid to prepare the polymerizable composition (1) of the present invention. Here, the total amount of the 2-methoxymethacrylic acid part in the polymerizable composition (1) is 27.2 mmol, and the valence of sodium ions derived from sodium 2-methoxymethacrylate is 1, mol. The number is 2.8 mmol, so the cation ratio based on the following calculation formula (I) is 0.10.

(In the calculation formula (I), the total valence of the cations derived from the carboxylate is the sum of (the valence of the cations derived from the carboxylate × the molar number of the cation); the 2-oxymethacrylic acid moiety The total amount is the mole number of 2-oxymethacrylic acid (A) + the mole number of 2-oxymethacrylate ions derived from the salt of 2-oxymethacrylic acid (A)). Then, a non-heating desolvation and dehydration operation was performed in the same manner as in Comparative Example 1. After the operation was completed, the contents of the test tube were confirmed. Contents are transparent.

[Comparative Example 2] Add 3.40 g of 2-allyloxymethacrylic acid and 0.60 g of ultrapure water to a 50 ml frosted test tube with a stirring rod and stir evenly. Then, non-heating desolvation and dehydration operations were performed in the same manner as in Comparative Example 1. After the operation was completed, the contents of the test tube were confirmed, and the result was white turbidity. The white turbid content was reprecipitated and the precipitated material was dried in the same manner as in Comparative Example 1, and ¹ H-NMR of the obtained solid was measured. As a result, a polymer was confirmed. The molecular weight of the obtained solid was measured using the APC system, and the result was that the molecular weight was 142,000.

[Example 2] Add 3.10 g (21.1 mmol) of 2-allyloxymethacrylic acid, 0.77 g (2.3 mmol) of 50% aqueous sodium 2-allyloxymethacrylate solution, and ultrapure sodium 2-allyloxymethacrylate into a 50 ml frosted test tube with a stirring rod. 0.23 g of water and stir evenly to prepare the polymerizable composition (2) of the present invention. Here, the total amount of 2-allyloxymethacrylic acid part in the polymerizable composition (2) is 23.4 mmol, and the valence number of sodium ions derived from sodium 2-allyloxymethacrylate is 1. The molar number is 2.3 mmol, so the cation ratio becomes 0.10. Then, non-heating desolvation and dehydration operations were performed in the same manner as in Comparative Example 1, and the contents of the test tube were confirmed after the operation. Contents are transparent.

[Example 3] Add 3.30 g (22.4 mmol) of 2-allyloxymethacrylic acid, 0.23 g (0.7 mmol) of 50% aqueous sodium 2-allyloxymethacrylate solution, and ultrapure sodium 2-allyloxymethacrylate into a 50 ml frosted test tube with a stirring rod. 0.49 g of water and stir evenly to prepare the polymerizable composition (3) of the present invention. Here, the total amount of 2-allyloxymethacrylic acid part in the polymerizable composition (3) is 23.1 mmol, and the valence number of sodium ions derived from sodium 2-allyloxymethacrylate is 1. The molar number is 0.7 mmol, so the cation ratio becomes 0.03. Then, non-heating desolvation and dehydration operations were performed in the same manner as in Comparative Example 1, and the contents of the test tube were confirmed after the operation. Contents are transparent.

[Example 4] Add 3.40 g (23.1 mmol) of 2-allyloxymethacrylic acid, 0.14 g (3.5 mmol) of magnesium oxide powder, and 0.60 g of ultrapure water into a 50 ml frosted test tube with a stirring rod and stir at 45°C. The polymerizable composition (4) of the present invention was prepared by salting 15 mol% of 2-allyloxymethacrylic acid with magnesium. Here, the total amount of 2-allyloxymethacrylic acid part in the polymerizable composition (4) is 23.1 mmol, and the valence number of magnesium ions derived from 2-allyloxymethacrylic acid magnesium is 2. The molar number is 3.5 mmol, so the cation ratio becomes 0.30. Then, non-heating desolvation and dehydration operations were performed in the same manner as in Comparative Example 1, and the contents of the test tube were confirmed after the operation. Contents are transparent.

[Example 5] Add 3.40 g (23.1 mmol) of 2-allyloxymethacrylic acid, 0.56 g (6.9 mmol) of zinc oxide powder, and 0.60 g of ultrapure water into a 50 ml frosted test tube with a stirring rod and stir at 45°C. The polymerizable composition (5) of the present invention was prepared by salting 60 mol% of 2-allyloxymethacrylic acid with zinc. Here, the total amount of 2-allyloxymethacrylic acid part in the polymerizable composition (5) is 23.1 mmol, and the valence number of zinc ions derived from zinc 2-allyloxymethacrylate is 2. The molar number is 6.9 mmol, so the cation ratio becomes 0.60. Then, non-heating desolvation and dehydration operations were performed in the same manner as in Comparative Example 1, and the contents of the test tube were confirmed after the operation. Contents are transparent.

[Example 6] Add 3.40 g (23.1 mmol) of 2-allyloxymethacrylic acid and 0.51 g (3.4 mmol) of N,N'-bis(2-hydroxyethyl)ethylenediamine into a 50 ml frosted test tube with a stirring rod. , 0.60 g of ultrapure water and stirred at 45°C to salt 30 mol% amine of 2-allyloxymethacrylic acid to prepare the polymerizable composition (6) of the present invention. Here, the total amount of 2-allyloxymethacrylic acid part in the polymerizable composition (6) is 23.1 mmol, and the valence number of the amine constituting the amine salt of 2-allyloxymethacrylic acid is 2. The molar number is 3.4 mmol, so the cation ratio becomes 0.30. Then, non-heating desolvation and dehydration operations were performed in the same manner as in Comparative Example 1, and the contents of the test tube were confirmed after the operation. Contents are transparent.

[Example 7] The moisture content of 2-allyloxymethacrylic acid was measured using a Karl Fischer method moisture meter, and the result was 1.25%. That is, the moisture ratio based on the following calculation formula (II) is 0.013.

Put it into a 1.5 ml glass vial until it reaches 70%, and store it in the cold room of the refrigerator (approximately 4°C). It was confirmed every three months that no polymer was produced even after 18 months of storage.

[Comparative example 3] Add the prepared 10.0 g of 2-allyloxymethacrylic acid and 5.0 g of ethyl acetate into a 50 ml frosted round-bottomed flask with a stirring rod. While heating to 60°C, slowly reduce the pressure to perform azeotropy. Dehydration. The pressure was finally reduced to 0.5 kPa, maintained for 20 minutes after reaching 0.5 kPa, and then decompressed. Fill the filter holder of the air extraction filtration device with 1 g of silica gel (Wakogel C-200, manufactured by Fujifilm and Wako Pure Chemical Industries, Ltd.) as a filter aid. Acrylic acid was extracted and filtered. The moisture content after filtration was measured using a Karl Fischer moisture meter and the result was 0.07%. That is, the moisture ratio based on the above calculation formula (II) becomes 0.0007. Put it into a 1.5 ml glass vial until it reaches 70%, and store it in the cold room of the refrigerator (approximately 4°C). Confirmation is performed every 3 months, and the results are solidified on the 15th month.

[Example 8] The content of the non-heated solvent removal and dehydration operation obtained in Example 5 (a mixture of 2-allyloxymethacrylic acid and zinc 2-allyloxymethacrylate) 1.0 g, 2.0 g of 2-ethylhexyl acrylate, and 0.09 g of 1-hydroxycyclohexyl phenyl ketone were mixed and stirred to prepare a uniform solution. Using a bar coater (Bar coater) No. 2, the obtained solution was coated on a heat-resistant acrylic film (obtained by a melt extruder using the method described in Production Example 7 of Japanese Patent Application Laid-Open No. 2019-179124 After the particles are made into a film with a thickness of 140 μm), polymerization is performed using a belt conveyor-type UV irradiation device (illuminance 500 mW/cm ² , cumulative light intensity 5 J/cm ² ). The adhesion of the polymer layer was evaluated based on JIS K 5600-5-6 (Cross-cut test). That is, the number of remaining grids without peeling or damage among all grids (10 × 10 grids = 100 grids) is evaluated, and the result is 100.

From the results of Examples 1 to 6, it is clear that the polymerizable composition of the present invention can suppress the generation of polymerization products in non-heated desolvation and dehydration operations. In addition, it is clear from the results of Example 7 that the generation of polymerization products during storage at low temperature is suppressed. Furthermore, from the results of Example 8, it is clear that the polymerizable composition of the present invention has good photoradical polymerizability.

without

without

Claims (8)

A polymerizable composition containing the following formula (1): (In the formula, R represents a hydrogen atom or a saturated or unsaturated hydrocarbon group with a carbon number of 10 or less) The 2-oxymethacrylic acid (A), carboxylate and/or water represented is characterized by: The cation ratio expressed by the following calculation formula (I) is at least 0.01 and less than 1; or the moisture ratio expressed by the following calculation formula (II) is at least one of 0.01 or more, (In the calculation formula (I), the total valence of the cations derived from the carboxylate is the sum of [the valence of the cations derived from the carboxylate × the molar number of the cation]; the 2-oxymethacrylic acid moiety The total amount is the sum of the moles of 2-oxymethacrylic acid (A) and the moles of 2-oxymethacrylate ions derived from 2-oxymethacrylic acid (A)) . The polymerizable composition of claim 1, wherein the cations derived from carboxylates include 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. More than one cation. The polymerizable composition of claim 1 or 2, wherein the carboxylate salt includes a salt selected from the group consisting of a salt of 2-oxymethacrylic acid (A), a salt of acrylic acid, and a salt of methacrylic acid. More than 1 type of carboxylate. The polymerizable composition according to any one of claims 1 to 3, wherein the amount of 2-oxymethacrylate ions contained in the carboxylate salt is relative to the amount of carboxylate ions contained in the carboxylate salt. The total amount is above 50 mol% and below 100 mol%. The polymerizable composition according to any one of claims 1 to 4, wherein R in the general formula (1) is allyl or metallyl. A polymer obtained by polymerizing the polymerizable composition of any one of claims 1 to 5 under free radical generation conditions. A method of preserving 2-oxymethacrylic acid (A), wherein the 2-oxymethacrylic acid (A) is represented by the following formula (1): (In the formula, R represents a hydrogen atom, or a saturated or unsaturated hydrocarbon group with a carbon number of 10 or less) The preservation method of the 2-oxymethacrylic acid (A) is based on the cation represented by the following calculation formula (I) The 2-oxymethacrylic acid (A) is stored in the presence of a carboxylate with a ratio of 0.01 or more and less than 1, and/or in the presence of water with a moisture ratio of 0.01 or more represented by the following calculation formula (II). ), (In the calculation formula (I), the total valence of the cations derived from the carboxylate is the sum of [the valence of the cations derived from the carboxylate × the molar number of the cation], and the 2-oxymethacrylic acid moiety The total amount is the sum of the moles of 2-oxymethacrylic acid (A) and the moles of 2-oxymethacrylate ions derived from 2-oxymethacrylic acid (A)) . A polymeric material containing the following formula (1): (In the formula, R represents a hydrogen atom, or a saturated or unsaturated hydrocarbon group with a carbon number of 10 or less) The represented 2-oxymethacrylic acid (A), carboxylate and/or water, and free radical polymerization The starting agent is characterized in that: the cation ratio expressed by the following calculation formula (I) is 0.01 or more and less than 1; or the moisture ratio expressed by the following calculation formula (II) is at least either one of 0.01 or more , (In the calculation formula (I), the total valence of the cations derived from the carboxylate is the sum of [the valence of the cations derived from the carboxylate × the molar number of the cation], and the 2-oxymethacrylic acid moiety The total amount is the sum of the moles of 2-oxymethacrylic acid (A) and the moles of 2-oxymethacrylate ions derived from 2-oxymethacrylic acid (A)) .