WO2023167186A1

WO2023167186A1 - Polymerizable composition

Info

Publication number: WO2023167186A1
Application number: PCT/JP2023/007317
Authority: WO
Inventors: 知正金子
Original assignee: 株式会社日本触媒
Priority date: 2022-03-02
Filing date: 2023-02-28
Publication date: 2023-09-07
Also published as: TW202346488A

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

Polymerizable composition

The present invention relates to polymerizable compositions with improved stability.

α-substituted methyl acrylate is known to undergo radical polymerization, and although the polymerization rate is low, the termination rate is also low, so it is known that in some cases a polymer with a high degree of polymerization can be obtained (for example, non- Patent Document 1, Non-Patent Document 2). α-allyloxymethyl acrylates, which are α-substituted methyl acrylate structures, are known to have cyclization polymerizability and to exhibit radical polymerization activity similar to that of acrylates (for example, Non-Patent Document 3, Patent Document 1). In addition, a technique for suppressing radical polymerization of α-allyloxymethyl acrylates to improve high-temperature stability and storage stability has been disclosed (eg, Patent Document 2).

JP 2011-137123 A JP 2014-31510 A

Although there are many examples of studies on the polymerizability of α-substituted methyl acrylates, there are few studies on the polymerizability of α-substituted methyl acrylates. , These may be simply referred to as 2-oxymethyl acrylic acid), for example, during manufacturing, storage, transportation, composition preparation operations, etc., it is not known that polymerization products are likely to occur. Ta.

Accordingly, an object of the present invention is to provide a polymerizable composition containing 2-oxymethylacrylic acid capable of suppressing the generation of polymerization products during the manufacturing process.

The present inventor conducted various studies to achieve the above object, and found that 2-oxymethylacrylic acid tends to generate undesirable polymerization products by a reaction that is considered to be cationic polymerization, and that the polymerization reaction is It was found that this reaction is unique to 2-oxymethylacrylic acid and does not occur in 2-oxymethylacrylate or 2-oxymethylacrylate. Then, by making a composition in which 2-oxymethyl acrylic acid contains a carboxylate or water acting as a base so that the cation ratio or water ratio falls within a predetermined range, the polymerization product is generated. The inventors have found that it is possible to satisfactorily suppress the above, and arrived at the present invention. That is, the present invention is described in [1] to [8] below.
[1] Formula (1) below:

(Wherein, R represents a hydrogen atom or a saturated or unsaturated hydrocarbon group having 10 or less carbon atoms.)
A polymerizable composition containing 2-oxymethyl acrylic acid (A) represented by and a carboxylate and / or water,
At least either the cation ratio represented by the following formula (I) is 0.01 or more and less than 1, or the water ratio represented by the following formula (II) is 0.01 or more A polymerizable composition characterized by satisfying

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

[2] The cations derived from the carboxylate contain one or more cations selected from the group consisting of metal ions, metal oxide ions, and cations containing non-metallic atoms of group 15 of the periodic table. The polymerizable composition according to [1] above, characterized in that:
[3] The carboxylate comprises one or more carboxylates selected from the group consisting of salts of 2-oxymethylacrylic acid (A), salts of acrylic acid, and salts of methacrylic acid. The polymerizable composition according to the above [1] or [2].
[4] The amount of 2-oxymethylacrylate ions contained in the carboxylate is 50 mol% or more and 100 mol% or less with respect to the total amount of carboxylate ions contained in the carboxylate. The polymerizable composition according to any one of [1] to [3] above.
[5] The polymerizable composition as described in any one of [1] to [4] above, wherein R in the general formula (1) is an allyl group or a methallyl group.
[6] A polymer obtained by polymerizing the polymerizable composition according to any one of [1] to [5] above under radical generation conditions.
[7] Formula (1) below;

(Wherein, R represents a hydrogen atom or a saturated or unsaturated hydrocarbon group having 10 or less carbon atoms.)
A method for storing 2-oxymethyl acrylic acid (A) represented by
The 2-oxymethyl acrylic acid (A) is treated in the presence of a carboxylate having a cation ratio represented by the following formula (I) of 0.01 or more and less than 1, and / or ), a method for storing 2-oxymethyl acrylic acid (A) in the presence of water having a water ratio of 0.01 or more.

[8] the following formula (1);

(Wherein, R represents a hydrogen atom or a saturated or unsaturated hydrocarbon group having 10 or less carbon atoms.)
A polymerized material containing 2-oxymethyl acrylic acid (A) represented by, a carboxylate and / or water, and a radical polymerization initiator,
At least either the cation ratio represented by the following formula (I) is 0.01 or more and less than 1, or the water ratio represented by the following formula (II) is 0.01 or more A polymeric material characterized by satisfying

According to the present disclosure, it is possible to provide a polymerizable composition containing 2-oxymethylacrylic acid that exhibits good radical polymerizability during use while suppressing the generation of polymerization products due to a reaction thought to be cationic polymerization. The above-mentioned polymerizable composition can be suitably used for various applications such as components of curable compositions used for various coatings, adhesions, sealings, and three-dimensional modeling, and raw materials for copolymers.

Preferred embodiments of the present disclosure will be specifically described below, but the present disclosure is not limited to the following description, and can be appropriately modified and applied without changing the gist of the present disclosure. In addition, the form which combined 2 or 3 or more individual preferable forms of this disclosure described below also corresponds to the preferable form of this disclosure. (Meth)acryl means acryl or methacryl. (Meth)allyl means allyl or methallyl.

The present disclosure provides the following formula (1):

(Wherein, R represents a hydrogen atom or a saturated or unsaturated hydrocarbon group having 10 or less carbon atoms.)
A polymerizable composition containing 2-oxymethyl acrylic acid (A) represented by and a carboxylate and / or water, wherein the cation ratio represented by the following formula (I) is 0.01 The polymerizable composition satisfies at least one of a water ratio of at least 1 and a water ratio represented by the following formula (II) of 0.01 or more.

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

The present inventor believes that a compound having a structure such as 2-oxymethylacrylic acid (A) represented by the above formula (1) has a high electron-donating property of the RO—CH ₂ group, so that the RO— A carbocation is likely to occur on the carbon to which the _CH2 group and the carboxyl group are bonded, and the carboxyl group can also be a catalyst or initiator for cationic polymerization, so compounds commonly used as cationic polymerization catalysts or initiators (e.g., sulfonic acid It was thought that cationic polymerization was likely to occur without the addition of a boron-based compound or a boron-based compound). Then, they thought that the coexistence of a base would suffice in order to suppress the formation of carbocations or to inactivate them even if they are formed. As it is known that carboxylates and water act as anionic polymerization initiators for vinyl compounds (such as 2-cyanoacrylic acid esters and methylene malonates) having carbon activated with electron-withdrawing groups, weak bases can act as The reason why the configuration of the present disclosure can suppress the formation of a polymer that is thought to occur in the cationic polymerization mechanism of 2-oxymethyl acrylic acid (A) is that the carboxylate and water act as a base and contain more than a certain amount. It is presumed that this is because the inhibitory force exceeds the force that initiates and advances cationic polymerization.

Components constituting the polymerizable composition of the present disclosure will be described.
<2-oxymethyl acrylic acid (A)>
2-oxymethyl acrylic acid (A) has the following formula (1);

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

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

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

From the viewpoint of good radical polymerizability, the number of carbon atoms in the saturated or unsaturated hydrocarbon group represented by R is preferably 8 or less, more preferably 6 or less, and still more preferably 4 or less. The above saturated or unsaturated hydrocarbon group is preferably a hydrocarbon group containing an unsaturated bond, most preferably an allyl group exhibiting polymerization activity similar to (meth)acrylate due to having cyclic polymerizability, It is a methallyl group.

Methods for analyzing the content of 2-oxymethyl acrylic acid (A) include gas chromatography; liquid chromatography based on various separation modes such as partition, adsorption, ion exchange, ion exclusion, size exclusion, affinity; electrophoresis; spectroscopic techniques such as ¹ H-NMR; and the like, but are not limited to these examples. Ion chromatography and capillary electrophoresis are preferable from the viewpoint of being detectable as 2-oxymethylacrylate ions, and ¹ H-NMR is preferable from the viewpoint of performing measurement in a short time. Among them, capillary electrophoresis is preferable from the viewpoint of sensitivity and maintainability of the apparatus.

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

When the carboxylate ion portion of the carboxylate is specifically indicated by the compound name of carboxylic acid, for example, monovalent saturated carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, myristic acid and stearic acid polyvalent saturated carboxylic acids such as oxalic acid, malonic acid, succinic acid, adipic acid and cyclohexanetricarboxylic acid; aromatic carboxylic acids such as benzoic acid, phthalic acid, terephthalic acid and trimellitic acid; acrylic acid, methacrylic acid, Carboxylic acids having a double bond conjugated with a carboxyl group such as maleic acid, fumaric acid, itaconic acid, and not 2-oxymethylacrylic acid (A) of the present disclosure; 2-hydroxymethylacrylic acid, 2 - 2-oxymethyl acrylic acid (A) of the present disclosure, such as methoxymethyl acrylic acid, 2-allyloxymethyl acrylic acid, 2-methallyloxymethyl acrylic acid; Instead, the carboxylate ion portion of the carboxylate may be a combination of two or more carboxylate ions.

From the viewpoint of making the polymerizable composition of the present disclosure a composition with good radical polymerizability, the carboxylate ion portion of the carboxylate is preferably a carboxylate ion having a double bond conjugated with a carboxyl group, In particular, acrylic acid, methacrylic acid, and carboxylic acid ions of the above-mentioned 2-oxymethylacrylic acid (A) are preferred, and 2-oxymethylacrylic acid ions are more preferred. Carboxylate ions of 2-allyloxymethylacrylic acid and 2-methallyloxymethylacrylic acid are most preferred. Thus, the carboxylate preferably contains one or more carboxylates selected from the group consisting of salts of 2-oxymethyl acrylic 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 50 mol % or more and 100 mol % or less with respect to the total amount of carboxylate ions in the carboxylate. It is preferably 70 mol % or more and 100 mol % or less, and still more preferably 90 mol % or more and 100 mol % or less. The most preferred 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 with respect to the total amount of carboxylate ions in the carboxylate.

Methods for analyzing the content of carboxylate ion moieties of carboxylates include liquid chromatography based on various separation modes such as partition, adsorption, ion exchange, ion exclusion, size exclusion, affinity; ^capillary electrophoresis; Spectroscopic techniques such as NMR; and the like, but are not limited to these examples. Ion chromatography and capillary electrophoresis are preferable from the viewpoint of being able to detect carboxylate ions, and ¹ H-NMR is preferable from the viewpoint of being able to perform measurement in a short time. Among them, capillary electrophoresis is preferable from the viewpoint of sensitivity and maintainability of the apparatus.

The cation that forms the carboxylate together with the carboxylate ion portion may be either an inorganic cation or an organic cation, and may be appropriately selected according to the purpose and application.

Examples of inorganic cations include metal ions and metal oxide ions. Specific examples of element names or metal oxide names include group 1 elements of the periodic table such as lithium, sodium, and potassium; magnesium and calcium; , barium, etc.; transition metal elements or transition metal oxides such as lanthanum, zirconium oxide, iron, cobalt, nickel, and copper; periodic table 12, such as zinc, aluminum, tin, lead, and bismuth Typical metal elements of Groups 1 to 15; etc., but not limited to these examples, and combinations of ions of two or more metals or metal oxides may be used. From the viewpoint of making the polymerizable composition of the present disclosure colorless, the inorganic cation portion of the carboxylate includes typical metal elements, metals belonging to Group 3 and Group 4 of the periodic table, and metal oxides. is preferred, and from the viewpoint of availability and toxicity, lithium, sodium, potassium, magnesium, calcium, zinc and aluminum are more preferred.

Organic cations include cations containing non-metallic elements of group 15 of the periodic table. Nitrogen, phosphorus, and arsenic are examples of non-metallic elements belonging to Group 15 of the periodic table. Preferably, nitrogen atom is cationized (ammonium ion, protonated amine, quaternary ammonium ion), phosphorus atom is cationized (phosphonium ion, protonated phosphine, quaternary phosphonium ion) However, ions in which a nitrogen atom is positively ionized are preferable from the viewpoint of biosafety and availability.

Specific examples of protonated amines are methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, ethanolamine, diethanolamine, triethanolamine, tris(2- aminoethyl)amine, hexamethylenediamine, iminobispropylamine, methyliminobispropylamine, 3,6,9,12-tetraoxa-tetradecane-1,14diamine, N,N'-bis(2-hydroxyethyl)ethylenediamine , 1,3-bisaminomethylcyclohexane, 1,4-bisaminomethylcyclohexane, 3-aminomethyl-3,5,6-trimethylcyclohexylamine, isophoronediamine, 2,5 (or 2,6)-bis(amino methyl)bicyclo[2,2,1]heptane, 2,6 (or 2,7)-bis(aminomethyl)bicyclo[3,2,1]octane, 2,5 (or 2,6)-bis(amino methyl)-7-dimethylbicyclo[2,2,1]heptane, 2,6-bis(aminomethyl)adamantane, m-xylylenediamine, p-phenylenediamine, bis(4-aminophenyl)methane, 1,4 (or 2,6 or 2,7)-bis(aminomethyl)naphthalene, piperazine, aminoethylpiperazine, bisaminopropylpiperazine, 2,4,6-triamino-1,3,5-triazine, polyethyleneimine, etc., nitrogen Examples of the structure of the atomic portion include primary to tertiary amines, and various types of amines having monovalent and divalent or higher valences can be exemplified, but the present disclosure is not limited to such examples.

Specific examples of quaternary ammonium ions include tetramethylammonium ion, tetraethylammonium ion, tetrabutylammonium ion, benzyltrimethylammonium ion, hexadecyltrimethylammonium ion and the like, but the present disclosure is only such examples. is not limited to

Thus, the carboxylate-derived cations include one or more cations selected from the group consisting of metal ions, metal oxide ions, and cations containing non-metallic atoms of group 15 of the periodic table. is preferred.

Methods for analyzing the content of the cationic portion of the carboxylate include ICP emission spectroscopy, atomic absorption, fluorescent X-rays, ion chromatography, capillary electrophoresis, etc., but are not limited to these examples. do not have. Ion chromatography and capillary electrophoresis are preferred, and capillary electrophoresis is particularly preferred, from the viewpoints of cation detection, maintenance of the apparatus, and ease of sample pretreatment.

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

<Cation ratio, moisture ratio>
The polymerizable composition of the present disclosure has a cation ratio represented by the above formula (I) of 0.01 or more and less than 1, or a water ratio represented by the above formula (II) of 0.01. satisfy at least one of 01 or more. The polymerizable composition of the present disclosure contains a carboxylic acid salt, together with the 2-oxymethylacrylic acid (A), so that the cation ratio represented by the formula (I) is at least 0.01 or more and less than 1. or it preferably contains water so that the water ratio represented by the above formula (II) is 0.01 or more, and even if it contains a carboxylate and water in a predetermined amount good.

The cation ratio is more preferably 0.95 or less, still more preferably 0.9 or less, and particularly preferably 0.8 or less, from the viewpoint of reducing the amount of carboxylate depending on the application. From the viewpoint of suppressing the production of polymers that are thought to occur by 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. be. 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, still more preferably 0.02 or more and 0.9 or less, and particularly preferably It is 0.03 or more and 0.8 or less.

The water 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 polymer. Although there is no upper limit to the water ratio from the viewpoint of suppressing the formation of a polymer, it is preferably 50 or less, more preferably 40 or less, from the viewpoint of increasing the content of 2-oxymethylacrylic acid (A). , more preferably 30 or less, particularly preferably 20 or less. That is, the water ratio is preferably from 0.01 to 50, more preferably from 0.01 to 40, even more preferably from 0.01 to 30, and particularly preferably from 0.01 to 20. It is below.

Among others, the polymerizable composition of the present disclosure preferably includes the following first and second forms.
(first form)
A first preferred embodiment of the present disclosure is a polymerizable composition containing 2-oxymethylacrylic acid (A) represented by the above formula (1) and the above carboxylate, wherein the above calculation formula (I ) is a polymerizable composition having a cation ratio of 0.01 or more and less than 1.
Water may not be included as long as the carboxylate is included so that the above cation ratio is achieved, but water may be included. When the above water is included, the water ratio represented by the above formula (II) is preferably 0.0005 or more, more preferably 0.001 or more.
The preferred cation ratio in the first form is as described above.

(Second form)
A preferred second form of the present disclosure is a polymerizable composition containing 2-oxymethyl acrylic acid (A) represented by the above formula (1) and water, and is represented by the above calculation formula (II) It is a polymerizable composition having a water content ratio of 0.01 or more.
The carboxylate does not have to be contained as long as it contains water so as to achieve the above water ratio, but the carboxylate may be contained.
The preferred water content ratio in the second mode is as described above.

<Other ingredients>
The polymerizable composition of the present disclosure may contain components other than the 2-oxymethylacrylic acid (A), carboxylate, and water, depending on its purpose, application, and the like. Such components include radical polymerization inhibitors, radically polymerizable compounds, radical polymerization initiators, compounds having reactive groups other than radically polymerizable groups, organic solvents, thermoplastic resins, organic or inorganic fine particles, fillers, and dyes. , pigments, dispersants, ultraviolet absorbers, leveling agents, surface modifiers, antistatic agents, adhesion improvers, coupling agents, release agents, viscosity modifiers, etc., but the present disclosure is limited to these. not something.

Main components among other components are specifically shown below, but the present disclosure is not limited to such examples.

[Radical polymerization inhibitor]
From the viewpoint of suppressing undesired radical polymerization during various operations such as storage, transportation, composition preparation and processing, the polymerizable composition of the present disclosure includes a primary antioxidant having radical chain-blocking properties and/or A suitable amount of a secondary antioxidant having peroxide decomposability may be used.

Primary antioxidants include, for example, hydroquinones, benzoquinones, phenols, aromatic amines, phenothiazines, dithiocarbamate metal salts, nitroso compounds, etc., but the present disclosure is limited only to such examples. not something. Examples of secondary antioxidants include phosphorus compounds such as phosphine and phosphite, sulfur compounds such as thioether, mercaptobenzimidazole, and thiourea, but the present disclosure is limited only to such examples. isn't it. Although the primary antioxidant and the secondary antioxidant may be used alone, it is more preferable to use them together.

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

Phenols include, for example, monoetherified hydroquinones, hindered phenols and their multimers (including dimers) or multimer derivatives, semi-hindered phenols and their multimers (including dimers) or derivatives of multimers, etc., but the present disclosure is not limited only to such examples. These phenols may be used alone or in combination of two or more.

Monoetherified hydroquinones include, for example, hydroquinone monomethyl ether, hydroquinone mono n-butyl ether, hydroquinone monobenzyl ether, hydroquinone monocyclohexyl ether, 4-methoxy-1-naphthol, etc., but the present disclosure provides only such examples. is not limited to These monoetherified hydroquinones may be used alone or in combination of two or more.

Examples of hindered phenols include 2,6-bis(tert-butyl)-4-methylphenol, octadecyl-3-(3,5-ditert-butyl-4-hydroxyphenyl)propionate, isooctyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylanilino)-1,3, 5-triazine, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate-diethyl ester and the like, but the present disclosure is not limited to only such exemplification. Hindered phenol multimers or multimer derivatives include, for example, pentaerythrityl tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,2-thio-diethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamamide), 1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)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 and the like, but the present disclosure is not limited only to such examples. do not have. Hindered phenols and their multimers (including dimers) or multimer derivatives may be used alone, or two or more of them may be used in combination.

Examples of semi-hindered phenols include 6-tert-butyl-o-cresol, 6-tert-butyl-2,4-xylenol, 2,4,8,10-tetra-tert-butyl-6-[3 -(3-methyl-4-hydroxy-5-t-butylphenyl)propoxy]dibenzo[d,f][1,3,2]dioxaphosphepin, 2,4-dimethyl-6-(1-methyl pentadecyl)phenol, 2,4-bis(octylthiomethyl)-o-cresol, 2,4-bis(dodecylthiomethyl)-o-cresol, 2-tert-butylphenol, 2,4-ditert-butylphenol, 2-tert-amylphenol, 2,4-di-tert-amylphenol, etc., but the present disclosure is not limited to such examples. Semi-hindered phenol multimers or multimer derivatives include, for example, methylenebis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate], triethylene glycol bis[β -(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 4,4′-thiobis(2-methyl-6-tert-butylphenol), bis(3-methyl-4-hydroxy-5- tert-butylbenzyl)sulfide, terephthaloyl-di(2,6-dimethyl-4-tert-butyl-3-hydroxybenzylsulfide), 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′-butylidenebis(6-tert-butyl-3 -methylphenol), 4,4′-thiobis(6-tert-butyl-3-methylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 2 , 2′-methylenebis(4-methyl-6-tert-butylphenol), 2,2′-methylenebis(4-ethyl-6-tert-butylphenol), 2,2′-thiobis(4-methyl-6-tert- butylphenol), 2-[1-(2-hydroxy-3,5-ditert-pentylphenyl)ethyl]-4,6-ditert-pentylphenyl acrylate, 2-tert-butyl-6-(3-tert- butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate and the like, but the present disclosure is not limited to such examples only. The semi-hindered phenols and their multimers (including dimers) or multimer derivatives may be used alone or in combination of two or more.

Phosphines include, for example, triethylphosphine, tributylphosphine, tris(2-ethylhexyl)phosphine, triphenylphosphine, etc., but the present disclosure is not limited to such examples. These phosphines may be used alone or in combination of two or more.

Examples of phosphites include diethyl hydrogen phosphite, bis(2-ethylhexyl) hydrogen phosphite, dilauryl hydrogen phosphite, dioleyl hydrogen phosphite, diphenyl hydrogen phosphite, triethyl phosphite, tributyl phosphite, tris(2 -ethylhexyl)phosphite, triisodecylphosphite, trilaurylphosphite, tris(tridecylphosphite), trioleylphosphite, tristearylphosphite, phenyldiisodecylphosphite, diphenylmethylphosphite, 2-ethylhexyldiphenylphosphite Phyto, isodecyldiphenylphosphite, tridecyldiphenylphosphite, bis(2,4-di-tert-butyl-6-methylphenyl)ethylphosphite, triphenylphosphite, tricresylphosphite, tris(nonylphenyl) Phosphite, tris(2,4-ditert-butylphenyl)phosphite, bis(isodecyl)pentaerythritol diphosphite, bis(tridecyl)pentaerythritol diphosphite, bis(stearyl)pentaerythritol diphosphite, bis( nonylphenyl)pentaerythritol diphosphite, bis(2,4-ditert-butylphenyl)pentaerythritol diphosphite, bis(2,6-ditert-butyl-6-methylphenyl)pentaerythritol diphosphite, 4 ,4′-butylidenebis(3-methyl-6-tert-butylphenyldiisotridecyl)phosphite, tetraphenyldipropylene glycol diphosphite, tetraphenyltetra(tridecyl)pentaerythritol tetraphosphite, tetra(C12-C15 alkyl )-4,4′-isopropylidene diphenyl phosphite, tetra(tridecyl)-1,1,3-tris(2-methyl-5-tert-butyl-4-hydroxyphenyl)butane diphosphite, 2,4, 8,10-tetra-tert-butyl-6-[3-(3-methyl-4-hydroxy-5-tert-butylphenyl)propoxy]dibenzo[d,f][1,3,2]dioxaphosphate Pin, 2,2-methylenebis(4,6-tert-butylphenyl)-2-ethylhexylphosphite, trilauryltrithiophosphite, etc., but the present disclosure is not limited to such examples only. Each of these phosphites may be used alone, or two or more of them may be used in combination.

Thioethers include, for example, 2,2′-thiodiglycolic acid, (ethylenedithio)diacetic acid, 2,2′-(ethylenedithio)diethanol, 3,3′-thiodipropionic acid, 3,3′-thio Dimethyl dipropionate, 3-laurylthiopropionic acid, methyl 3-laurylthiopropionate, (3-octylthiopropionic acid) pentaerythritol tetraester, (3-decylthiopropionic acid) pentaerythritol tetraester, (3-lauryl) thiopropionic acid) pentaerythritol tetraester, (3-oleylthiopropionic acid) pentaerythritol tetraester, (3-stearylthiopropionic acid) pentaerythritol tetraester, (3-laurylthiopropionic acid)-4,4'-thiodiene (3-methyl-5-tert-butyl-4-phenol) ester, dioctyl thiodipropionate, didecyl thiodipropionate, dilauryl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate , lauryl stearyl thiodipropionate, distearyl-β,β'-thiodibutyrate, dimethyl sulfide, methyl dodecyl sulfide, dilauryl sulfide, distearyl sulfide, 2,4-bis(octylthiomethyl)-o-cresol, 2,4-bis(dodecylthiomethyl)-o-cresol and the like, but the present disclosure is not limited only to such examples. These thioethers may be used alone or in combination of two or more.

The content of the radical polymerization inhibitor is determined from the viewpoint of suppressing radical polymerization during various operations such as storage, transportation, composition preparation and treatment, and ensuring the radical polymerizability according to the application. Monomer component) is preferably from 0.005 to 2 parts by mass, more preferably from 0.01 to 1 part by mass, and still more preferably from 0.02 to 0.5 parts by mass with respect to a total of 100 parts by mass. In this specification, the radically polymerizable component refers to, for example, 2-oxymethylacrylic acid, the radically polymerizable carboxylate, and the radically polymerizable compound described later.

[Radical polymerizable compound]
The polymerizable composition of the present disclosure, for example, can be applied to components of curable compositions used for various coatings and three-dimensional modeling, copolymer raw materials, etc., other than 2-oxymethyl acrylic acid (A) of the present disclosure It may contain a radically polymerizable compound.

The radically polymerizable compound includes a monofunctional radically polymerizable monomer, which is a compound having one radically polymerizable group in the same molecule, and a polyfunctional compound, which is a compound having two or more radically polymerizable groups in the same molecule. can be classified into radically polymerizable compounds.

[Monofunctional Radical Polymerizable Monomer]
Examples of the monofunctional radically polymerizable monomer (a) include (meth)acrylic acid esters, (meth)acrylamides, 2-(meth)allyloxymethyl acrylic acid esters, unsaturated monocarboxylic acids, and unsaturated polyvalent carboxylic acids, unsaturated monocarboxylic acids with chain extension between unsaturated groups and carboxyl groups, unsaturated acid anhydrides, aromatic vinyls, N-substituted maleimides, conjugated dienes, vinyl esters, vinyl ethers, N-vinyl compounds, Examples include unsaturated isocyanates, but the present disclosure is not limited to such examples. These monofunctional radically polymerizable monomers may be used alone or in combination of two or more.

Examples of (meth)acrylic esters include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, n-amyl (meth)acrylate, sec-amyl (meth)acrylate, tert-amyl (meth)acrylate, (meth)acrylic acid n-hexyl, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, tridecyl (meth)acrylate, cyclohexyl (meth)acrylate, cyclohexylmethyl (meth)acrylate, octyl (meth)acrylate, ( Lauryl (meth)acrylate, Stearyl (meth)acrylate, Benzyl (meth)acrylate, Phenyl (meth)acrylate, Isobornyl (meth)acrylate, Adamantyl (meth)acrylate, Tricyclodecanyl (meth)acrylate , 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate , (meth) 4-hydroxybutyl acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, (meth) ) glycidyl acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, (3,4-epoxycyclohexyl)methyl (meth)acrylate, N,N-dimethyl (meth)acrylate Examples include aminoethyl, methyl α-hydroxymethyl acrylate, ethyl α-hydroxymethyl acrylate, and the like, but the present disclosure is not limited to only such examples. These (meth)acrylic acid esters may be used alone or in combination of two or more.

(Meth)acrylamides include, for example, N,N-dimethyl(meth)acrylamide, N-methylol(meth)acrylamide, acryloylmorpholine, etc., but the present disclosure is not limited to such examples. These (meth)acrylamides may be used alone or in combination of two or more.

Examples of 2-(meth)allyloxymethyl acrylic esters include methyl 2-(meth)allyloxymethyl acrylate, ethyl 2-(meth)allyloxymethyl acrylate, and 2-(meth)allyloxymethyl acrylic acid. n-propyl, isopropyl 2-(meth)allyloxymethylacrylate, n-butyl 2-(meth)allyloxymethylacrylate, sec-butyl 2-(meth)allyloxymethylacrylate, 2-(meth)allyl tert-butyl oxymethyl acrylate, n-amyl 2-(meth) allyloxymethyl acrylate, sec-amyl 2-(meth) allyloxymethyl acrylate, tert-amyl 2-(meth) allyloxymethyl acrylate, 2-(meth) neopentyl allyloxymethyl acrylate, n-hexyl 2-(meth) allyloxymethyl acrylate, sec-hexyl 2-(meth) allyloxymethyl acrylate, 2-(meth) allyloxymethyl acrylate n-heptyl, 2-(meth) n-octyl allyloxymethyl acrylate, sec-octyl 2-(meth) allyloxymethyl acrylate, tert-octyl 2-(meth) allyloxymethyl acrylate, 2-(meth) ) 2-ethylhexyl allyloxymethyl acrylate, 2-(meth) capryloxymethyl acrylate, nonyl 2-(meth) allyloxymethyl acrylate, 2-(meth) allyloxymethyl decyl acrylate, 2-(meth) ) undecyl allyloxymethyl acrylate, lauryl 2-(meth) allyloxymethyl acrylate, tridecyl 2-(meth) allyloxymethyl acrylate, myristyl 2-(meth) allyloxymethyl acrylate, 2-(meth) allyl Pentadecyl oxymethyl acrylate, 2-(meth) allyloxymethyl cetyl acrylate, 2-(meth) allyloxymethyl heptadecyl acrylate, 2-(meth) allyloxymethyl stearyl acrylate, 2-(meth) allyloxymethyl acrylate Nonadecyl acrylate, 2-(meth)allyloxymethyl eicosyl acrylate, 2-(meth)allyloxymethyl ceryl acrylate, 2-(meth)allyloxymethyl acrylate melisyl, 2-(meth)allyloxymethyl acrylate Crotyl, 1,1-dimethyl-2-propenyl 2-(meth)allyloxymethylacrylate, 2-methylbutenyl 2-(meth)allyloxymethylacrylate, 3-methyl-2-(meth)allyloxymethylacrylate 2-butenyl, 3-methyl-3-butenyl 2-(meth)allyloxymethylacrylate, 2-methyl-3-butenyl 2-(meth)allyloxymethylacrylate, 2-(meth)allyloxymethylacrylate Oleyl, linoleic 2-(meth) allyloxymethyl acrylate, linolene 2-(meth) allyloxymethyl acrylate, cyclopentyl 2-(meth) allyloxymethyl acrylate, cyclopentyl methyl 2-(meth) allyloxymethyl acrylate , 2-(meth) allyloxymethyl cyclohexyl acrylate, 2-(meth) allyloxymethyl cyclohexylmethyl acrylate, 2-(meth) allyloxymethyl acrylate 4-methylcyclohexyl, 2-(meth) allyloxymethyl acrylate acid 4-tert-butylcyclohexyl, 2-(meth) allyloxymethyl tricyclodecanyl acrylate, 2-(meth) allyloxymethyl acrylate isobornyl, 2-(meth) allyloxymethyl acrylate adamantyl acrylate, 2-( meth) dicyclopentanyl allyloxymethyl acrylate, 2-(meth) dicyclopentenyl allyloxymethyl acrylate, phenyl 2-(meth) allyloxymethyl acrylate, 2-(meth) methyl phenyl allyloxymethyl acrylate , dimethylphenyl 2-(meth) allyloxymethyl acrylate, trimethylphenyl 2-(meth) allyloxymethyl acrylate, 4-tert-butylphenyl 2-(meth) allyloxymethyl acrylate, 2-(meth) allyl benzyl oxymethyl acrylate, 2-(meth) allyloxymethyl acrylate diphenylmethyl acrylate, 2-(meth) allyloxymethyl acrylate diphenylethyl acrylate, 2-(meth) allyloxymethyl acrylate triphenylmethyl acrylate, 2-(meth) ) cinnamyl allyloxymethyl acrylate, 2-(meth) allyloxymethyl acrylate naphthyl, 2-(meth) allyloxymethyl acrylate anthranyl, 2-(meth) allyloxymethyl acrylate methoxyethyl, 2-(meth) Methoxyethoxyethyl allyloxymethyl acrylate, Methoxyethoxyethyl 2-(meth) allyloxymethyl acrylate, 3-Methoxybutyl 2-(meth) allyloxymethyl acrylate, 2-(Meth) allyloxymethyl acrylate Ethoxyethyl, 2-(meth)allyloxymethyl acrylate, ethoxyethoxyethyl acrylate, 2-(meth)allyloxymethyl cyclopentoxyethyl acrylate, 2-(meth)allyloxymethyl acrylate, cyclohexyloxyethyl acrylate, 2-(meth) ) Cyclopentoxyethoxyethyl allyloxymethyl acrylate, 2-(meth) allyloxymethyl cyclohexyloxyethoxyethyl acrylate, 2-(meth) allyloxymethyl acrylate dicyclopentenyloxyethyl, 2-(meth) allyloxy phenoxyethyl methyl acrylate, phenoxyethoxyethyl 2-(meth) allyloxymethyl acrylate, glycidyl 2-(meth) allyloxymethyl acrylate, β-methylglycidyl 2-(meth) allyloxymethyl acrylate, 2-( β-ethylglycidyl meth) allyloxymethyl acrylate, 3,4-epoxycyclohexylmethyl 2-(meth) allyloxymethyl acrylate, 2-oxetane methyl 2-(meth) allyloxymethyl acrylate, 2-(meth) 3-methyl-3-oxetanemethyl allyloxymethyl acrylate, 3-ethyl-3-oxetanemethyl 2-(meth)allyloxymethyl acrylate, 2-(meth)allyloxymethyl tetrahydrofuranyl acrylate, 2-(meth) ) tetrahydrofurfuryl allyloxymethyl acrylate, tetrahydropyranyl 2-(meth) allyloxymethyl acrylate, dioxazolanyl, dioxanyl 2-(meth) allyloxymethyl acrylate, etc., but the present disclosure is only such examples. is not limited to These 2-(meth)allyloxymethyl acrylic acid esters may be used alone or in combination of two or more.

Examples of unsaturated monocarboxylic acids include (meth)acrylic acid, crotonic acid, cinnamic acid, and vinyl benzoic acid, but the present disclosure is not limited to such examples. Each of these unsaturated monocarboxylic acids may be used alone, or two or more of them may be used in combination.

Examples of unsaturated polycarboxylic acids include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid, but the present disclosure is not limited to such examples. Each of these unsaturated polycarboxylic acids may be used alone, or two or more of them may be used in combination.

Examples of the unsaturated monocarboxylic acid having chain extension between the unsaturated group and the carboxyl group include mono(2-acryloyloxyethyl) succinate and mono(2-methacryloyloxyethyl) succinate. , the present disclosure is not limited to only such exemplifications. These unsaturated monocarboxylic acids in which the chain is extended between the unsaturated group and the carboxyl group may be used alone, or two or more of them may be used in combination.

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

Examples of vinyl aromatics include styrene, α-methylstyrene, vinyltoluene, methoxystyrene, and the like, but the present disclosure is not limited to such examples. These aromatic vinyls may be used alone or in combination of two or more.

Examples of N-substituted maleimides include methylmaleimide, ethylmaleimide, isopropylmaleimide, cyclohexylmaleimide, phenylmaleimide, benzylmaleimide, naphthylmaleimide, and the like, but the present disclosure is not limited to such examples. Each of these N-substituted maleimides may be used alone, or two or more of them may be used in combination.

Conjugated dienes include, for example, 1,3-butadiene, isoprene, chloroprene, and the like, but the present disclosure is not limited to such examples. These conjugated dienes may be used alone or in combination of two or more.

Vinyl esters include, for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, and the like, but the present disclosure is not limited to such examples. These vinyl esters may be used alone or in combination of two or more.

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

Examples of N-vinyl compounds include N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylimidazole, N-vinylmorpholine, N-vinylacetamide, etc., but the present disclosure is limited only to such examples. not something. Each of these N-vinyl compounds may be used alone, or two or more of them may be used in combination.

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

The content of the monofunctional radically polymerizable monomer (a) may be adjusted depending on the application and purpose, and may not be included. It is preferably 1 to 98% by mass, more preferably 2 to 95% by mass, still more preferably 3 to 90% by mass.

[Polyfunctional Radical Polymerizable Compound]
The polyfunctional radically polymerizable compound (b) is, as described above, a compound having two or more radically polymerizable groups in the same molecule. The radically polymerizable group in the polyfunctional radically polymerizable compound is preferably a carbon-carbon double bond, more preferably a carbon-carbon double bond covalently activated by adjacent functional groups.

Examples of covalently activated carbon-carbon double bonds include carbon-carbon double bonds in which adjacent carbon-carbon double bonds are conjugated, such as 1,3-butadiene structure, and carbon-carbon double bonds in which carbonyl groups are adjacently conjugated. carbon-carbon double bonds with adjacent conjugated cyano groups, carbon-carbon double bonds with adjacent conjugated aromatic rings, etc., but the present disclosure is only such examples. is not limited to Among these covalently activated carbon-carbon double bonds, carbon-carbon double bonds with adjacent conjugated carbonyl groups and carbon-carbon double bonds with adjacent conjugated cyano groups are considered from the viewpoint of enhancing polymerization activity. A carbon-carbon double bond in which the double bond and the aromatic ring are adjacently conjugated is preferable, and a carbon-carbon double bond in which the carbonyl group is adjacently conjugated is more preferable, (meth)acryloyl group, 2-(meth) An allyloxymethylacryloyl group and a maleimide group are more preferred.

Therefore, among polyfunctional radically polymerizable compounds, polyfunctional (meth)acrylic compounds having one or more (meth)acryloyl groups and other radically polymerizable groups, and 2-(meth)allyloxymethyl acryloyl groups Polyfunctional 2-(meth)allyloxymethyl acrylic compounds having one or more and other radically polymerizable groups, and polyfunctional maleimide compounds having one or more maleimide groups and other radically polymerizable groups are preferred, Polyfunctional (meth)acrylic compounds having two or more (meth)acryloyl groups, polyfunctional 2-(meth)allyloxymethyl acrylic compounds having two or more 2-(meth)allyloxymethylacryloyl groups, and maleimide Polyfunctional maleimide compounds having two or more groups are more preferred.

Examples of polyfunctional radically polymerizable compounds include polyfunctional (meth)acrylic acid esters, vinyl ether group-containing (meth)acrylic acid esters, allyl group-containing (meth)acrylic acid esters, and polyfunctional (meth)acryloyl group-containing isocyanurates. , Polyfunctional urethane (meth) acrylate and other polyfunctional (meth) acrylic compounds; Polyfunctional 2-(meth) allyloxymethyl acrylate; Multifunctional maleimide compounds; Multifunctional vinyl ethers; Multifunctional allyl compounds; functionalized aromatic vinyls, and the like, but the present disclosure is not limited to only such exemplifications. These polyfunctional radically polymerizable compounds may be used alone or in combination of two or more.

Polyfunctional (meth)acrylic esters include, for example, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butylene glycol di(meth) Acrylates, hexanediol di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, bisphenol A alkylene oxide di(meth)acrylate, bisphenol F alkylene oxide di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylol Propane tetra(meth)acrylate, glycerin tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethylene oxide added trimethylolpropane tri(meth)acrylate , ethylene oxide-added ditrimethylolpropane tetra(meth)acrylate, ethylene oxide-added pentaerythritol tetra(meth)acrylate, ethylene oxide-added dipentaerythritol hexa(meth)acrylate, propylene oxide-added trimethylolpropane tri(meth)acrylate, propylene oxide-added ditrimethylol Propane tetra(meth)acrylate, propylene oxide-added pentaerythritol tetra(meth)acrylate, propylene oxide-added dipentaerythritol hexa(meth)acrylate, ε-caprolactone-added trimethylolpropane tri(meth)acrylate, ε-caprolactone-added ditrimethylolpropane Examples include tetra(meth)acrylate, ε-caprolactone-added pentaerythritol tetra(meth)acrylate, and ε-caprolactone-added dipentaerythritol hexa(meth)acrylate, but the present disclosure is not limited only to such examples. . These polyfunctional (meth)acrylic acid esters may be used alone or in combination of two or more.

Vinyl ether group-containing (meth)acrylic esters include, for example, 2-vinyloxyethyl (meth)acrylate, 3-vinyloxypropyl (meth)acrylate, 1-methyl-2-vinyloxyethyl (meth)acrylate, (meth)acrylate, 2-vinyloxypropyl acrylate, 4-vinyloxybutyl (meth)acrylate, 4-vinyloxycyclohexyl (meth)acrylate, 5-vinyloxypentyl (meth)acrylate, 6-vinyloxyhexyl (meth)acrylate, 4-vinyloxymethylcyclohexylmethyl (meth)acrylate, p-vinyloxymethylphenylmethyl (meth)acrylate, 2-(vinyloxyethoxy)ethyl (meth)acrylate, 2-(vinyloxy)acrylate (meth) ethoxyethoxyethoxy)ethyl and the like, but the present disclosure is not limited only to such exemplifications. These vinyl ether group-containing (meth)acrylic acid esters may be used alone or in combination of two or more.

Examples of allyl group-containing (meth)acrylic acid esters include allyl (meth)acrylate and the like, but the present disclosure is not limited to such examples.

Polyfunctional (meth)acryloyl group-containing isocyanurates include, for example, tri(acryloyloxyethyl) isocyanurate, tri(methacryloyloxyethyl) isocyanurate, alkylene oxide-added tri(acryloyloxyethyl) isocyanurate, alkylene oxide-added tri( methacryloyloxyethyl)isocyanurate, etc., but the present disclosure is not limited to such examples only. These polyfunctional (meth)acryloyl group-containing isocyanurates may be used alone or in combination of two or more.

Examples of polyfunctional urethane (meth)acrylates include polyfunctional isocyanates such as tolylene diisocyanate, isophorone diisocyanate, and xylylene diisocyanate, and hydroxyl groups such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate. Polyfunctional urethane (meth)acrylates obtained by reaction with contained (meth)acrylic acid esters may be mentioned, but the present disclosure is not limited only to such exemplifications.

Examples of polyfunctional 2-(meth)allyloxymethyl acrylates include polyfunctional 2-(meth)allyloxymethyl acrylates described in Japanese Patent No. 05689628, and the like. The examples are not intended to be limiting. Each of these polyfunctional 2-(meth)allyloxymethyl acrylates may be used alone, or two or more of them may be used in combination.

Polyfunctional maleimide compounds include, for example, 4,4′-diphenylmethanebismaleimide, m-phenylenebismaleimide, bisphenol A diphenyletherbismaleimide, 3,3′-dimethyl-5,5′-diethyl-4,4′- diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, 1,6-bismaleimido-(2,2,4-trimethyl)hexane, phenylmethanemaleimide oligomers, and the like, although the present disclosure provides such examples. is not limited to only These polyfunctional maleimide compounds may be used alone or in combination of two or more.

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

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

Polyfunctional aromatic vinyls include, for example, divinylbenzene and the like, but the present disclosure is not limited to such examples.

The polyfunctional radically polymerizable compound may be an oligomer or polymer in which the backbone portion other than the radically polymerizable group has repeating units based on monomers. When the molecular weight of the polyfunctional radical polymerizable compound is less than 1000, it can be classified as an oligomer, and when the molecular weight is 1000 or more, it can be classified as a polymer.

The oligomer or polymer skeleton of the multifunctional radically polymerizable compound includes, for example, a polyester skeleton, a polyether skeleton, a polyurethane skeleton, a conjugated diene polymer skeleton such as polybutadiene and polyisoprene, a poly(meth)acrylate skeleton, Phenol resin skeletons, aniline resin skeletons, polyolefin skeletons, polyamide skeletons, cycloolefin polymer skeletons, polysiloxane skeletons, etc. may be mentioned, but the present disclosure is not limited to these examples. Among these skeletons, a polyester skeleton, a polyether skeleton, a polyurethane skeleton, a conjugated diene polymer skeleton, a poly(meth)acrylate skeleton, a phenolic resin skeleton and an aniline resin skeleton are preferred. The skeleton portion and the radically polymerizable group may be bonded by a covalent bond, but are preferably bonded via an ester bond and/or a urethane bond.

Examples of oligomers or polymers of polyfunctional radically polymerizable compounds include urethane (meth)acrylate polymerizable oligomers in which (meth)acryloyl groups are bonded to the skeleton via urethane bonds, and (meth)acryloyl groups as the skeleton. Urethane (meth)acrylate-based polymer bonded to a moiety through a urethane bond, epoxy (meth)acrylate-based polymerization having a structure in which (meth)acrylic acid is added to an epoxy resin (oligomer or polymer having an epoxy group) Epoxy oligomer, epoxy resin (oligomer or polymer having an epoxy group), epoxy (meth)acrylate polymer having a structure in which (meth)acrylic acid is added, (meth)acryloyl group via polyester skeleton and ester bond Bonded polyester (meth)acrylate polymerizable oligomer, polyester (meth)acrylate polymer in which (meth)acryloyl group is bonded to polyester skeleton via ester bond, (meth)acryloyl group is phenolic resin skeleton and phenylmethane (meth)acrylate-based polymerizable oligomer bonded via an ester bond, a phenylmethane (meth)acrylate-based polymer in which a (meth)acryloyl group is bonded to a phenolic resin skeleton via an ester bond, aniline Phenylmethanemaleimide-based polymerizable oligomers in which maleimide groups are directly bonded to the resin skeleton, phenylmethanemaleimide-based polymers in which maleimide groups are directly bonded to the aniline resin skeleton, and the like, but the present disclosure is limited to such examples. It is not limited.

Polyfunctional radically polymerizable compounds are readily commercially available. Commercially readily available polyfunctional radically polymerizable compounds include, for example, products manufactured by Kyoeisha Chemical Co., Ltd., trade names: Light Acrylate 3EG-A, Light Acrylate 4EG-A, Light Acrylate 9EG-A, Light Acrylate 14EG-A, light acrylate NP-A, light acrylate 1,6-HX-A, light acrylate 1,9ND-A, light acrylate DCP-A, light acrylate BP-4EA, light acrylate BP-4PA, light acrylate TMP -A, light acrylate TMP-3EO-A, light acrylate TMP-6EO-3A, light acrylate PE-3A, light acrylate PE-4A, light acrylate DPE-6A, light acrylate BA-134, light acrylate HPP-A, light Acrylate PTMGA-250, Light acrylate DTMP-4A, Light ester EG, Light ester 2EG, Light ester 3EG, Light ester 4EG, Light ester 9EG, Light ester 14EG, Light ester NP, Light ester 1/3BG, Light ester 1,4 -BG, Light ester 1,6-HX, Light ester 1,9ND, Light ester 1/10DC, Light ester TMP, Light ester G-101P, Light ester G-201P, Light ester BP-2EM, Epoxy ester 40EM, Epoxy Ester 70PA, Epoxy Ester 200PA, Epoxy Ester 80MFA, Epoxy Ester 3002M, Epoxy Ester 3002A, Epoxy Ester 1600A, Epoxy Ester 3000M, Epoxy Ester 3000A, Epoxy Ester 200EA, Epoxy Ester 400EA, AH-600, AT-600, UA-306H , AI-600, UA-101T, UA-101I, UA-306T, UA-306I, etc.;

SR212, SR213, SR230, SR238F, SR247, SR259, SR268, SR272, SR306H, SR344, SR349, CD406, SR508, CD536, CD560, CD561, CD562, CD564, CD580, CD 581, CD582, SR601, SR602, SR610, CD802, SR833, SR9003, CD9038, CD9043, SR9045, SR9209A, SR101, SR150, SR205, SR206, SR209, SR210, SR214, SR239, SR248, SR252, CD262 , SR297, SR348, CD401, SR480, CD540, SR541, CD542, SR603, SR644, SR740, SR9036, SR351S, SR368, SR415, SR444, SR454, SR492, SR499, CD501, SR502, SR9020, 9021, SR9035, SR350, SR9009 , SR9011, SR295, SR355, SR494, SR399, SR9041, SR9012, CD9051, CD9053, CN929, CN940, CN944B85, CN959, CN961, CN961E75, CN961H81, CN962, CN963, CN963A80, CN963B80, CN963E75, CN963 E80, CN963J75, CN964, CN964A85, CN964E75, CN965, CN965A80, CN966, CN966A80, CN966B85, CN966H90, CN966J75, CN966R60, CN968, CN980, CN981, CN981A75, CN981B88, CN982, CN982A75, CN982B88, CN982E75, CN982P90, CN983, C N985B88, 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, CN 973A80, CN973H85, CN973J75, CN975, CN977C70, CN978, CN992, CN994, CN997, CN999, CN9165, CN9782, CN9783, CN1963, CN2901, CN2902, CN2920, CN2921, CN3210, CN3211, CN104, CN104A80, CN104B80, CN104D80, CN111US, CN112 C60, CN113D70, CN115, CN116, CN117, CN118, CN119, CN120, CN120A75, CN120B60, CN120B80, CN120C60, CN120C80, CN120D80, CN120E50, CN120M50, CN121, CN132, CN133, CN136, CN137, CN151, CN152, CNUVE151, CNUVE150/ 80, CN160, CN2100, CN2101, CN2102E, CN292, CN293, CN394, CN296, CN299, CN2200, CN2203, CN2250, CN2251, CN2252, CN2253, CN2254, CN2255, CN2256, CN2257, CN2258, CN2259, CN2260, CN2261, CN2262, CN2270, CN2 271E, CN2272, CN2273, CN2276, CN2278, CN2279, CN2280, CN2281, CN2282, CN2285, CN2297A, CN2298, CN2470, CN2300, CN2301, CN2302, CN2303, CN2304, CN147, CN301, CN303, CN307, CN371, CN501, CN550, CN551, CN 2201, CN736, CN738, CN9101, CN2600, CN990, CN9800, etc. ;

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.;

Nippon Synthetic Chemical Industry Co., Ltd., product names: Shiko UV-1700B, Shiko UV-6300B, Shiko UV-7550B, Shiko UV-7600B, Shiko UV-7605B, Shiko UV-7610B, Shiko UV-7620EA, Shiko UV- 7630B, purple light UV-7640B, purple light UV-7650B, purple light UV-6630B, purple light UV-7000B, purple light UV-7510B, purple light UV-7461TE, purple light UV-2000B, purple light UV-2750B, purple light UV-3000B, purple light UV- 3200B, Violet UV-3210EA, Violet UV-3300B, Violet UV-3310B, Violet UV-3500BA, Violet UV-3520TL, Violet UV-3700B, Violet UV-6640B;

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

Nippon Shokubai Co., Ltd., product names: VEEA, VEEM, etc.; Kuraray Co., Ltd., product number: UC-203; Daiwa Kasei Kogyo Co., Ltd., product numbers: BMI-1000, BMI-2000, BMI-2300, BMI -3000, BMI-4000, BMI-5100, BMI-7000, BMI-TMH, etc.; manufactured by Maruzen Petrochemical Co., Ltd., product numbers: BANI-X, BANI-M, etc., but the present disclosure is only such examples is not limited to These polyfunctional radically polymerizable compounds may be used alone or in combination of two or more.

The content of the polyfunctional radically polymerizable compound (b) may be adjusted according to the application and purpose, but when used, it is preferably 1 to 98% by mass, more preferably 2 to 95% by mass, and still more preferably 3 to 90% by mass.

The content of the radically polymerizable compound (that is, the total content of the monofunctional radically polymerizable monomer (a) and the multifunctional radically polymerizable compound (b)) may be adjusted according to the application and purpose. However, when used, it is preferably 1 to 98% by mass, more preferably 2 to 95% by mass, and still more preferably 3 to 90% by mass, based on 100% by mass of the total radically polymerizable components.

[Radical polymerization initiator]
Radical polymerization initiators can be classified into photoradical initiators that generate radicals by irradiation with active energy rays and thermal radical initiators that generate radicals by heating. An initiator and a thermal radical initiator may be used in combination.

Examples of photoradical initiators include alkylphenone-based compounds, benzophenone-based compounds, benzoin-based compounds, ketal-based compounds, anthraquinone-based compounds, phosphine oxide-based compounds, thioxanthone-based compounds, halomethylated triazine-based compounds, and halomethylated oxadiazoles. compounds, biimidazole-based compounds, oxime ester-based compounds, titanocene-based compounds, benzoic acid ester-based compounds, acridine-based compounds, etc., but the present disclosure is not limited only to such examples. These photoradical initiators may be used alone, respectively, or two or more of them may be used in combination.

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

2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, etc. phosphine oxide compounds of; Thioxanthone compounds such as thioxanthene-2-yl)oxy-2-hydroxypropyl]-trimethylazanium chloride; 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-sec-triazine, 2- (4-Methoxynaphthyl)-4,6-bis(trichloromethyl)-sec-triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-sec-triazine, 2-(4-ethoxy Halomethylated triazine compounds such as carboxynylnaphthyl)-4,6-bis(trichloromethyl)-sec-triazine; 2-trichloromethyl-5-[β-(2′-benzofuryl)vinyl]-1,3,4 -oxadiazole, 2-trichloromethyl-5-[β-(2′-(6″-benzofuryl)vinyl)]-1,3,4-oxadiazole, 2-trichloromethyl-5-furyl-1 Halomethylated oxadiazole compounds such as ,3,4-oxadiazole; 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole , 2,2′-bis(2,4-dichlorophenyl)-4,4′,5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis(2,4,6-tri Biimidazole compounds such as chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole; 1-[4-(phenylthio)-,2-(O-benzoyloxime)]- Oxime ester compounds such as 1,2-octanedione, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime)ethanone; Titanocene compounds such as (η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium; bis(2,4, Acylphosphine oxide compounds such as 6-trimethylbenzoyl)-phenylphosphine oxide and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide; benzoic acid esters such as p-dimethylaminobenzoic acid and p-diethylaminobenzoic acid compounds; acridine-based compounds such as 9-phenylacridine; and the like, but the present disclosure is not limited only to such examples.

As the thermal radical initiator, organic peroxide initiators and azo initiators are suitable, and specific examples thereof include the following.

methyl ethyl ketone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide, methyl acetoacetate peroxide, acetyl acetate peroxide, 1,1-bis(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1- bis(t-hexylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)-2-methylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)cyclododecane, 1,1-bis(t-butylperoxy)butane, 2,2-bis(4 ,4-di-t-butylperoxycyclohexyl)propane, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-hexyl Hydroperoxide, t-butyl hydroperoxide, α,α'-bis(t-butylperoxy)diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy) Hexane, t-butyl cumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexyne-3, isobutyryl peroxide, 3,5,5- trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, succinic acid peroxide, m-toluoyl benzoyl peroxide, benzoyl peroxide, di-n-propylperoxydicarbonate, diisopropylperoxide carbonate, bis(4-t-butylcyclohexyl)peroxydicarbonate, di-2-ethoxyethylperoxydicarbonate, di-2-ethoxyhexylperoxydicarbonate, di-3-methoxybutylperoxydicarbonate, di -s-butyl peroxydicarbonate, di(3-methyl-3-methoxybutyl)peroxydicarbonate, α,α'-bis(neodecanoylperoxy)diisopropylbenzene, cumyl peroxyneodecanoate, 1 , 1,3,3,-tetramethylbutyl peroxyneodecanoate, 1-cyclohexyl-1-methylethyl peroxyneodecanoate, t-hexyl peroxyneodecanoate, t-butyl peroxyneodecanoate noate, t-hexyl peroxypivalate, t-butyl peroxypivalate, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, 2,5-dimethyl-2,5- Bis(2-ethylhexanoylperoxy)hexanoate, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2 -ethylhexanoate, t-hexylperoxyisopropyl monocarbonate, t-butylperoxyisobutyrate, t-butylperoxymalate, t-butylperoxy-3,5,5-trimethylhexanoate, t -butyl peroxylaurate, t-butyl peroxy isopropyl monocarbonate, t-butyl peroxy-2-ethylhexyl monocarbonate, t-butyl peroxy acetate, t-butyl peroxy-m-toluyl benzoate, t-butyl peroxy oxybenzoate, bis(t-butylperoxy)isophthalate, 2,5-dimethyl-2,5-bis(m-toluylperoxy)hexane, t-hexylperoxybenzoate, 2,5-dimethyl-2,5 -bis(benzoylperoxy)hexane, t-butylperoxyallylmonocarbonate, t-butyltrimethylsilylperoxide, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 2,3- organic peroxide initiators such as dimethyl-2,3-diphenylbutane;

2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, 1-[(1-cyano-1-methylethyl)azo]formamide, 1,1′-azobis(cyclohexane-1-carbonitrile), 2, 2′-azobis(2-methylbutyronitrile), 2,2′-azobisisobutyronitrile, 2,2′-azobis(2,4-dimethylvaleronitrile), 2,2′-azobis(2, 4-dimethyl-4-methoxyvaleronitrile), 2,2′-azobis(2-methylpropionamidine) dihydrochloride, 2,2′-azobis(2-methyl-N-phenylpropionamidine) dihydrochloride, 2,2 '-azobis[N-(4-chlorophenyl)-2-methylpropionamidine]dihydrochloride, 2,2'-azobis[N-(4-hydrophenyl)-2-methylpropionamidine]dihydrochloride, 2,2' -azobis[2-methyl-N-(phenylmethyl)propionamidine]dihydrochloride, 2,2'-azobis[2-methyl-N-(2-propenyl)propionamidine]dihydrochloride, 2,2'-azobis[ N-(2-hydroxyethyl)-2-methylpropionamidine]dihydrochloride, 2,2'-azobis[2-(5-methyl-2-imidazolin-2-yl)propane]dihydrochloride, 2,2'- Azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride, 2,2′-azobis[2-(4,5,6,7-tetrahydro-1H-1,3-diazepin-2-yl) Propane]dihydrochloride, 2,2′-azobis[2-(3,4,5,6-tetrahydropyrimidin-2-yl)propane]dihydrochloride, 2,2′-azobis[2-(5-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 ]propionamide}, 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-methylpropionamide), 2,2′-azobis(2,4,4-trimethylpentane), 2,2′-azobis(2-methylpropane) , dimethyl-2,2-azobis (2-methylpropionate), 4,4'-azobis (4-cyanopentanoic acid), 2,2'-azobis [2-(hydroxymethyl) propionitrile] and the like Azo initiator.

These may be used individually by 1 type, and may use 2 or more types together.

Although the content of the radical polymerization initiator is not particularly limited, it is preferably 0.05 to 10.0 parts by mass, more preferably 0.1 to 7.0 parts by mass, based on 100 parts by mass of the total radically polymerizable components. parts by mass, more preferably 0.2 to 5.0 parts by mass.

[Compound having a reactive group other than radically polymerizable]
In order to improve various properties such as heat resistance and adhesion depending on the application, a low-molecular-weight compound, an oligomer, or a high-molecular compound having a reactive group other than radically polymerizable groups may be used.

Examples of such compounds include compounds having cationic polymerizable groups such as epoxy groups, oxetanyl groups, and vinyl ether groups; compounds having functional groups that react with carboxyl groups such as epoxy groups, oxazoline groups, carbodiimide groups, and aziridine groups; a compound having a group, and a compound having a functional group that reacts with a hydroxyl group such as an amino resin;

The content of the compound having a reactive group other than radically polymerizable may be adjusted according to the application and purpose, and may not be contained, but when used, the total amount of the radically polymerizable component is 100 parts by mass. , preferably 1 to 300 parts by mass, more preferably 2 to 200 parts by mass, still more preferably 3 to 100 parts by mass.

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

Examples of organic solvents include monoalcohols such as methanol, ethanol, isopropanol, n-butanol and sec-butanol; glycols such as ethylene glycol and propylene glycol; cyclic ethers such as tetrahydrofuran and dioxane; Glycol monoethers such as ethyl 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; ethylene glycol dimethyl ether , ethylene glycol diethyl ether, ethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, Ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene Esters of glycol monoethers such as glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, 3-methoxybutyl acetate; methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, methyl propionate, ethyl propionate, propionate Alkyl such as butyl acid, methyl lactate, ethyl lactate, butyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl acetoacetate, ethyl acetoacetate Ester; Acetone, methyl ethyl ketone, methyl isobutyl ketone, ketone such as cyclohexanone; Aromatic hydrocarbon compounds such as benzene, toluene, xylene, ethylbenzene; Aliphatic hydrocarbon compounds such as hexane, cyclohexane, octane; Dimethylformamide, dimethylacetamide, N - amides such as methylpyrrolidone; and the like, but the present disclosure is not limited to only such exemplifications. These organic solvents may be used alone or in combination of two or more.

The content of the organic solvent may be adjusted depending on the application and purpose, but when used, it is preferably 1 to 1000 parts by mass with respect to the total 100 parts by mass of the radically polymerizable components. More preferably 2 to 700 parts by mass, still more preferably 3 to 500 parts by mass.

In addition, the content of other components other than the components described above may be adjusted according to the application and purpose, and may not be included. is 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 disclosure>
The present disclosure is also a polymer obtained by polymerizing the polymerizable composition of the present disclosure under radical generation conditions.

The method of generating radicals includes a method of heating the polymerizable composition of the present disclosure and/or a method of irradiating the polymerizable composition of the present disclosure with active energy rays. Heating or irradiation with active energy rays may be performed in one step or in two or more steps. Heating and irradiation with active energy rays may be combined, may be combined simultaneously, or may be combined separately. When heating or irradiating with an active energy ray, the polymerizable composition of the present disclosure is more preferably in a state containing the aforementioned radical polymerization initiator.

The heating temperature may be appropriately selected according to the presence or absence, type, content, and application of the radical polymerization initiator. °C or higher.

As the active energy ray, one 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 these, gamma rays, X-rays, ultraviolet rays, visible rays, and electron beams are preferable, ultraviolet rays, visible rays, and electron beams are more preferable, and ultraviolet rays are most preferable, in terms of energy intensity, energy ray generator, and the like. . When a photoradical initiator is not used, it is preferable to use active energy rays with high energy such as gamma rays, X-rays, and electron beams. Active energy rays, which are relatively weak but are easy to generate and economical, can be preferably used.

Since the polymerizable composition of the present disclosure has good radical polymerizability as described above, it can be Dental materials, lenses, molding materials, various types of three-dimensional modeling (inkjet, SLA, DLP), intermediate layers of optical films, negative resist resins, water-absorbing resins, etc., for electrical and electronic parts, optical parts, medical use It can be suitably used for various industrial products or medical applications in which radical polymerization is performed by heating or irradiation with active energy rays, such as.

<How to save>
The present disclosure also provides a method for storing 2-oxymethyl acrylic acid (A) represented by formula (1) above, wherein the 2-oxymethyl acrylic acid (A) is represented by formula (I) above. Preserved in the presence of a carboxylate having a cation ratio of 0.01 or more and less than 1 and/or in the presence of water having a water ratio represented by the above formula (II) of 0.01 or more A method for storing 2-oxymethyl acrylic acid (A), comprising:

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

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

The storage method is not particularly limited, but the 2-oxymethyl acrylic acid (A) is stored in the presence of a carboxylate that satisfies a predetermined range of cation ratios and/or in the presence of water that satisfies a predetermined range of water ratios. It can be stored by a known method, such as putting it in a container or the like under the ground and allowing it to stand still.

The storage temperature is preferably 0 to 50.degree. C., more preferably 5 to 40.degree. C., from the viewpoints of suppressing radical polymerization and allowing easy temperature control.

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

<Polymerization material>
The present disclosure also provides a polymerized material containing 2-oxymethyl acrylic acid (A) represented by the above formula (1), a carboxylate and / or water, and a radical polymerization initiator, wherein the above calculation formula The cation ratio represented by (I) is 0.01 or more and less than 1, or the water ratio represented by the above formula (II) is 0.01 or more. A polymeric material characterized by

The polymer material of the present disclosure can suppress the generation of polymerization products due to cationic polymerization of the 2-oxymethyl acrylic acid (A), has excellent storage stability, and can provide a polymer having desired properties. can.

The 2-oxymethyl acrylic acid (A), carboxylate, water, and radical polymerization initiator contained in the polymerizable material of the present disclosure are the same as those described above. Moreover, the cation ratio and water ratio are also as described above.

The polymeric material of the present disclosure can be made into a polymerizable composition by mixing with other components. Examples of the other components include those similar to the other components used in the polymerizable composition described above. The polymerizable composition thus obtained is suitably used for manufacturing various industrial products or medical products.

EXAMPLES The present disclosure will be described in more detail with examples below, but the present disclosure is not limited only to these examples. Unless otherwise specified, "part" means "mass part" and "%" means "mass %".

<Measurement of carboxylate ion>
○ Measuring device Capillary electrophoresis system Agilent 7100 (Agilent Technologies, Inc.)
○Measurement conditions Measured by an indirect absorption method using a background absorber.
Capillary: bubble cell fused silica capillary (inner diameter 75 μm×length 80.5 cm)
Electrophoresis liquid: electrophoresis liquid for anion analysis (pH = 8.2)
Applied voltage: -20 kV
○ Quantitative method Quantified by the internal standard method (internal standard substance: sodium propionate) based on the area ratio.
Preparation of standard sample: After dissolving sodium propionate and the substance to be quantified (sodium salt of carboxylate ion) in heavy water and quantifying the molar ratio by ¹ H-NMR, further dilute with ultrapure water to create a calibration curve. It was used as a standard sample for
Preparation of measurement sample: A sodium propionate aqueous solution and a test sample were weighed and diluted with a 0.1N sodium hydroxide aqueous solution and ultrapure water to obtain a measurement sample.

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

<2-oxymethyl acrylic acid (A) and carboxylate>
○ 2-methoxymethyl acrylic acid:
2-Methoxymethyl acrylic acid with a purity of 97.3% (2-methoxymethyl acrylic acid concentration of 8.38 mmol/g) containing 0.05% (with respect to the total liquid amount) of hydroquinone monomethyl ether as a radical polymerization inhibitor prepared. Purity was measured using a capillary electrophoresis system.

○ 2-allyloxymethyl acrylic acid:
Contains 0.04% hydroquinone monomethyl ether (relative to the total amount of liquid) and 0.06% (relative to the total amount of liquid) of 2,2'-(ethylenedithio)diethanol as radical polymerization inhibitors, with a purity of 96.7 % (6.80 mmol/g as 2-allyloxymethylacrylic acid concentration) 2-allyloxymethylacrylic acid was prepared. Purity was measured using a capillary electrophoresis system.

○ 50% aqueous solution of sodium 2-allyloxymethyl acrylate:
After neutralization by adding an equivalent amount (equivalent to 100% neutralization) of 2-allyloxymethyl acrylic acid to a 10% sodium carbonate aqueous solution, hydroquinone monomethyl as a radical polymerization inhibitor was added again by concentrating and adding an appropriate amount of water. Sodium 2-allyloxymethyl acrylate concentration of 50%, containing 0.02% (relative to the total liquid volume) of ether and 0.03% (relative to the total volume of liquid) of 2,2'-(ethylenedithio)diethanol (3.05 mmol/g) of sodium 2-allyloxymethyl acrylate aqueous solution was prepared. The concentration of sodium 2-allyloxymethyl acrylate was obtained by measuring 2-allyloxymethyl acrylate ion with a capillary electrophoresis system, and using the resulting concentration as the concentration of sodium 2-allyloxymethyl acrylate.

[Comparative Example 1]
3.25 g of 2-methoxymethylacrylic acid and 0.75 g of ultrapure water were placed in a 50 ml test tube with a slide and a stirring bar, and the mixture was stirred and homogenized.
Next, non-heating solvent removal and dehydration operations were performed according to the following procedure.
4.0 g of diisopropyl ether and 3.0 g of acetone were added and stirred for homogenization. The test tube was connected to a vacuum line, and at room temperature, the degree of pressure reduction was gradually increased while paying attention to bumping. After the pressure reached 0.2 kPa, it was maintained for 30 minutes.
After the dehydration operation was completed, the pressure was returned to normal pressure, the stirring was stopped, and when the stirring bar was taken out and the state of the contents was checked, it was cloudy.
When the cloudy contents were allowed to stand overnight, a white precipitate settled. Liquid was removed from the test tube by decantation. 1.0 g of methanol was put into a test tube and dissolved, and the mixture was added dropwise to a mixed solvent of acetone/hexane=1/1 (weight ratio) to reprecipitate. The precipitate was removed by suction filtration and vacuum dried at room temperature. The resulting solid was dissolved in heavy water with a sodium carbonate concentration of 2%, and 1H-NMR was measured to confirm that it was a polymer. When the molecular weight of the obtained solid was measured using an APC system, the molecular weight was 99,000.

[Example 1]
0.15 g (1.4 mmol) of sodium carbonate and 0.75 g of ultrapure water were placed in a 50 ml test tube with a grinder containing a stirrer and stirred to dissolve the sodium carbonate. 25 g (27.2 mmol) was added and stirred for homogenization, and 10 mol % of 2-methoxymethylacrylic acid was sodium chloride to obtain the polymerizable composition (1) of the present disclosure. Here, the total amount of 2-methoxymethyl acrylic acid moieties in the polymerizable composition (1) is 27.2 mmol, the valence of sodium ions derived from sodium 2-methoxymethyl acrylate is 1, and the number of moles is 2.8 mmol. Therefore, the cation ratio based on the following formula (I) is 0.10.

(In formula (I), the total valence of cations derived from carboxylate is the sum of (valence of cations derived from carboxylate x mole number of cations). 2-oxymethyl The total amount of acrylic acid moieties is the number of moles of 2-oxymethylacrylic acid (A) + the number of moles of 2-oxymethylacrylate ions derived from the salt of 2-oxymethylacrylic acid (A).)
Next, solvent removal and dehydration were performed without heating in the same manner as in Comparative Example 1, and after the operation was completed, the contents of the test tube were checked. The contents were transparent.

[Comparative Example 2]
3.40 g of 2-allyloxymethylacrylic acid and 0.60 g of ultrapure water were placed in a 50 ml test tube with a slide and a stirring bar, and the mixture was stirred and homogenized.
Next, solvent removal and dehydration were performed without heating in the same manner as in Comparative Example 1. After completion of the operation, the content of the test tube was checked to find that it was cloudy.
The cloudy contents were reprecipitated and dried in the same manner as in Comparative Example 1, and ¹ H-NMR of the obtained solid was measured, confirming that it was a polymer. When the molecular weight of the obtained solid was measured using an APC system, the molecular weight was 142,000.

[Example 2]
3.10 g (21.1 mmol) of 2-allyloxymethylacrylic acid, 0.77 g (2.3 mmol) of 50% aqueous solution of sodium 2-allyloxymethyl acrylate, ultrapure 0.23 g of water was added, and the mixture was stirred and homogenized to obtain the polymerizable composition (2) of the present disclosure. Here, the total amount of 2-allyloxymethyl acrylic acid moieties in the polymerizable composition (2) is 23.4 mmol, the valence of sodium ions derived from sodium 2-allyloxymethyl acrylate is 1, and the number of moles is 2. Since it is 3 mmol, the cation ratio is 0.10.
Next, solvent removal and dehydration were performed without heating in the same manner as in Comparative Example 1, and after the operation was completed, the contents of the test tube were checked. The contents were transparent.

[Example 3]
3.30 g (22.4 mmol) of 2-allyloxymethylacrylic acid, 0.23 g (0.7 mmol) of 50% aqueous solution of sodium 2-allyloxymethyl acrylate, ultrapure 0.49 g of water was added and stirred to homogenize to obtain a polymerizable composition (3) of the present disclosure. Here, the total amount of 2-allyloxymethylacrylic acid moieties in the polymerizable composition (3) is 23.1 mmol, the valence of sodium ions derived from sodium 2-allyloxymethylacrylate is 1, and the number of moles is 0.1 mmol. Since it is 7 mmol, the cation ratio is 0.03.
Next, solvent removal and dehydration were performed without heating in the same manner as in Comparative Example 1, and after the operation was completed, the contents of the test tube were checked. The contents were transparent.

[Example 4]
3.40 g (23.1 mmol) of 2-allyloxymethylacrylic acid, 0.14 g (3.5 mmol) of magnesium oxide powder, and 0.60 g of ultrapure water were placed in a 50 ml test tube with a slide and a stirrer. ° C., and 15 mol % of 2-allyloxymethyl acrylic acid was magnesium chloride to give the polymerizable composition (4) of the present disclosure. Here, the total amount of 2-allyloxymethyl acrylic acid moieties in the polymerizable composition (4) was 23.1 mmol, the valence of magnesium ions derived from magnesium 2-allyloxymethyl acrylate was 2, and the number of moles was 3. Since it is 5 mmol, the cation ratio is 0.30.
Next, solvent removal and dehydration were performed without heating in the same manner as in Comparative Example 1, and after the operation was completed, the contents of the test tube were checked. The contents were transparent.

[Example 5]
3.40 g (23.1 mmol) of 2-allyloxymethylacrylic acid, 0.56 g (6.9 mmol) of zinc oxide powder, and 0.60 g of ultrapure water were placed in a 50 ml test tube with a slide and a stirring bar. ℃, and 60 mol% of 2-allyloxymethylacrylic acid was zinc chloride to obtain the polymerizable composition (5) of the present disclosure. Here, the total amount of 2-allyloxymethylacrylic acid moieties in the polymerizable composition (5) was 23.1 mmol, the valence of zinc ions derived from zinc 2-allyloxymethylacrylate was 2, and the number of moles was 6. Since it is 9 mmol, the cation ratio is 0.60.
Next, solvent removal and dehydration were performed without heating in the same manner as in Comparative Example 1, and after the operation was completed, the contents of the test tube were checked. The contents were transparent.

[Example 6]
3.40 g (23.1 mmol) of 2-allyloxymethylacrylic acid, 0.51 g (3.4 mmol) of N,N'-bis(2-hydroxyethyl)ethylenediamine, 0.60 g of ultrapure water was added and stirred at 45° C., and 30 mol % of 2-allyloxymethylacrylic acid was subjected to amine conversion to obtain the polymerizable composition (6) of the present disclosure. Here, the total amount of 2-allyloxymethylacrylic acid moieties in the polymerizable composition (6) is 23.1 mmol, the valence of the amine constituting the amine salt of 2-allyloxymethylacrylic acid is 2, and the number of moles is Since it is 3.4 mmol, the cation ratio is 0.30.
Next, solvent removal and dehydration were performed without heating in the same manner as in Comparative Example 1, and after the operation was completed, the contents of the test tube were checked. The contents were transparent.

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

This was placed up to the 7th minute in a 1.5 ml glass vial and stored in the cold compartment of a refrigerator (approximately 4°C). Confirmation was made every 3 months, and no polymer was formed even after storage for 18 months.

[Comparative Example 3]
10.0 g of the prepared 2-allyloxymethylacrylic acid and 5.0 g of ethyl acetate were placed in a 50 ml eggplant-shaped flask containing a stirrer, and azeotropic dehydration was performed by gradually reducing the pressure while heating to 60°C. . Finally, the pressure was reduced to 0.5 kPa, and after reaching 0.5 kPa, the pressure was released after maintaining the pressure for 20 minutes. 1 g of silica gel (Wakogel C-200, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was spread over a filter holder of a suction filtration device, and the dehydrated 2-allyloxymethyl acrylic acid was suction-filtered. The water content after filtration was measured with a Karl Fischer moisture meter and found to be 0.07%. That is, the moisture ratio based on the above formula (II) is 0.0007.
This was placed in a 1.5 ml glass vial up to the 7th minute and stored in the cold compartment of a refrigerator (approximately 4°C). When confirmed every 3 months, it was solidified in the 15th month.

[Example 8]
1.0 g of contents (mixture of 2-allyloxymethyl acrylic acid and zinc 2-allyloxymethyl acrylate) after unheated solvent removal and dehydration operations obtained in Example 5, 2.0 g of 2-ethylhexyl acrylate , and 0.09 g of 1-hydroxycyclohexylphenyl ketone were mixed and stirred to form a uniform solution.
Bar coater no. 2, the obtained liquid was applied to a heat-resistant acrylic film (a film having a thickness of 140 μm using a melt extruder from the pellets obtained by the method described in Production Example 7 of JP-A-2019-179124), Polymerization was carried out using a belt conveyor type UV irradiation device (illuminance of 500 mW/cm ² , integrated light intensity of 5 J/cm ² ).
Adhesion of the polymer layer was evaluated according to JIS K 5600-5-6 (cross-cut method). That is, the number of squares remaining without peeling or breakage among all squares (10×10 squares=100 squares) was evaluated to be 100.

From the results of Examples 1 to 6, it was revealed that the polymerizable composition of the present disclosure suppresses the generation of polymerization products in the non-heated desolvation/dehydration operation. Moreover, the results of Example 7 revealed that the generation of polymerization products during storage at low temperatures was suppressed. Furthermore, the results of Example 8 revealed that the polymerizable composition of the present disclosure has good photoradical polymerizability.

Claims

Formula (1) below:

(Wherein, R represents a hydrogen atom or a saturated or unsaturated hydrocarbon group having 10 or less carbon atoms.)
A polymerizable composition containing 2-oxymethyl acrylic acid (A) represented by and a carboxylate and / or water,
At least either the cation ratio represented by the following formula (I) is 0.01 or more and less than 1, or the water ratio represented by the following formula (II) is 0.01 or more A polymerizable composition characterized by satisfying

(In formula (I), the total valence of cations derived from carboxylate is the sum of [valence of cations derived from carboxylate x number of moles of cations]. 2-oxymethyl acryl The total amount of acid moieties is the sum of the number of moles of 2-oxymethylacrylic acid (A) and the number of moles of 2-oxymethylacrylate ions derived from 2-oxymethylacrylic acid (A).)
The cations derived from the carboxylate contain one or more cations selected from the group consisting of metal ions, metal oxide ions, and cations containing non-metallic atoms of group 15 of the periodic table. The polymerizable composition according to claim 1, wherein
The carboxylate comprises one or more carboxylates selected from the group consisting of salts of 2-oxymethyl acrylic acid (A), salts of acrylic acid, and salts of methacrylic acid. Item 3. The polymerizable composition according to Item 1 or 2.
The amount of 2-oxymethylacrylate ions contained in the carboxylate is 50 mol % or more and 100 mol % or less with respect to the total amount of carboxylate ions contained in the carboxylate. Item 4. The polymerizable composition according to any one of Items 1 to 3.
5. The polymerizable composition according to any one of claims 1 to 4, wherein R in the general formula (1) is an allyl group or a methallyl group.
A polymer obtained by polymerizing the polymerizable composition according to any one of claims 1 to 5 under radical generation conditions.
the following formula (1);

(Wherein, R represents a hydrogen atom or a saturated or unsaturated hydrocarbon group having 10 or less carbon atoms.)
A method for storing 2-oxymethyl acrylic acid (A) represented by
The 2-oxymethyl acrylic acid (A) is treated in the presence of a carboxylate having a cation ratio represented by the following formula (I) of 0.01 or more and less than 1, and / or ), a method for storing 2-oxymethyl acrylic acid (A) in the presence of water having a water ratio of 0.01 or more.

(In formula (I), the total valence of cations derived from carboxylate is the sum of [valence of cations derived from carboxylate x number of moles of cations]. 2-oxymethyl acryl The total amount of acid moieties is the sum of the number of moles of 2-oxymethylacrylic acid (A) and the number of moles of 2-oxymethylacrylate ions derived from 2-oxymethylacrylic acid (A).)
the following formula (1);

(Wherein, R represents a hydrogen atom or a saturated or unsaturated hydrocarbon group having 10 or less carbon atoms.)
A polymerized material containing 2-oxymethyl acrylic acid (A) represented by, a carboxylate and / or water, and a radical polymerization initiator,
At least either the cation ratio represented by the following formula (I) is 0.01 or more and less than 1, or the water ratio represented by the following formula (II) is 0.01 or more A polymeric material characterized by satisfying

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