Radical polymerizable composition and polymerized product thereof

Abstract

The purpose of the present invention is to provide a radical polymerizable composition that is liquid and can form a resin of an ionomer structure easily. The present invention is a radical polymerizable composition that contains a water-immiscible radical polymerizable compound (A) and an anion represented by formula (1) (in the formula, R represents a C10 or fewer saturated or unsaturated hydrocarbon group.), in which the content of the anion is 1-120 mass parts per 100 mass parts of the water-immiscible radical polymerizable compound (A).

Description

Radical polymerizable composition and polymer thereof

[0001] The present invention relates to a radically polymerizable composition and a polymer thereof.

[0002] Ionomers are basically resins in which a hydrophobic host polymer is crosslinked with ions, and numerous ionomers have been developed to date. Typical ionomers include ethylene-based ionomers, styrene-based ionomers, perfluorocarbon-based ionomers, telechelic ionomers, and polyurethane ionomers, which are synthesized by synthesizing a host polymer having ionizable functional groups and then ionizing (neutralizing) them (Non-Patent Document 1, pp. 2-6).

[0003] In particular, ethylene-based ionomers are the most widely used ionomers in industrial applications, and are resins in which the molecules of a copolymer of ethylene and an unsaturated carboxylic acid such as (meth)acrylic acid are ionically crosslinked with metal ions such as sodium or zinc, or amines. Unlike covalently crosslinked materials, ethylene-based ionomers are thermoplastic despite being crosslinked, and are known to exhibit various excellent properties such as transparency, toughness, abrasion resistance, low-temperature resistance, solvent resistance, heat-sealing properties, adhesive properties, and self-repairing properties (see, for example, Non-Patent Document 1, p. 171; Non-Patent Document 2; Patent Documents 1 to 3).

[0004] JP 2016-079408 A JP 2005-054019 A JP 11-029672 A

[0005] "Development of Ionomer Ionic Polymer Materials," CMC Publishing, 2009, Journal of the Robotics Society of Japan, Vol. 24, No. 4, p. 442, 2006

[0006] As described above, it is known to copolymerize ethylene / unsaturated carboxylic acid and ionize the copolymer to obtain an ethylene-based ionomer.

[0007] However, conventional ionomers are synthesized by synthesizing a host polymer having an ionizable functional group and then ionizing (neutralizing) it. Therefore, such resins are poorly soluble in common organic solvents, making it difficult to prepare liquid compositions.

[0008] Furthermore, metal salts of (meth)acrylic acid are widely used as monomers for carboxylates with high radical polymerizability. However, since these are miscible only with water or highly polar organic substances, it is difficult to dissolve them uniformly in low-polarity vinyl compounds to form a liquid.

[0009] Furthermore, if a nonionic polyfunctional vinyl compound such as a polyfunctional (meth)acrylic acid ester is used as a monomer, it can be uniformly dissolved in a low-polarity vinyl compound, and the resulting polymer will be a crosslinked product. However, the crosslinking is a covalent bond, and it is difficult to achieve the properties seen in ionomers, such as thermoplasticity.

[0010] Therefore, an object of the present invention is to provide a radically polymerizable composition that is liquid, can easily form a resin having an ionomer structure, and can be applied to, for example, various printing applications.

[0011] The present inventors have conducted various studies to achieve the above object and have arrived at the present invention. That is, the object of the present invention is achieved by the following [1] to [4]. [1] A water-immiscible radical polymerizable compound (A) and a polymerizable compound represented by the following formula (1):

[0012]

[0013] (wherein R represents a saturated or unsaturated hydrocarbon group having 10 or less carbon atoms), and the content of the anion is 1 to 120 parts by mass per 100 parts by mass of the water-immiscible radically polymerizable compound (A). [2] The radically polymerizable composition according to the above item [1], wherein R in formula (1) represents an allyl group or a methallyl group. [3] The radically polymerizable composition according to the above item [1] or [2], further comprising a cation, wherein the cation is one or more cations selected from the group consisting of metal ions, metal oxide ions, and cations containing non-metallic elements of Group 15 of the periodic table. [4] A polymer of the radically polymerizable composition according to any one of the above items [1] to [3].

[0014] The radical polymerizable composition of the present disclosure is liquid, can easily form a resin having an ionomer structure, and can give a cured product excellent in various properties such as adhesion, tensile properties, thermoplasticity, etc. Therefore, the radical polymerizable composition of the present disclosure can be suitably used for applications such as various printings, various coatings, adhesion, sealing, and three-dimensional modeling.

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

[0016] First, the components constituting the radical polymerizable composition of the present disclosure will be described.

[0017] <Radically polymerizable compound (A) immiscible with water> In the present invention, in order to obtain an ionic crosslinker having an ionomer structure, a radically polymerizable compound (A) immiscible with water is used as a main component for forming a polymer backbone. Here, "immiscible with water" is determined by whether or not it can be homogenized when mixed with water in equal masses. Furthermore, "homogeneous" refers to a state in which, when equal amounts of the radically polymerizable compound (A) and water are mixed, no precipitate is visually observed and the mixture is transparent. Furthermore, homogeneity can be determined by whether or not it is homogenous at the temperature and pressure at which polymerization is performed. However, more simply, it can be determined whether or not it is homogenous at room temperature and normal pressure. Furthermore, the temperature and pressure at which mixing is performed do not have to be room temperature and normal pressure. Here, the temperature and pressure used for determination are most preferably 20°C and 101.3 kPa.

[0018] The water-immiscible radically polymerizable compound (A) (hereinafter sometimes simply referred to as "polymerizable compound (A)") is a compound that is immiscible with water and has a radically polymerizable group, and can be classified into a monofunctional type that forms a linear polymer by polymerization, and a polyfunctional type that forms a covalently crosslinked compound. The radically polymerizable group may be any unsaturated bond that is radically polymerizable, preferably a carbon-carbon double bond, and more preferably a carbon-carbon double bond that has been activated by bonding a functional group.

[0019] Examples of activated carbon-carbon double bonds include, but are not limited to, a carbon-carbon double bond having a carbonyl group bonded thereto, a carbon-carbon double bond having a cyano group bonded thereto, a carbon-carbon double bond having a nitrogen atom bonded thereto, a carbon-carbon double bond having an aromatic ring bonded thereto, a carbon-carbon double bond having an oxygen atom bonded thereto, a carbon-carbon double bond having a conjugated carbon-carbon double bond bonded thereto, and a carbon-carbon double bond having a halogen atom bonded thereto. Of these, preferred are a carbon-carbon double bond having a carbonyl group bonded thereto, a carbon-carbon double bond having a cyano group bonded thereto, a carbon-carbon double bond having a nitrogen atom bonded thereto, and a carbon-carbon double bond having an aromatic ring bonded thereto.

[0020] Examples of the compound having a carbon-carbon double bond to which a carbonyl group is bonded include (meth)acrylic acid esters, 2-(meth)allyloxymethylacrylic acid esters, (meth)acrylamides, N-substituted maleimides, maleic acid esters, fumaric acid esters, and itaconic acid esters.

[0021] Examples of compounds having a carbon-carbon double bond bonded to a cyano group include (meth)acrylonitrile and 2-cyanoacrylic acid esters. Examples of compounds having a carbon-carbon double bond bonded to a nitrogen atom include N-vinylamides and vinylamines. Examples of compounds having a carbon-carbon double bond bonded to an aromatic ring include aromatic vinyls. Examples of compounds having a carbon-carbon double bond bonded to an oxygen atom include vinyl esters and vinyl ethers. Examples of compounds having conjugated carbon-carbon double bonds include 1,3-dienes. The present disclosure is not limited to these examples.

[0022] Among these, from the viewpoints of polymerization activity and the variety of structures that can be synthesized, compounds having a carbon-carbon double bond bonded to a carbonyl group are preferred, and (meth)acrylic acid esters and 2-(meth)allyloxymethylacrylic acid esters are more preferred. Furthermore, from the viewpoints of polymerization activity and the ability to effectively introduce a low-polarity structure, compounds having a carbon-carbon double bond bonded to an aromatic ring are preferred, and aromatic vinyls are more preferred.

[0023] Specific examples of compounds belonging to (meth)acrylic acid esters, 2-(meth)allyloxymethylacrylic acid esters, and aromatic vinyls as the polymerizable compound (A) are shown below, but the present disclosure is not limited to these examples.

[0024] Examples of monofunctional (meth)acrylic acid esters include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, n-amyl (meth)acrylate, sec-amyl (meth)acrylate, tert-amyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, Alkyl esters such as isodecyl (meth)acrylate, tridecyl (meth)acrylate, lauryl (meth)acrylate, and stearyl (meth)acrylate; alicyclic esters such as cyclohexyl (meth)acrylate, cyclohexylmethyl (meth)acrylate, 3,5,5-trimethylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, and tricyclodecanyl (meth)acrylate; benzyl (meth)acrylate, phenyl (meth)acrylate, and the like. Examples of aromatic esters include: ether structure-containing esters such as 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, phenoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, glycidyl (meth)acrylate, (3,4-epoxycyclohexyl)methyl (meth)acrylate, and (3-ethyloxetan-3-yl)methyl (meth)acrylate; esters in which some or all of the hydrogen atoms at the ester moiety have been substituted with fluorine atoms, such as 2,2,2-trifluoroethyl (meth)acrylate and 2,2,3,3,3-pentafluoropropyl (meth)acrylate; esters in which some or all of the hydrogen atoms at the ester moiety have been substituted with silyl groups or silyloxy groups, such as trimethylsilylmethyl (meth)acrylate and 3-[tris(trimethylsilyloxy)silyl]propyl (meth)acrylate; however, the present disclosure is not limited to these examples, and any ester having a (meth)acrylic acid ester structure and immiscible with water is sufficient.

[0025] Examples of polyfunctional (meth)acrylic acid esters include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, hexanediol di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, bisphenol A alkylene oxide di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate. esters of alcohols having a vinyl ether group such as 2-vinyloxyethyl (meth)acrylate and 2-(vinyloxyethoxy)ethyl (meth)acrylate; oligomers / polymers having a (meth)acrylic acid ester structure such as urethane (meth)acrylate oligomers / polymers, epoxy (meth)acrylate oligomers / polymers, and polyester (meth)acrylate oligomers / polymers; however, the present disclosure is not limited to these examples, and any oligomers / polymers having a (meth)acrylic acid ester structure and immiscible with water may be used.

[0026] Examples of monofunctional 2-(meth)allyloxymethyl acrylate esters include methyl 2-(meth)allyloxymethyl acrylate, ethyl 2-(meth)allyloxymethyl acrylate, n-propyl 2-(meth)allyloxymethyl acrylate, isopropyl 2-(meth)allyloxymethyl acrylate, n-butyl 2-(meth)allyloxymethyl acrylate, sec-butyl 2-(meth)allyloxymethyl acrylate, tert-butyl 2-(meth)allyloxymethyl acrylate, 2-(meth)allyloxymethyl acrylate, alkyl esters such as n-amyl 2-(meth)allyloxymethylacrylate, sec-amyl 2-(meth)allyloxymethylacrylate, tert-amyl 2-(meth)allyloxymethylacrylate, n-hexyl 2-(meth)allyloxymethylacrylate, 2-ethylhexyl 2-(meth)allyloxymethylacrylate, isodecyl 2-(meth)allyloxymethylacrylate, tridecyl 2-(meth)allyloxymethylacrylate, lauryl 2-(meth)allyloxymethylacrylate, and stearyl 2-(meth)allyloxymethylacrylate; alicyclic esters such as cyclohexyl 2-(meth)allyloxymethylacrylate, cyclohexylmethyl 2-(meth)allyloxymethylacrylate, 3,5,5-trimethylcyclohexyl 2-(meth)allyloxymethylacrylate, isobornyl 2-(meth)allyloxymethylacrylate, adamantyl 2-(meth)allyloxymethylacrylate, and tricyclodecanyl 2-(meth)allyloxymethylacrylate; aromatic esters such as benzyl 2-(meth)allyloxymethylacrylate and phenyl 2-(meth)allyloxymethylacrylate; Ether structure-containing esters such as 2-methoxyethyl 2-(meth)allyloxymethylacrylate, 2-ethoxyethyl 2-(meth)allyloxymethylacrylate, phenoxyethyl 2-(meth)allyloxymethylacrylate, tetrahydrofurfuryl 2-(meth)allyloxymethylacrylate, glycidyl 2-(meth)allyloxymethylacrylate, (3,4-epoxycyclohexyl)methyl 2-(meth)allyloxymethylacrylate, and (3-ethyloxetan-3-yl)methyl 2-(meth)allyloxymethylacrylate;Examples include esters in which some or all of the hydrogen atoms at the ester moiety have been substituted with fluorine atoms, such as 2,2,2-trifluoroethyl 2-(meth)allyloxymethyl acrylate and 2,2,3,3,3-pentafluoropropyl 2-(meth)allyloxymethyl acrylate; esters in which some or all of the hydrogen atoms at the ester moiety have been substituted with silyl groups or silyloxy groups, such as trimethylsilylmethyl 2-(meth)allyloxymethyl acrylate and 3-[tris(trimethylsilyloxy)silyl]propyl 2-(meth)allyloxymethyl acrylate; however, the present disclosure is not limited to these examples, and any ester having a 2-(meth)allyloxymethyl acrylate structure and immiscible with water is sufficient.

[0027] Examples of polyfunctional 2-(meth)allyloxymethyl acrylate esters include ethylene glycol di(2-(meth)allyloxymethyl acrylate), propylene glycol di(2-(meth)allyloxymethyl acrylate), butylene glycol di(2-(meth)allyloxymethyl acrylate), hexanediol di(2-(meth)allyloxymethyl acrylate), cyclohexanedimethanol di(2-(meth)allyloxymethyl acrylate), bisphenol A alkylene oxide di(2-(meth)allyloxymethyl acrylate), trimethylolpropane tri(2-(meth)allyloxymethyl acrylate), pentaerythritol tetra(2-(meth)allyloxymethyl acrylate), dipentaerythritol penta(2-(meth)allyloxymethyl acrylate), dipentaerythritol esters of alcohols having a vinyl ether group, such as 2-vinyloxyethyl 2-(meth)allyloxymethylacrylate and 2-(vinyloxyethoxy)ethyl 2-(meth)allyloxymethylacrylate; oligomers / polymers having a 2-(meth)allyloxymethyl acrylate structure, such as urethane(2-(meth)allyloxymethyl acrylate)-based oligomers / polymers, epoxy(2-(meth)allyloxymethyl acrylate)-based oligomers / polymers, and polyester(2-(meth)allyloxymethyl acrylate)-based oligomers / polymers; however, the present disclosure is not limited to these examples, and any oligomers / polymers having a 2-(meth)allyloxymethyl acrylate structure and immiscible with water are acceptable.

[0028] Examples of monofunctional or polyfunctional aromatic vinyl compounds include styrene, α-methylstyrene, vinyltoluene, methoxystyrene, and divinylbenzene, but the present disclosure is not limited to these examples, and any compound may be used as long as it has a carbon-carbon double bond to which an aromatic ring is bonded and is immiscible with water.

[0029] The number of carbon atoms in the polymerizable compound (A) is preferably 4 to 90, more preferably 5 to 80, and even more preferably 6 to 70, from the viewpoints of making the polymerizable compound (A) immiscible with water and having a low viscosity even if it is a polyfunctional compound.

[0030] The polymerizable compounds (A) may be used alone or in combination of two or more types depending on the purpose and application.

[0031] From the viewpoint of achieving a good balance between the viscosity of the composition and the mechanical properties of the polymer, such as toughness, the content of the polymerizable compound (A) is preferably 10 to 97% by mass, more preferably 20 to 94% by mass, and even more preferably 30 to 90% by mass, relative to 100% by mass of the radically polymerizable composition.

[0032] <Anion Represented by Formula (1)> The radical polymerizable composition of the present disclosure includes an anion represented by the following formula (1):

[0033]

[0034] (where R represents a saturated or unsaturated hydrocarbon group having 10 or fewer carbon atoms.) Conventional ionomers are synthesized by synthesizing a host polymer having ionizable functional groups and then ionizing (neutralizing) it. Such resins are poorly soluble in ordinary organic solvents, making them difficult to prepare into liquid compositions. Even if they can be liquefied, the resin concentration must be significantly reduced. On the other hand, it is believed that a resin having an ionomer structure can be formed by radically polymerizing a composition consisting of a radically polymerizable salt and a low-polarity radically polymerizable compound. Furthermore, metal (meth)acrylate salts, which are commonly used as radically polymerizable salts, are highly radically polymerizable but are miscible only with water or highly polar organic substances, making it difficult to dissolve them uniformly in low-polarity vinyl compounds and liquefy them. Furthermore, although polyvalent acrylic esters can be mixed with low-polarity monomers and form crosslinked products, the crosslinking is covalent, making it difficult to achieve the thermoplastic and other properties seen in ionomers. In the present invention, by using the above anion, it is possible to uniformly dissolve even a low-polarity vinyl compound and prepare a liquid polymerizable composition, and it is also possible to satisfactorily form a resin having an ionomer structure by a simple method such as coating or printing.

[0035] In order to obtain the radical polymerizable composition of the present invention containing the anion represented by the above formula (1), it is preferable to use, as a component for forming an ionic crosslinked structure, a radical polymerizable carboxylate compound (B) composed of an anionic component containing the anion represented by the above formula (1) and a cationic component. That is, the radical polymerizable composition of the present invention preferably contains a radical polymerizable carboxylate compound (B) formed from an anion containing at least the anion represented by the above formula (1) and a cation.

[0036] From the viewpoint of solubility in the polymerizable compound (A) and in organic solvents, R preferably has 3 or more carbon atoms, and more preferably has 3 to 10 carbon atoms. From the viewpoint of forming a polar structure by cyclopolymerization, R is further preferably a (meth)allyl group.

[0037] In the radical polymerizable composition of the present invention, when the content of the anion represented by the above formula (1) is 1 to 120 parts by mass relative to 100 parts by mass of the polymerizable compound (A), a good balance can be achieved between the viscosity of the composition and the mechanical properties of the polymer, such as toughness. The content of the anion represented by the above formula (1) is preferably 2 to 115 parts by mass, more preferably 3 to 110 parts by mass, even more preferably 10 to 105 parts by mass, and still more preferably 20 to 100 parts by mass relative to 100 parts by mass of the polymerizable compound (A).

[0038] Hereinafter, the anion represented by the above formula (1) may be referred to as a "2-oxymethylacrylic acid ion," and the radical polymerizable carboxylate compound (B) containing the anion represented by the above formula (1) may be referred to as a "polymerizable salt compound (B)."

[0039] The polymerizable salt compound (B) may contain only a 2-oxymethylacrylic acid ion as the anion constituting the polymerizable salt compound (B), or may contain a 2-oxymethylacrylic acid ion and an anion other than the 2-oxymethylacrylic acid ion. The anion other than the 2-oxymethylacrylic acid ion is not particularly limited, but is preferably an anion of an organic protonic acid from the viewpoint of solubility in the polymerizable compound (A) and in organic solvents. Specific examples of such anions in terms of the name of protonic acid include carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, myristic acid, stearic acid, oxalic acid, malonic acid, succinic acid, adipic acid, cyclohexanetricarboxylic acid, benzoic acid, phthalic acid, terephthalic acid, trimellitic acid, acrylic acid, methacrylic acid, maleic acid, fumaric acid, and itaconic acid; organic phosphoric acids such as 2-ethylhexyl acid phosphate and 2-methacryloyloxyethyl acid phosphate; and organic sulfonic acids such as dodecylbenzenesulfonic acid, p-toluenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, and p-styrenesulfonic acid, but the present disclosure is not limited to these examples.

[0040] The cation constituting the polymerizable salt compound (B) may be an inorganic cation or an organic cation, and may be appropriately selected depending on the purpose and application. The polymerizable salt compound (B) may contain one or more types of cations. That is, the radical polymerizable composition of the present invention may further contain a cation, and the cation is preferably the cation constituting the polymerizable salt compound (B).

[0041] Examples of inorganic cations include metal ions or metal oxide ions, and specific examples of these cations by element or metal oxide name include elements of Group 1 of the periodic table, such as lithium, sodium, and potassium; elements of Group 2 of the periodic table, such as magnesium, calcium, and barium; transition metal elements or transition metal oxides, such as lanthanum, zirconium oxide, iron, cobalt, nickel, and copper; and typical metal elements of Groups 12 to 15 of the periodic table, such as zinc, aluminum, tin, lead, and bismuth. However, the cations are not limited to these examples, and may be a combination of ions of two or more metals or metal oxides. From the viewpoint of rendering the polymerizable composition of the present disclosure colorless, the metal ion portion of the metal carboxylate is preferably an ion of a typical metal element or a metal or metal oxide belonging to Groups 3 and 4 of the periodic table. Taking into account availability and toxicity, lithium, sodium, potassium, magnesium, calcium, zinc, and aluminum are more preferred.

[0042] Examples of organic cations include cations containing nonmetallic elements of Group 15 of the periodic table. Examples of nonmetallic elements of Group 15 of the periodic table include nitrogen, phosphorus, and arsenic. Preferred examples include ions in which nitrogen atoms are cationized (ammonium ions, protonated amines, and quaternary ammonium ions) and ions in which phosphorus atoms are cationized (phosphonium ions, protonated phosphines, and quaternary ammonium ions). However, from the viewpoints of biological safety and availability, ions in which nitrogen atoms are cationized are preferred.

[0043] Specific examples of protonated amines that are named using the names of the amines before protonation include methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, ethanolamine, diethanolamine, triethanolamine, tris(2-aminoethyl)amine, hexamethylenediamine, iminobispropylamine, methyliminobispropylamine, 3,6,9,12-tetraoxa-tetradecane-1,14diamine, N,N '-bis(2-hydroxyethyl)ethylenediamine, 1,3-bisaminomethylcyclohexane, 1,4-bisaminomethylcyclohexane, 3-aminomethyl-3,5,6-trimethylcyclohexylamine, isophoronediamine, 2,5 (or 2,6)-bis(aminomethyl)bicyclo[2,2,1]heptane, 2,6 (or 2,7)-bis(aminomethyl)bicyclo[3,2,1]octane, 2,5 (or 2,6)-bis(aminomethyl)-7-dimethylbicyclo[2 ,2,1]heptane, 2,6-bis(aminomethyl)adamantane, m-xylylenediamine, p-phenylenediamine, bis(4-aminophenyl)methane, 1,4 (or 2,6 or 2,7)-bis(aminomethyl)naphthalene, diallylamine, piperazine, aminoethylpiperazine, bisaminopropylpiperazine, 2,4,6-triamino-1,3,5-triazine, 2-methylimidazole, 2-ethyl-4-methylimidazole, diazabicycloundecene, diazabicyclopentene, Examples of the amines include various amines having primary to tertiary structures at the nitrogen atom moiety and monovalent and divalent or higher amine valencies, such as xabicyclononene, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, polyethyleneimine, and diallylamine polymers; however, the present disclosure is not limited to these examples.

[0044] Specific examples of quaternary ammonium ions include tetramethylammonium ion, tetraethylammonium ion, tetrabutylammonium ion, benzyltrimethylammonium ion, and hexadecyltrimethylammonium ion, but the present disclosure is not limited to these examples.

[0045] The cation is preferably one or more cations selected from the group consisting of metal ions, metal oxide ions, and cations containing non-metallic elements of Group 15 of the periodic table.

[0046] The method for preparing the polymerizable salt compound (B) includes the step of reacting a compound represented by the following formula (2):

[0047]

[0048] (wherein R represents a saturated or unsaturated hydrocarbon group having 10 or less carbon atoms), with one or more bases. The protonic acid may be completely or partially neutralized. When the protonic acid is partially neutralized, a mixture of a salt compound and the protonic acid is produced.

[0049] R in the above formula (2) is the same as R in the above formula (1). Examples of protonic acids that can be used other than 2-oxymethylacrylic acid represented by formula (2) include the organic protonic acids described above. Examples of the base include inorganic bases such as hydroxides and oxides of metal elements belonging to Groups 1 to 15 of the periodic table, and organic bases containing non-metallic elements of Group 15 of the periodic table, such as ammonia, amines, and ammonium hydroxide. The neutralization is not particularly limited and can be carried out by a known method.

[0050] The radically polymerizable composition of the present disclosure may contain only one type of the polymerizable salt compound (B), or may contain two or more types.

[0051] <Other Components> The polymerizable composition of the present disclosure may contain components other than the polymerizable compound (A) and the polymerizable salt compound (B) depending on the intended use, application, etc. Examples of such components include a radical polymerization inhibitor, a radical polymerization initiator, a solvent, a radically polymerizable compound miscible with water, a compound that undergoes a thermal addition reaction or a thermal condensation reaction with an active hydrogen group, a thermoplastic resin, organic or inorganic fine particles, a filler, a dye, a pigment, a dispersant, an ultraviolet absorber, a leveling agent, a surface conditioner, an antistatic agent, an adhesion improver, a coupling agent, a mold release agent, and a viscosity modifier, but the present disclosure is not limited to these.

[0052] Among the other components, the main ones are specifically shown below, but the present disclosure is not limited to these examples.

[0053] [Radical Polymerization Inhibitor] From the viewpoint of inhibiting undesired radical polymerization during various operations such as storage, transportation, and preparation and processing of the composition, the radical polymerizable composition of the present disclosure may contain an appropriate amount of a primary antioxidant having a radical chain inhibitory property and / or a secondary antioxidant having a peroxide decomposition property.

[0054] Examples of primary antioxidants include hydroquinones, benzoquinones, phenols, aromatic amines, phenothiazines, dithiocarbamic acid metal salts, and nitroso compounds, but the present disclosure is not limited to these examples. Examples of secondary antioxidants include phosphorus-based compounds such as phosphine and phosphites, and sulfur-based compounds such as thioethers, mercaptobenzimidazole, and thiourea, but the present disclosure is not limited to these examples. The primary antioxidants and secondary antioxidants may be used alone, but it is more preferable to use them in combination.

[0055] Among primary antioxidants, phenols are preferred from the viewpoint of inhibiting coloration, and among secondary antioxidants, thioethers are preferred from the viewpoint of acid resistance and hydrolysis resistance.

[0056] Examples of phenols include monoetherified hydroquinones, hindered phenols and their polymers (including dimers) or derivatives of the polymers, and semi-hindered phenols and their polymers (including dimers) or derivatives of the polymers, but the present disclosure is not limited to these examples. These phenols may be used alone or in combination of two or more.

[0057] Examples of monoetherified hydroquinones include hydroquinone monomethyl ether, hydroquinone mono-n-butyl ether, hydroquinone monobenzyl ether, hydroquinone monocyclohexyl ether, 4-methoxy-1-naphthol, etc., but the present disclosure is not limited to these examples. These monoetherified hydroquinones may be used alone or in combination of two or more.

[0058] Examples of hindered phenols include 2,6-bis(tert-butyl)-4-methylphenol, octadecyl-3-(3,5-ditert-butyl-4-hydroxyphenyl)propionate, isooctyl-3-(3,5-ditert-butyl-4-hydroxyphenyl)propionate, 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-ditert-butylanilino)-1,3,5-triazine, and 3,5-ditert-butyl-4-hydroxybenzylphosphonate-diethyl ester, but the present disclosure is not limited to these examples.

[0059] Examples of the oligomers or derivatives of oligomers of hindered phenols include pentaerythrityl tetrakis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propionate], 2,2-thio-diethylenebis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-ditert-butyl-4-hydroxy-hydrocinnamamide), 1,6-hexanediol-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propionate], tris-(3,5-ditert-butyl-4-hydroxybenzyl)isocyanurate, and 1,3,5-trimethyl-2,4,6-tris(3,5-ditert-butyl-4-hydroxybenzyl)benzene, but the present disclosure is not limited to these examples. The hindered phenols and their polymers (including dimers) or derivatives of the polymers may be used either alone or in combination of two or more kinds.

[0060] Examples of semi-hindered phenols include 6-tert-butyl-o-cresol, 6-tert-butyl-2,4-xylenol, 2,4,8,10-tetra-tert-butyl-6-[3-(3-methyl-4-hydroxy-5-t-butylphenyl)propoxy]dibenzo[d,f][1,3,2]dioxaphosphepine, 2,4-dimethyl-6-(1-methylpentadecyl)phenol, 2,4-bis(octylthiomethyl)-o-cresol, 2,4-bis(dodecylthiomethyl)-o-cresol, 2-tert-butylphenol, 2,4-di-tert-butylphenol, 2-tert-amylphenol, and 2,4-di-tert-amylphenol, but the present disclosure is not limited to these examples.

[0061] Examples of the polymerized products or derivatives of polymerized products of semi-hindered phenols include methylenebis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate], triethylene glycol bis[β-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 4,4'-thiobis(2-methyl-6-tert-butylphenol), bis(3-methyl-4-hydroxy-5-tert-butylbenzyl)sulfide, terephthaloyl-di(2,6-dimethyl-4-tert-butyl-3-hydroxybenzyl sulfide), 3,9-bis[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, 4,4'-butyl- Examples of suitable hydroxyl groups include 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, and 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate, but the present disclosure is not limited to these examples. The semi-hindered phenols and their polymers (including dimers) or derivatives of the polymers may be used either alone or in combination of two or more kinds.

[0062] Examples of phosphines include, but are not limited to, triethylphosphine, tributylphosphine, tris(2-ethylhexyl)phosphine, triphenylphosphine, etc. These phosphines may be used alone or in combination of two or more.

[0063] Examples of phosphites include diethyl hydrogen phosphite, bis(2-ethylhexyl) hydrogen phosphite, dilauryl hydrogen phosphite, dioleyl hydrogen phosphite, diphenyl hydrogen phosphite, triethyl phosphite, tributyl phosphite, tris(2-ethylhexyl) phosphite, triisodecyl phosphite, trilauryl phosphite, tris(tridecyl phosphite), trioleyl phosphite, tristearyl phosphite, phenyl diisodecyl phosphite, Sodecyl phosphite, diphenyl methyl phosphite, 2-ethylhexyl diphenyl phosphite, isodecyl diphenyl phosphite, tridecyl diphenyl phosphite, bis(2,4-ditert-butyl-6-methylphenyl)ethyl phosphite, triphenyl phosphite, tricresyl phosphite, tris(nonylphenyl) phosphite, tris(2,4-ditert-butylphenyl) phosphite, bis(isodecyl)pentaerythritol diphosphite, bis(tridecyl)pentaerythritol tetritol diphosphite, bis(stearyl)pentaerythritol diphosphite, bis(nonylphenyl)pentaerythritol diphosphite, bis(2,4-ditert-butylphenyl)pentaerythritol diphosphite, bis(2,6-ditert-butyl-6-methylphenyl)pentaerythritol diphosphite, 4,4'-butylidenebis(3-methyl-6-tert-butylphenyldiisotridecyl)phosphite, tetraphenyldipropylene glycol diphosphite, tetraphenyl te tetra(tridecyl)pentaerythritol tetraphosphite, tetra(C12-C15 alkyl)-4,4'-isopropylidenediphenyl phosphite, tetra(tridecyl)-1,1,3-tris(2-methyl-5-tert-butyl-4-hydroxyphenyl)butane diphosphite, 2,4,8,10-tetra-tert-butyl-6-[3-(3-methyl-4-hydroxy-5-tert-butylphenyl)propoxy]dibenzo[d,f][1,3,2]dioxaphosphepine, 2,2-methylenebis(4,Examples of suitable phosphites include (6-tert-butylphenyl)-2-ethylhexyl phosphite and trilauryl trithiophosphite, but the present disclosure is not limited to these examples. These phosphites may be used alone or in combination of two or more types.

[0064] Examples of thioethers include 2,2'-thiodiglycolic acid, (ethylenedithio)diacetic acid, 2,2'-(ethylenedithio)diethanol, 3,3'-thiodipropionic acid, dimethyl 3,3'-thiodipropionate, 3-laurylthiopropionic acid, methyl 3-laurylthiopropionate, (3-octylthiopropionic acid) pentaerythritol tetraester, (3-decylthiopropionic acid) pentaerythritol tetraester, (3-laurylthiopropionic acid) pentaerythritol tetraester, (3-oleylthiopropionic acid) pentaerythritol tetraester, (3-stearylthiopropionic acid) pentaerythritol tetraester, (3-laurylthiopropionic acid) pentaerythritol tetraester, Examples of thioethers include 4,4'-thiodi(3-methyl-5-tert-butyl-4-phenol) ester of laurylthiopropionic acid, dioctyl thiodipropionate, didecyl thiodipropionate, dilauryl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, laurylstearyl thiodipropionate, distearyl-β,β'-thiodibutyrate, dimethyl sulfide, methyl dodecyl sulfide, dilauryl sulfide, distearyl sulfide, 2,4-bis(octylthiomethyl)-o-cresol, and 2,4-bis(dodecylthiomethyl)-o-cresol, but the present disclosure is not limited to these examples. These thioethers may be used alone or in combination of two or more types.

[0065] The amount of the radical polymerization inhibitor is preferably 0.005 to 2 parts by mass, more preferably 0.01 to 1 part by mass, and even more preferably 0.02 to 0.5 parts by mass, relative to 100 parts by mass of the total of the radically polymerizable components, from the viewpoint of suppressing radical polymerization during storage, transportation, and various operations in composition preparation and processing, while also ensuring radical polymerizability appropriate for the application.

[0066] [Radical Polymerization Initiator] Radical polymerization initiators can be classified into photoradical initiators that generate radicals upon irradiation with active energy rays and thermal radical initiators that generate radicals upon heating. They can be selected according to the application and purpose, and a photoradical initiator and a thermal radical initiator may be used in combination.

[0067] Examples of photoradical initiators include alkylphenone compounds, benzophenone compounds, benzoin compounds, ketal compounds, anthraquinone compounds, phosphine oxide compounds, thioxanthone compounds, halomethylated triazine compounds, halomethylated oxadiazole compounds, biimidazole compounds, oxime ester compounds, titanocene compounds, benzoic acid ester compounds, and acridine compounds, but the present disclosure is not limited to these examples. These photoradical initiators may be used alone or in combination of two or more.

[0068] Specific examples include acetophenone, 1,1-dichloroacetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl] alkylphenone compounds such as {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]-1-[4-(4-morpholinyl)phenyl]-1-butanone; benzophenone, 4,4'-bis(dimethylamino)benzophenone, 2-carboxybenzophenone, 4-benzoyl-4'-methyldiphenyl benzophenone compounds such as sulfides; benzoin compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; ketal compounds such as acetophenone dimethyl ketal and benzil dimethyl ketal; anthraquinone compounds such as 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-chloroanthraquinone, and 2-amylanthraquinone; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis-(2,6-dimethoxy phosphine oxide compounds such as bis(2,4,6-trimethylbenzoyl)-2,4,4-trimethylpentylphosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; thioxanthone compounds such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, and [3-(3,4-dimethyl-9-oxothioxanthen-2-yl)oxy-2-hydroxypropyl]-trimethylazanium chloride;Halomethylated triazine compounds such as 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, and 2-(4-ethoxycarboxynylnaphthyl)-4,6-bis(trichloromethyl)-sec-triazine; 2-trichloromethyl-5-[β-(2'-benzofuryl)vinyl]-1,3 halomethylated oxadiazole compounds such as 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-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis Biimidazole compounds such as (2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole; oxime ester compounds such as 1-[4-(phenylthio)-, 2-(O-benzoyloxime)]-1,2-octanedione, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime)ethanone; bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H- Examples of suitable compounds include titanocene compounds such as (pyrrol-1-yl)-phenyl)titanium; acylphosphine oxide compounds such as bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide; benzoic acid ester compounds such as p-dimethylaminobenzoic acid and p-diethylaminobenzoic acid; and acridine compounds such as 9-phenylacridine, but the present disclosure is not limited to these examples.

[0069] As the thermal radical initiator, an organic peroxide initiator or an azo initiator is suitable, and specific examples thereof include the following.

[0070] Methyl ethyl ketone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide, methyl acetoacetate peroxide, acetylacetate peroxide, 1,1-bis(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-hexylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)-2-methylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane Cyclohexane, 1,1-bis(t-butylperoxy)cyclododecane, 1,1-bis(t-butylperoxy)butane, 2,2-bis(4,4-di-t-butylperoxycyclohexyl)propane, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-hexyl hydroperoxide, t-butyl hydroperoxide, α,α'-bis(t-butylperoxy)diisopropylbenzene, diisopropylbenzene Cumyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, t-butylcumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexyne-3, isobutyryl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, succinic acid peroxide, m-toluoylbenzoyl peroxide, benzoyl peroxide, di-n-propyl peroxide Oxydicarbonate, diisopropyl peroxydicarbonate, bis(4-t-butylcyclohexyl)peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, di-2-ethoxyhexyl peroxydicarbonate, di-3-methoxybutyl peroxydicarbonate, di-s-butyl peroxydicarbonate, di(3-methyl-3-methoxybutyl)peroxydicarbonate, α,α'-bis(neodecanoylperoxy)diisopropylbenzene, cumyl peroxyneodecanoate, 1,1,3,3,-tetramethylbutylperoxyneodecanoate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, t-hexylperoxyneodecanoate, t-butylperoxyneodecanoate, t-hexylperoxypivalate, t-butylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexanoate, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-hexylperoxyisopropyl monocarbonate, t-butylperoxyisobutyrate, t-butylperoxymalate, t-butylperoxy-3, Organic peroxide initiators such as 5,5-trimethylhexanoate, t-butylperoxylaurate, t-butylperoxyisopropyl monocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate, t-butylperoxyacetate, t-butylperoxy-m-toluylbenzoate, t-butylperoxybenzoate, bis(t-butylperoxy)isophthalate, 2,5-dimethyl-2,5-bis(m-toluylperoxy)hexane, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane, t-butylperoxyallyl monocarbonate, t-butyltrimethylsilyl peroxide, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, and 2,3-dimethyl-2,3-diphenylbutane.

[0071] 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, 1-[(1-cyano-1-methylethyl)azo]formamide, 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile), 2,2'-azobis(2-methylpropionamidine) dihydrochloride, 2,2'-azobis(2- 2,2'-azobis[N-(4-chlorophenyl)-2-methylpropionamidine]dihydrochloride, 2,2'-azobis[N-(4-hydrophenyl)-2-methylpropionamidine]dihydrochloride, 2,2'-azobis[2-methyl-N-(phenylmethyl)propionamidine]dihydrochloride, 2,2'-azobis[2-methyl-N-(2-propenyl)propionamidine]dihydrochloride, 2,2'-azobis[N-(2-hydroxyethyl) -2-methylpropionamidine] dihydrochloride, 2,2'-azobis[2-(5-methyl-2-imidazolin-2-yl)propane] dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride, 2,2'-azobis[2-(4,5,6,7-tetrahydro-1H-1,3-diazepin-2-yl)propane] dihydrochloride, 2,2'-azobis[2-(3,4,5,6-tetrahydropyrimidin-2-yl)propane] dihydrochloride, 2,2'-azobis[2-(5-hydroxy-1H-pyrimidin-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-[1,1-bis(hydroxymethyl)ethyl]propionamide}, 2,Azo initiators such as 2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], 2,2'-azobis(2-methylpropionamide), 2,2'-azobis(2,4,4-trimethylpentane), 2,2'-azobis(2-methylpropane), dimethyl-2,2-azobis(2-methylpropionate), 4,4'-azobis(4-cyanopentanoic acid), and 2,2'-azobis[2-(hydroxymethyl)propionitrile].

[0072] These may be used alone or in combination of two or more.

[0073] The content of the radical polymerization initiator is not particularly limited, but is preferably 0.05 to 10.0 parts by mass, more preferably 0.1 to 7.0 parts by mass, and even more preferably 0.2 to 5.0 parts by mass, relative to 100 parts by mass of the total of the radical polymerizable components.

[0074] [Solvent] From the viewpoint of adjusting viscosity, adjusting the thickness of the coating film, dissolving the resin, compounding the hydrophilic component, and the like, an appropriate amount of organic solvent or water may be contained.

[0075] Examples of organic solvents include monoalcohols such as methanol, ethanol, isopropanol, n-butanol, and sec-butanol; glycols such as ethylene glycol and propylene glycol; cyclic ethers such as tetrahydrofuran and dioxane; glycol monoethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, and 3-methoxybutanol; glycol ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol dimethyl ether, and propylene glycol diethyl ether; ethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol mono esters of glycol monoethers such as dipropylene glycol monobutyl ether acetate, dipropylene glycol monobutyl ether acetate, and 3-methoxybutyl acetate; alkyl esters such as methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl lactate, ethyl lactate, butyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl acetoacetate, and ethyl acetoacetate;Examples of suitable organic solvents include, but are not limited to, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; aromatic hydrocarbon compounds such as benzene, toluene, xylene, and ethylbenzene; aliphatic hydrocarbon compounds such as hexane, cyclohexane, and octane; and amides such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. These organic solvents may be used alone or in combination of two or more.

[0076] [Radically Polymerizable Compound Miscible with Water] The radically polymerizable composition of the present invention may contain an appropriate amount of a radically polymerizable compound miscible with water depending on the purpose and application. Specific examples of the radically polymerizable compound miscible with water include (meth)acrylic acid, salts of (meth)acrylic acid, 2-acrylamido-2-methylpropanesulfonic acid, salts of 2-acrylamido-2-methylpropanesulfonic acid, 2-hydroxyethyl (meth)acrylate, glycerol mono(meth)acrylate, (meth)acrylamide, acryloylmorpholine, N-vinylacetamide, N-vinylpyrrolidone, and polyethylene glycol di(meth)acrylate. However, any compound that is miscible with water and has a radically polymerizable group may be used.

[0077] [Compound that undergoes a thermal addition reaction or a thermal condensation reaction with an active hydrogen group] The radical polymerizable composition of the present invention may contain an appropriate amount of one or more compounds that undergo a thermal addition reaction or a thermal condensation reaction with an active hydrogen group, from the viewpoint of improving the heat resistance and hardness of the cured product. The functional group possessed by such a compound may be any functional group that undergoes a thermal addition reaction or a thermal condensation reaction with an active hydrogen group, and may have only one type or two or more types in the same molecule. Furthermore, it may have only one type or two or more types in the same molecule.

[0078] Examples of functional groups that undergo a thermal addition reaction or a thermal condensation reaction with an active hydrogen group include an epoxy group, an oxetanyl group, a carbodiimide group, an oxazoline group, an aziridine group, an isocyanate group, an alkoxysilyl group, and a hydroxymethyl group or alkoxymethyl group bonded to a nitrogen atom, but the present disclosure is not limited to these examples.

[0079] Examples of compounds having an epoxy group include glycidyl (meth)acrylate, 2-ethylhexyl glycidyl ether, p-tert-butylphenyl glycidyl ether, N-glycidyl phthalimide, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, resorcinol diglycidyl ether, neopentyl glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, sorbitol polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol compounds having a glycidyl group such as ol polyglycidyl ether, phenol novolac polyglycidyl ether, o-cresol novolac polyglycidyl ether, triglycidyl isocyanurate, and 4,4'-methylenebis(N,N-diglycidylaniline); compounds having an alicyclic epoxy group such as (3,4-epoxycyclohexyl)methyl(meth)acrylate, (3,4-epoxycyclohexylmethyl)3,4-epoxycyclohexanecarboxylate, 1,2-epoxy-4-vinyl-1-cyclohexene, bis(3,4-epoxycyclohexylmethyl)adipate, and 4-vinylcyclohexene dioxide; radical (co)polymers of compounds having a radical polymerizable group and an epoxy group such as glycidyl(meth)acrylate and (3,4-epoxycyclohexyl)methyl(meth)acrylate; but the present disclosure is not limited to these examples.

[0080] Examples of compounds having an oxetanyl group include low molecular weight compounds such as (3-ethyl-3-oxetanyl)methyl(meth)acrylate, 3-allyloxymethyl-3-ethyloxetane, 2-ethylhexylmethyl-3-ethyloxetane, bis(3-ethyl-3-oxetanylmethyl)ether, bis[(3-ethyl-3-oxetanyl)methyl]isophthalate, and 4,4'-bis[(3-ethyl-3-oxetanyl)methoxymethyl]biphenyl; and radical (co)polymers of compounds having an oxetanyl group and a radical polymerizable group such as (3-ethyl-3-oxetanyl)methyl(meth)acrylate; however, the present disclosure is not limited to these examples.

[0081] Examples of compounds having a carbodiimide group include N,N'-diisopropylcarbodiimide, N,N'-di-tert-butylcarbodiimide, N,N'-dicyclohexylcarbodiimide, bis(2,6-diisopropylphenyl)carbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, and Carbodista (product name, Teijin Limited), but the present disclosure is not limited to these examples.

[0082] Examples of compounds having an oxazoline group include EPOCROS WS-300 (product name, Nippon Shokubai Co., Ltd.), EPOCROS WS-500 (product name, Nippon Shokubai Co., Ltd.), EPOCROS WS-700 (product name, Nippon Shokubai Co., Ltd.), and EPOCROS RPS-1005 (product name, Nippon Shokubai Co., Ltd.), but the present disclosure is not limited to these examples.

[0083] Examples of compounds having an aziridine group include Chemitite PZ-33 (product name, Nippon Shokubai Co., Ltd.) and Chemitite DZ-22E (product name, Nippon Shokubai Co., Ltd.), but the present disclosure is not limited to these examples.

[0084] Examples of compounds having an isocyanate group include low molecular weight compounds such as 2-isocyanatoethyl (meth)acrylate, tolylene diisocyanate, xylylene diisocyanate, bis(isocyanatomethyl)cyclohexane, hexamethylene diisocyanate, isophorone diisocyanate, and diphenylmethane diisocyanate (monomeric MDI); polymeric compounds such as radical (co)polymers of compounds having a radical polymerizable group and an isocyanate group, such as polymeric MDI and 2-isocyanatoethyl (meth)acrylate; and isocyanate-terminated prepolymers obtained by reacting a polyol with an excess of polyisocyanate; however, the present disclosure is not limited to these examples. The isocyanate group may be an isocyanate group masked with a blocking agent such as phenol, ε-caprolactam, methyl ethyl ketone oxime, diethyl malonate, ethyl acetoacetate, or dimethylpyrazole.

[0085] Examples of compounds having an alkoxysilyl group include tetramethoxysilane, tetraethoxysilane, hydrolysis and polycondensation oligomers of tetramethoxysilane, hydrolysis and polycondensation oligomers of tetraethoxysilane, 3-(trimethoxysilyl)propyl(meth)acrylate, 3-[dimethoxy(methyl)silyl]propyl(meth)acrylate, 3-(triethoxysilyl)propyl(meth)acrylate, 3-[diethoxy(methyl)silyl]propyl(meth)acrylate, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3 low molecular weight compounds such as N-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride, vinyltrimethoxysilane, vinyltriethoxysilane, tris[3-(trimethoxysilyl)propyl]isocyanurate, bis[3-(trimethoxysilyl)propyl]amine, 1,6-bis(trimethoxysilyl)hexane; and polymeric compounds such as alkoxysilyl-terminated polydimethylsiloxane, radical (co)polymers of compounds having a radical polymerizable group and an alkoxysilyl group, such as 3-(trimethoxysilyl)propyl(meth)acrylate and 3-(triethoxysilyl)propyl(meth)acrylate; however, the present disclosure is not limited to these examples.

[0086] Examples of compounds having a hydroxymethyl group or an alkoxymethyl group bonded to a nitrogen atom include hydroxymethylated (meth)acrylamide compounds such as N-(hydroxymethyl)(meth)acrylamide, N-(methoxymethyl)(meth)acrylamide, and radical (co)polymers of N-(hydroxymethyl)(meth)acrylamide and N-(methoxymethyl)(meth)acrylamide; melamine resins such as hexamethylol melamine, partially or completely methyl etherified products of hexamethylol melamine, partially methylolated melamine, and methyl etherified products of partially methylolated melamine; benzoguanamine resins such as tetramethylolbenzoguanamine and methyl etherified products of tetramethylolbenzoguanamine; and urea resins such as 1,3,4,6-tetrakis(methoxymethyl)glycoluril, dimethylol dihydroxyethylene urea, and methyl etherified products of dimethylol dihydroxyethylene urea; however, the present disclosure is not limited to these examples.

[0087] The content of the compound that undergoes a thermal addition reaction or a thermal condensation reaction with these active hydrogen groups may be adjusted depending on the application or purpose, and it does not have to be included; however, when used, the content is preferably 1 part by mass or more and 90 parts by mass or less, more preferably 2 parts by mass or more and 85 parts by mass or less, and even more preferably 3 parts by mass or more and 80 parts by mass or less, relative to 100 parts by mass of the polymerizable composition of the present disclosure.

[0088] <Polymer of the Present Disclosure> A polymer of the present disclosure is obtained by reacting the radical polymerizable composition of the present disclosure, and the reaction method includes at least generating radicals in the radical polymerizable composition of the present disclosure to carry out radical polymerization. A radical polymer of the radical polymerizable composition of the present disclosure, which is a polymer obtained by polymerizing such a radical polymerizable composition of the present disclosure under radical-generating conditions, also constitutes part of the present disclosure.

[0089] Examples of radical generation methods include a method of heating the radical polymerizable composition of the present disclosure and / or a method of irradiating the radical polymerizable composition of the present disclosure with active energy rays. Heating or irradiation with active energy rays may be performed in one step, or may be performed in two or more separate steps. Heating and irradiation with active energy rays may be combined, may be performed simultaneously, or may be performed separately. When heating or irradiating with active energy rays, it is more preferable that the radical polymerizable composition of the present disclosure contains the above-mentioned radical polymerization initiator.

[0090] When heating is performed, the temperature may be appropriately selected depending on the presence or absence, type, content, and application of a radical polymerization initiator. When a thermal radical initiator is used, the temperature is 40°C or higher, more preferably 50°C or higher, and even more preferably 60°C or higher.

[0091] As the active energy ray, those that are commonly used can be used, including electromagnetic waves such as gamma rays, X-rays, ultraviolet rays, visible light, and infrared rays, and particle rays such as electron beams, neutron beams, and proton beams.Among these, in terms of energy intensity, energy ray generator, etc., gamma rays, X-rays, ultraviolet rays, visible light, and electron beams are preferred, ultraviolet rays, visible light, and electron beams are more preferred, and ultraviolet rays are most preferred.When a photoradical initiator is not used, it is preferable to use active energy rays with high energy such as gamma rays, X-rays, and electron beams, and when a photoradical initiator is used, it is preferable to use active energy rays that have relatively low energy but are easy to generate and economical, such as ultraviolet rays and visible light.

[0092] The reaction for obtaining the polymer of the present disclosure includes at least generating radicals in the polymerizable composition of the present disclosure and carrying out radical polymerization, but may also include other reactions. Preferred examples of such reactions include a thermal addition reaction with an active hydrogen group and a thermal condensation reaction with an active hydrogen group. These reactions may be carried out before, simultaneously with, or after the radical polymerization. When carrying out a thermal addition reaction with an active hydrogen group or a thermal condensation reaction with an active hydrogen group, it is more preferred that the polymerizable composition of the present disclosure contains a compound that undergoes a thermal addition reaction or a thermal condensation reaction with the active hydrogen group.

[0093] The heating temperature may be appropriately selected depending on the type, content, and application of the compound that undergoes a thermal addition reaction or thermal condensation reaction with the active hydrogen group, but is preferably 40°C or higher, more preferably 70°C or higher, and even more preferably 90°C or higher.

[0094] The polymer of the present disclosure contains the structural unit (a) derived from the polymerizable compound (A) and the structural unit (b) derived from the 2-oxymethylacrylic acid ion, and may further contain a structural unit (c) derived from another polymerizable compound. The polymer may contain only one type of the structural unit (a), the structural unit (b), and the structural unit (c), or may contain two or more types of each of the structural units (a), (b), and (c).

[0095] A preferred content ratio of the structural unit (a) in the polymer is the same as the content ratio of the polymerizable compound (A) in the polymerizable composition of the present disclosure, and a preferred content ratio of the structural unit (b) is the same as the content ratio of the 2-oxymethylacrylic acid ion in the polymerizable composition of the present disclosure.

[0096] Here, the "structural unit (a) derived from the polymerizable compound (A)" and the "structural unit (b) derived from a 2-oxymethylacrylic acid ion" are structural units having the same structure as the structural units contained in a polymer obtained by radical polymerization of the "polymerizable compound (A)" and the "2-oxymethylacrylic acid ion," respectively.

[0097] The structural unit (a) and the structural unit (b) do not necessarily have to be structural units formed by actual radical polymerization of the polymerizable compound (A) and the 2-oxymethylacrylic acid ion, respectively, and may be structural units formed by another method, for example, a synthetic method, as long as they have the same structure as the structural unit obtained by radical polymerization.

[0098] Examples of structural units possessed by a polymer obtained by radically polymerizing a polymerizable composition containing the polymerizable compound (A) and the 2-oxymethylacrylic acid ion include, but are not limited to, (i) a structural unit in which at least one carbon-carbon double bond of the polymerizable compound (A) and the 2-oxymethylacrylic acid ion is replaced with a carbon-carbon single bond, and (ii) a structural unit formed by cyclopolymerization of the polymerizable compound (A) and the 2-oxymethylacrylic acid ion if the polymerizable compound (A) and the 2-oxymethylacrylic acid ion are cyclopolymerizable compounds. Examples of compounds containing the 2-oxymethylacrylic acid ion include the polymerizable salt compound (B).

[0099] <Applications of the radically polymerizable composition of the present disclosure> By adjusting the types and amounts of the polymerizable compound (A), polymerizable salt compound (B), and other components described above, the radically polymerizable composition of the present disclosure can be made into a liquid form that can be used in various printing applications. The polymerized product can exhibit the various excellent properties of conventional ionomers, and can therefore be used in a variety of applications, such as various coatings (anti-crack coatings for brittle films, protective coatings for decorative films, and phase difference adjusting coatings), primers, sealants, adhesives, sealants, pressure-sensitive adhesives, various methods of three-dimensional modeling (inkjet, SLA, DLP), thermoplastic molding, thermosetting molding, hot-melt adhesives, optical films, lenses, electronic components, prepregs, dental materials, paints, printing inks, fiber treatment agents, and resist materials for microfabrication.

[0100] The present disclosure will be described in more detail below with reference to examples, but the present disclosure is not limited to these examples. Unless otherwise specified, "parts" means "parts by mass" and "%" means "% by mass."

[0101] <2-Allyloxymethylacrylic acid> 2-Allyloxymethylacrylic acid with a purity of 96.5% was prepared. The acid contained 0.04% (based on the total solution volume) of hydroquinone monomethyl ether and 0.06% (based on the total solution volume) of 2,2'-(ethylenedithio)diethanol as radical polymerization inhibitors. The purity was measured using the following capillary electrophoresis system. Measurement equipment: Agilent 7100 capillary electrophoresis system (Agilent Technologies, Inc.) Measurement conditions: Indirect absorption method using background absorber. Capillary: Bubble self-fused silica capillary (inner diameter 75 μm x total length 80.5 cm) Running buffer: Running buffer for anion analysis (pH = 8.2) Applied voltage: -20 kV Quantitative method: Quantitative analysis was performed using the internal standard method based on area ratio (internal standard: sodium propionate). Preparation of standard sample: Dissolve sodium propionate and the substance to be quantified (sodium salt of carboxylic acid ion) in heavy water. １ After determining the molar ratio by H-NMR, the solution was further diluted with ultrapure water to prepare a standard sample for creating a calibration curve. Preparation of measurement samples: The sodium propionate aqueous solution and the test sample were weighed and diluted with 0.1 N sodium hydroxide aqueous solution and ultrapure water to prepare a measurement sample.

[0102] <Dissolution of Polymerizable Salt in Water-Immiscible Radically Polymerizable Compound> [Example 1-1] 0.26 g of zinc oxide, 2.8 g of methanol, and 1.04 g of 2-allyloxymethylacrylic acid were added, in this order, to a recovery flask containing a stirrer, and stirred at 50°C for 4 hours to obtain a homogeneous methanol solution (90 mol % of the 2-allyloxymethylacrylic acid was neutralized with zinc). The solution was returned to room temperature, and 2.8 g of 2-ethylhexyl acrylate was added. After that, the pressure was reduced with a vacuum pump while the temperature was still at room temperature to remove the methanol. Even after the methanol was removed, the contents remained a homogeneous, transparent liquid (zinc concentration 5.2%). The results are shown in Table 1.

[0103] [Example 1-2] The procedure of Example 1-1 was repeated except that 2-ethylhexyl acrylate was changed to cyclohexyl acrylate, and a homogeneous, transparent liquid composition with a zinc concentration of 5.2% was obtained. The results are shown in Table 1.

[0104] Comparative Example 1-1: 0.22 g of zinc oxide, 2.8 g of methanol, and 0.43 g of acrylic acid were added, in that order, to a recovery flask containing a stirrer, and stirred at 50°C for 4 hours to obtain a homogeneous methanol solution (90 mol % of the acrylic acid was neutralized with zinc). The solution was returned to room temperature, and 2.8 g of 2-ethylhexyl acrylate (an amount that would result in a zinc concentration of 5.2% when methanol was removed) was added. After that, the temperature was reduced with a vacuum pump while still at room temperature to remove the methanol. However, a white precipitate was formed during the removal of the methanol, and a homogeneous solution was not obtained. The results are shown in Table 1.

[0105] Comparative Example 1-2: The procedure of Comparative Example 1-1 was repeated except that 2-ethylhexyl acrylate was changed to cyclohexyl acrylate. However, a white precipitate was formed during the removal of methanol, and a homogeneous solution was not obtained. The results are shown in Table 1.

[0106] EHA 2-ethylhexyl acrylate CHA cyclohexyl acrylate AIO-A 2-allyloxymethylacrylic acid AIO-Zn 2-allyloxymethyl zinc acrylate AA acrylic acid AA-Zn zinc acrylate AIO- 2-allyloxymethyl acrylic acid ion

[0107] <Polymer Properties: Adhesion> [Example 2-1] 0.29 g of zinc oxide, 2.4 g of ethanol, and 1.05 g of 2-allyloxymethylacrylic acid were added, in this order, to a recovery flask containing a stirrer and stirred at 50°C for 4 hours to obtain a homogeneous ethanol solution (100 mol % of the 2-allyloxymethylacrylic acid was neutralized with zinc). The mixture was returned to room temperature, and 1.24 g of 2-ethylhexyl acrylate and 0.07 g of 1-hydroxycyclohexyl phenyl ketone were added and mixed with stirring to obtain a composition in the form of an ethanol solution containing 50% of the polymerizable components. The resulting composition was applied to a heat-resistant acrylic film (a 140 μm-thick film prepared by melt extruding pellets obtained by the method described in Production Example 7 of JP 2019-179124 A) using a bar coater No. 4, and then dried on a hot plate at 80°C for 5 minutes. The dried coating was then irradiated with a belt conveyor-type UV irradiation device (high-pressure mercury lamp, illuminance 200 mW / cm). ２), the cumulative light dose was 0.6 J / cm ２ The adhesion of the polymer layer was evaluated in accordance with JIS K 5600-5-6 (cross-cut method). That is, the number of squares that remained without peeling or damage out of all squares (10 × 10 squares = 100 squares) was evaluated, and the result was 100. The results are shown in Table 2.

[0108] [Example 2-2] An ethanol solution composition was prepared in the same manner as in Example 2-1, except that 2-ethylhexyl acrylate was changed to isobornyl acrylate, and the composition was applied to a heat-resistant acrylic film and dried. The dried coating film was polymerized using a belt conveyor-type UV irradiation device, and the cumulative light dose was 0.6 J / cm. ２ When the adhesiveness was evaluated, the number of squares remaining without peeling or damage was 100. The results are summarized in Table 2.

[0109] Example 2-3: 0.19 g of zinc oxide, 2.4 g of ethanol, and 1.14 g of 2-allyloxymethylacrylic acid were added, in this order, to a recovery flask containing a stirrer, and the mixture was stirred at 50°C for 3 hours to obtain a homogeneous ethanol solution (60 mol% of the 2-allyloxymethylacrylic acid was neutralized with zinc). The mixture was returned to room temperature, and 0.75 g of cyclohexyl acrylate, 0.5 g of dipentaerythritol hexaacrylate, and 0.07 g of 1-hydroxycyclohexyl phenyl ketone were added and stirred to obtain a composition in the form of an ethanol solution containing 50% of the polymerizable components. This composition was used to form a dry coating on a heat-resistant acrylic film in the same manner as in Example 2-1, and the dry coating was then irradiated with a belt conveyor-type UV irradiation device at an integrated light dose of 5 J / cm. ２ The adhesion of the polymerized layer was evaluated, and the number of squares that remained without peeling or damage was 100. The results are shown in Table 2.

[0110] Comparative Example 2-1: 1,4-butanediol diacrylate (length between radically polymerizable groups = 4 carbon atoms), an industrially readily available divalent acrylate ester, which is miscible with water-immiscible radically polymerizable compounds and has a short distance between radically polymerizable groups, was used instead of zinc 2-allyloxymethylacrylate. Specifically, 1.2 g of 1,4-butanediol diacrylate, 1.2 g of 2-ethylhexyl acrylate, and 0.07 g of 1-hydroxycyclohexyl phenyl ketone were mixed with stirring, and the resulting homogeneous, transparent liquid composition was applied to a heat-resistant acrylic film using a No. 2 bar coater. This was polymerized using a belt conveyor-type UV irradiation device in the same manner as in Example 2-1, resulting in an accumulated light dose of 5 J / cm. ２ When the adhesion of the polymer layer was evaluated, the number of squares that remained without peeling or damage was 0. The results are shown in Table 2.

[0111] [Comparative Example 2-2] A liquid composition was prepared in the same manner as in Comparative Example 2-1, except that 2-ethylhexyl acrylate was changed to isobornyl acrylate, and then coated onto a heat-resistant acrylic film. When the composition was polymerized using a belt conveyor-type UV irradiation device, the cumulative light dose was 5 J / cm. ２ When the adhesiveness was evaluated, the number of squares remaining without peeling or breakage was 0. The results are shown in Table 2.

[0112] Comparative Example 2-3 A liquid composition was prepared in the same manner as in Comparative Example 2-1, except that 0.72 g of cyclohexyl acrylate and 0.48 g of dipentaerythritol hexaacrylate were used instead of 1.2 g of 2-ethylhexyl acrylate, and then coated onto a heat-resistant acrylic film. The composition was then irradiated with a UV light source using a belt conveyor with an integrated light dose of 5 J / cm. ２ The adhesion of the polymerized layer was evaluated, and the number of squares that remained without peeling or damage was 22. The results are shown in Table 2.

[0113] EHA 2-ethylhexyl acrylate IBOA Isobornyl acrylate CHA Cyclohexyl acrylate DPHA Dipentaerythritol hexaacrylate BDDA 1,4-butanediol diacrylate AIO-A 2-allyloxymethyl acrylic acid AIO-Zn 2-allyloxymethyl zinc acrylate AIO- 2-allyloxymethyl acrylic acid ion

[0114] <Polymer Properties: Tensile Properties> [Example 3-1] 0.12 g of zinc oxide, 3.0 g of methanol, and 1.49 g of 2-allyloxymethylacrylic acid were added, in this order, to a recovery flask containing a stirrer and stirred at 50°C for 4 hours to obtain a homogeneous solution (29 mol % of the 2-allyloxymethylacrylic acid was neutralized with zinc). The mixture was returned to room temperature, and 3.57 g of 2-ethylhexyl acrylate was added. The temperature was reduced to room temperature using a vacuum pump to remove the methanol, followed by the addition of 0.15 g of 1-hydroxycyclohexyl phenyl ketone and stirring to obtain a homogeneous, transparent liquid polymerizable composition. A glass plate (15 cm x 7 cm) with a 2 mm thick polypropylene plate attached and an iron plate (15 cm x 7 cm) with a 2 mm thick polypropylene plate attached were placed facing each other, with the polypropylene plate facing inward. A 0.5 mm thick silicone sheet cut into a U-shape was sandwiched between them as a spacer and secured with clips. The resulting mixture was used for casting. The polymerizable composition was poured into the casting mold, and the composition was then heated in a belt conveyor-type UV irradiation device (high-pressure mercury lamp, illuminance 200 mW / cm ２ ) from the glass plate side with an integrated light intensity of 2 J / cm ２ After removing the clips and removing one of the plates, the UV was irradiated to a cumulative light dose of 1 J / cm. ２The specimen was irradiated with UV light until the thickness reached 13 cm. The plate and silicone sheet were removed, and the resulting sheet, approximately 13 cm x 5 cm x 0.5 mm thick, was punched into a No. 3 dumbbell shape (compliant with JIS K 6251) using a test piece punching machine. The thickness of the test piece was measured at the center, and then the tensile strength (maximum tensile force until the test piece broke), Young's modulus, and elongation at break were measured using a tensile tester (grip distance: 60 mm, tensile speed: 10 mm / min). The results are shown in Table 3. Furthermore, when the surplus specimens obtained during the preparation of the dumbbell-shaped test pieces were analyzed by X-ray diffraction, a peak derived from ion aggregation domains specific to ionomers was observed on the low-angle side (2θ = 2 to 4°).

[0115] Example 3-2: 1.42 g of 2-allyloxymethylacrylic acid, 3.43 g of 2-ethylhexyl acrylate, and 0.10 g of tris(2-aminoethyl)amine were added in this order to a screw tube containing a stirrer and mixed with stirring to obtain a homogeneous solution (29 mol % of the 2-allyloxymethylacrylic acid was neutralized with the amine). 0.15 g of 1-hydroxycyclohexyl phenyl ketone was then added and mixed with stirring to obtain a polymerizable composition as a homogeneous, transparent liquid. Using this polymerizable composition, dumbbell-shaped No. 3 test pieces were prepared in the same manner as in Example 3-1, and the tensile strength, Young's modulus, and elongation at break were measured. The results are shown in Table 3.

[0116] Comparative Example 3-1: 1,4-butanediol diacrylate, a divalent acrylic acid ester that is readily available commercially, is miscible with water-immiscible radically polymerizable compounds, and has a short distance between radically polymerizable groups (acryloyloxy groups) (the distance between acryloyloxy groups is four carbon atoms), was used instead of zinc 2-allyloxymethylacrylate. Specifically, 0.5 g of 1,4-butanediol diacrylate, 4.5 g of 2-ethylhexyl acrylate, and 0.15 g of 1-hydroxycyclohexyl phenyl ketone were mixed with stirring to obtain a polymerizable composition. Using this polymerizable composition, a dumbbell-shaped No. 3 test piece was prepared in the same manner as in Example 3-1. An attempt was made to perform a tensile test, but the test piece was so weak that the portion clamped by the clamp broke when it was set in the clamp, making the test impossible. The results are shown in Table 3.

[0117] Comparative Example 3-2 A polymerizable composition was obtained in the same manner as in Comparative Example 3-1, except that 1.5 g of 1,4-butanediol diacrylate and 3.5 g of 2-ethylhexyl acrylate were used instead of 0.5 g of 1,4-butanediol diacrylate and 4.5 g of 2-ethylhexyl acrylate. Using this polymerizable composition, dumbbell-shaped No. 3 test pieces were prepared in the same manner as in Example 3-1, and the tensile strength, Young's modulus, and elongation at break were measured. The results are shown in Table 3.

[0118] Example 3-3: 0.79 g of zinc oxide, 9.0 g of methanol, and 4.77 g of 2-allyloxymethylacrylic acid were added, in that order, to a recovery flask containing a stirrer and stirred at 50°C for 4 hours to obtain a homogeneous solution (60 mol % of the 2-allyloxymethylacrylic acid was neutralized with zinc). The solution was returned to room temperature, and 10.44 g of 2-ethylhexyl acrylate was added. The pressure was reduced with a vacuum pump while still at room temperature to remove the methanol, yielding approximately 16 g of initiator-free polymerizable composition. 5.0 g of the solution was taken, and 0.15 g of 1-hydroxycyclohexyl phenyl ketone was added. After stirring and mixing, dumbbell-shaped No. 3 test pieces were prepared in the same manner as in Example 3-1, and the tensile strength, Young's modulus, and elongation at break were measured. The results are shown in Table 3.

[0119] [Example 3-4] 0.10 g of 1-hydroxycyclohexyl phenyl ketone and 0.05 g of t-butylperoxy-2-ethylhexanoate were added to the initiator-free polymerizable composition obtained in Example 3-3, and the mixture was stirred and mixed. The mixture was poured into a casting mold in the same manner as in Example 3-1, and irradiated from the glass plate side with an integrated light dose of 1 J / cm using a belt conveyor-type UV irradiation device. ２ The mold was then placed in a 110°C oven and heated for 1 hour, after which the mold was removed to obtain a sheet measuring approximately 13 cm x 5 cm x 0.5 mm thick. Dumbbell-shaped No. 3 test pieces were then prepared in the same manner as in Example 3-1, and the tensile strength, Young's modulus, and elongation at break were measured. The results are shown in Table 3.

[0120] Example 3-5: To the initiator-free polymerizable composition obtained in Example 3-3, 0.10 g of t-butyl peroxypivalate and 0.05 g of 1,1-di(t-hexylperoxy)cyclohexane were added and mixed by stirring to prepare a polymerizable composition. Two iron plates (15 cm x 7 cm) with 2 mm thick polypropylene plates attached were placed facing each other with the polypropylene plates facing inward. A 0.5 mm thick U-shaped silicone sheet was sandwiched between them as a spacer and secured with clips to form a casting mold. The polymerizable composition was poured into the casting mold, and the casting mold was placed in a polypropylene bag and immersed in 60°C hot water while suspended for 2 hours. The casting mold was then placed in a 110°C oven and heated for 1 hour, after which the casting mold was removed to obtain a sheet measuring approximately 13 cm x 5 cm x 0.5 mm thick. Dumbbell-shaped No. 3 test pieces were prepared in the same manner as in Example 3-1, and the tensile strength, Young's modulus, and elongation at break were measured. The results are shown in Table 3.

[0121] Example 3-6 A polymerizable composition was prepared in the same manner as in Example 3-1, except that 1.53 g of a trimethylolpropane adduct of tolylene diisocyanate was further added. Specifically, 0.12 g of zinc oxide, 3.0 g of methanol, and 1.49 g of 2-allyloxymethylacrylic acid were added, in this order, to a recovery flask containing a stirrer and stirred at 50°C for 4 hours to obtain a homogeneous solution (29 mol % of the 2-allyloxymethylacrylic acid was neutralized with zinc). The mixture was returned to room temperature, 3.57 g of 2-ethylhexyl acrylate was added, and the methanol was removed by reducing the pressure with a vacuum pump while still at room temperature. 2.04 g of a 75% ethyl acetate solution of a trimethylolpropane adduct of tolylene diisocyanate was then added, and the ethyl acetate was removed again by reducing the pressure with a vacuum pump while still at room temperature. Finally, 0.15 g of 1-hydroxycyclohexyl phenyl ketone was added, and the mixture was stirred and mixed to obtain a homogeneous, transparent liquid polymerizable composition. This polymerizable composition was used to obtain a sheet measuring approximately 13 cm x 5 cm x 0.5 mm thick in the same manner as in Example 3-1. The sheet was cut in half with a cutter (two sheets of approximately 6.5 cm x 5 cm), and one half was placed in a 150°C oven for 30 minutes to react the carboxyl groups and isocyanate groups, after which the sheet was returned to room temperature. When the surface of the unheated sheet was wiped with a paper wiper soaked in methanol, it became white and sticky. On the other hand, when the surface of the heated sheet was wiped with a paper wiper soaked in methanol, it did not whiten or become sticky.

[0122] EHA 2-ethylhexyl acrylate BDDA 1,4-butanediol diacrylate AIO-A 2-allyloxymethylacrylic acid AIO-Zn 2-allyloxymethyl zinc acrylate AIO-TAEA Tris(2-aminoethyl)amine salt of 2-allyloxymethylacrylic acid AIO- 2-allyloxymethylacrylic acid ion

[0123] As is clear from the tensile test results of Examples 3-1 to 3-5 and Comparative Examples 3-1 and 3-2, the polymers of the present invention have excellent mechanical strength, and the X-ray diffraction results of Example 3-1 show that the polymers of the present invention have an ionomer structure. Furthermore, Example 3-6 shows that solvent resistance can be improved by adding a crosslinking agent that reacts with carboxyl groups in advance and then performing UV curing followed by heat curing, i.e., by using a dual-cure system.

[0124] <Polymer Properties: Thermoplasticity> [Example 4-1] 0.12 g of zinc oxide, 3.0 g of methanol, and 1.49 g of 2-allyloxymethylacrylic acid were added, in this order, to a recovery flask containing a stirrer and stirred at 50°C for 4 hours to obtain a homogeneous solution (29 mol% of the 2-allyloxymethylacrylic acid was neutralized with zinc). The mixture was returned to room temperature, and 3.57 g of cyclohexyl acrylate was added. The temperature was reduced to room temperature using a vacuum pump to remove the methanol, followed by the addition of 0.15 g of 1-hydroxycyclohexyl phenyl ketone and stirring to obtain a homogeneous, transparent liquid polymerizable composition. A glass plate (15 cm x 7 cm) with a 2 mm thick polypropylene plate attached and an iron plate (15 cm x 7 cm) with a 2 mm thick polypropylene plate attached were placed facing each other, with the polypropylene plate facing inward. A 0.5 mm thick silicone sheet cut into a U-shape was sandwiched between them as a spacer and secured with clips. The resulting mixture was used for casting. The polymerizable composition was poured into the casting mold, and the composition was then heated in a belt conveyor-type UV irradiation device (high-pressure mercury lamp, illuminance 200 mW / cm ２ ) from the glass plate side with an integrated light intensity of 2 J / cm ２ After removing the clips and removing one of the plates, the UV was irradiated to a cumulative light dose of 1 J / cm. ２UV was irradiated so that the sheet was 13 cm x 5 cm x 0.5 mm thick. The plate and silicone sheet were removed and the resulting sheet was cut into 10 cm x 4 cm strips using a cutter, and the cut edges were polished. The pencil hardness of the excess pieces obtained during cutting was measured using an electric pencil hardness tester with a load of 750 g, resulting in a value of H. Using an oven-equipped tensile tester, a 10 cm x 4 cm strip-shaped test piece was pulled at a gripper distance of 60 mm, a pulling speed of 30 mm / min, and an oven temperature of 120 ° C. The pulling was stopped when the elongation reached 100% (i.e., 2x stretched), the oven was removed, the test piece was returned to room temperature, and the test piece was then removed from the gripper. The resulting test piece was transparent. The pencil hardness of the test piece after 2x stretching was also measured (the scratch scanning direction was perpendicular to the stretching direction), and it had improved to 2H. The weight ratio of the polymerizable components and the thermoplasticity results (stretchable to 2 times: ◯, not stretchable: ×) are summarized in Table 4.

[0125] Comparative Example 4-1: 1,4-butanediol diacrylate, a divalent acrylic acid ester that is readily available commercially, is miscible with water-immiscible radically polymerizable compounds, and has a short distance between radically polymerizable groups (acryloyloxy groups) (the distance between acryloyloxy groups is four carbon atoms), was used instead of zinc 2-allyloxymethylacrylate. Specifically, 1.5 g of 1,4-butanediol diacrylate, 3.5 g of cyclohexyl acrylate, and 0.15 g of 1-hydroxycyclohexyl phenyl ketone were mixed with stirring to obtain a polymerizable composition. Using this polymerizable composition, 10 cm x 4 cm strip test specimens were prepared in the same manner as in Example 4-1. The pencil hardness of the surplus specimens obtained during the preparation of the strip test specimens was measured using an electric pencil hardness tester at a load of 750 g, resulting in a value of H. Using a tensile tester equipped with an oven, a rectangular test piece was pulled at a gripper distance of 60 mm, a pulling speed of 30 mm / min, and an oven temperature of 120°C, and broke when the elongation reached 5%. The weight ratio of the polymerization components and the thermoplasticity results (stretchable to 2 times: ○, not stretchable: ×) are summarized in Table 4.

[0126] Example 4-2: A 10 cm x 4 cm strip-shaped test specimen was prepared in the same manner as in Example 4-1, except that benzyl acrylate was used instead of cyclohexyl acrylate. Using a tensile tester equipped with an oven, the strip-shaped test specimen was stretched at a grip distance of 60 mm, a tension speed of 30 mm / min, and an oven temperature of 80°C. When the elongation reached 100% (i.e., 2x stretching), the tension was stopped, the oven was removed, the test specimen was returned to room temperature, and then the test specimen was removed from the grips. The resulting test specimen was transparent. The retardation of the test specimen after 2x stretching was measured at a wavelength of 550 nm using a RETS-100 manufactured by Otsuka Electronics Co., Ltd., and found to be a positive retardation of 210 nm per 100 μm thickness. The weight ratio of the polymerization components and the thermoplasticity results (stretchable to 2x: ○, unable to stretch: ×) are summarized in Table 4.

[0127] Comparative Example 4-2: A 10 cm x 4 cm strip test piece was prepared in the same manner as in Comparative Example 4-1, except that benzyl acrylate was used instead of cyclohexyl acrylate. Using a tensile tester equipped with an oven, the strip test piece was pulled at a gripper distance of 60 mm, a pulling speed of 30 mm / min, and an oven temperature of 120°C, and broke when the elongation reached 5%. The weight ratio of the polymerization components and the thermoplasticity results (stretchable to 2 times: ○, unable to stretch: ×) are summarized in Table 4.

[0128] Example 4-3: 0.11 g of calcium hydroxide, 3.0 g of methanol, 1.0 g of ultrapure water, and 1.51 g of 2-allyloxymethylacrylic acid were added, in this order, to a recovery flask containing a stirrer. The mixture was stirred at 50°C for 1 hour to obtain a homogeneous solution (29 mol% of the 2-allyloxymethylacrylic acid was neutralized with calcium). The mixture was returned to room temperature, and 3.53 g of cyclohexyl acrylate was added. The mixture was then depressurized with a vacuum pump while still at room temperature to remove the methanol. Then, 0.15 g of 1-hydroxycyclohexyl phenyl ketone was added and mixed with stirring to obtain a homogeneous, transparent liquid polymerizable composition. This polymerizable composition was used to prepare 10 cm x 4 cm strip test specimens in the same manner as in Example 4-1. The strip test specimens were tensioned using a tensile tester equipped with an oven at a gripper distance of 60 mm, a tension speed of 30 mm / min, and an oven temperature of 120°C. The tension was stopped when the elongation reached 100% (i.e., 2x stretching), the oven was removed, and the test specimen was allowed to return to room temperature. The test specimen was then removed from the clamps. The resulting test specimen was transparent. The weight ratio of the polymer components and the thermoplasticity results (stretchable to 2x: ○, not stretchable: ×) are summarized in Table 4.

[0129] Example 4-4: To a recovery flask containing a stirrer, 0.34 g of magnesium hydroxide, 2.0 g of methanol, 1.0 g of ultrapure water, and 1.91 g of 2-allyloxymethylacrylic acid were added, in that order, and stirred at 50°C for 1 hour to obtain a homogeneous solution. The solution was then connected to a vacuum pump to remove the methanol. Acetone was added to the flask, and the resulting powder was washed with acetone and filtered under reduced pressure. The powder was then dried under vacuum at room temperature to obtain magnesium 2-allyloxymethylacrylate powder. To a screw cap tube containing a stirrer, 0.46 g of magnesium 2-allyloxymethylacrylate powder, 1.08 g of 2-allyloxymethylacrylic acid, and 0.19 g of ultrapure water were placed, and the mixture was stirred while heated to 50°C until it became uniform and transparent. After returning the mixture to room temperature, 3.50 g of cyclohexyl acrylate and 0.15 g of 1-hydroxycyclohexyl phenyl ketone were added and stirred to obtain a polymerizable composition as a uniform, transparent liquid. Using this polymerizable composition, a 10 cm x 4 cm strip-shaped test specimen was prepared in the same manner as in Example 4-1. Using a tensile tester equipped with an oven, the strip-shaped test specimen was pulled at a gripper distance of 60 mm, a pulling rate of 30 mm / min, and an oven temperature of 120°C. Pulling was stopped when the elongation reached 100% (i.e., 2x stretching), the oven was removed, and the test specimen was allowed to return to room temperature, after which the test specimen was removed from the gripper. The obtained test specimen was transparent. The weight ratio of the polymerizable components and the thermoplasticity results (stretchable to 2x: ○, not stretchable: ×) are summarized in Table 4.

[0130] Example 4-5: 0.31 g of sodium carbonate, 3.0 g of methanol, 1.0 g of ultrapure water, and 1.49 g of 2-allyloxymethylacrylic acid were added, in that order, to a recovery flask containing a stirrer. The mixture was stirred at 50°C for 1 hour to obtain a homogeneous solution (29 mol% of the 2-allyloxymethylacrylic acid was neutralized with sodium). The mixture was returned to room temperature, and 3.51 g of cyclohexyl acrylate was added. The mixture was then depressurized with a vacuum pump while still at room temperature to remove the methanol. Then, 0.15 g of 1-hydroxycyclohexyl phenyl ketone was added and mixed with stirring to obtain a homogeneous, transparent liquid polymerizable composition. Using this polymerizable composition, 10 cm x 4 cm strip specimens were prepared in the same manner as in Example 4-1. The strip specimens were tensioned using a tensile tester equipped with an oven at a gripper distance of 60 mm, a tension speed of 30 mm / min, and an oven temperature of 120°C. The tension was stopped when the elongation reached 100% (i.e., 2x stretching), the oven was removed, and the test specimen was allowed to return to room temperature. The test specimen was then removed from the clamps. The resulting test specimen was transparent. The weight ratio of the polymer components and the thermoplasticity results (stretchable to 2x: ○, not stretchable: ×) are summarized in Table 4.

[0131] Example 4-6: 0.11 g of calcium hydroxide, 3.0 g of methanol, 1.0 g of ultrapure water, and 1.51 g of 2-allyloxymethylacrylic acid were added, in that order, to a recovery flask containing a stirrer. The mixture was stirred at 50°C for 1 hour to obtain a homogeneous solution (29 mol% of the 2-allyloxymethylacrylic acid was neutralized with calcium). The mixture was then returned to room temperature, and 2.52 g of cyclohexyl acrylate was added. The temperature was reduced to room temperature using a vacuum pump to remove the methanol. Then, 1.01 g of (3-ethyloxetan-3-yl)methyl acrylate and 0.15 g of 1-hydroxycyclohexyl phenyl ketone were added and mixed with stirring to obtain a homogeneous, transparent liquid polymerizable composition. This polymerizable composition was used to prepare 10 cm x 4 cm strip-shaped test specimens in the same manner as in Example 4-1. Using a tensile tester equipped with an oven, 10 cm x 4 cm strip-shaped test specimens were stretched at a gripper distance of 60 mm, a tensioning rate of 30 mm / min, and an oven temperature of 120°C. The tension was stopped when the elongation reached 100% (i.e., 2x stretching), the oven was removed, the test specimen was returned to room temperature, and then the test specimen was removed from the gripper. The resulting test specimen was transparent. Furthermore, the pencil hardness of the surplus specimens obtained when cutting out the strip-shaped test specimens was measured using an electric pencil hardness tester at a load of 750 g. The result was H. When the surface was wiped with a paper wiper soaked in acetone, some whitening occurred. Meanwhile, the pencil hardness of another surplus specimen was measured after heating it on a hot plate at 200°C for 5 minutes. The result was 3H. When the surface was wiped with a paper wiper soaked in acetone, no whitening occurred. The weight ratio of the polymerizable components and the thermoplasticity results (stretchable to 2x: ○, not stretchable: ×) are summarized in Table 4.

[0132] CHA Cyclohexyl acrylate BZA Benzyl acrylate OXEA (3-ethyloxetan-3-yl)methyl acrylate BDDA 1,4-butanediol diacrylate AIO-A 2-allyloxymethylacrylic acid AIO-Zn Zinc 2-allyloxymethylacrylate AIO-Ca Calcium 2-allyloxymethylacrylate AIO-Mg Magnesium 2-allyloxymethylacrylate AIO-Na Sodium 2-allyloxymethylacrylate AIO- 2-allyloxymethylacrylic acid ion

[0133] As is clear from the results of the heat tensile tests of Examples 4-1 to 4-6 and Comparative Examples 4-1 and 4-2, the polymers of the present invention are crosslinked yet possess thermoplasticity. The pencil hardness test result of Example 4-1 shows that scratch hardness is improved by heat stretching, and the retardation measurement result of Example 4-2 shows that heat stretching develops retardation. Furthermore, Example 4-6 shows that heat stretching at 120°C is possible, but heating at 200°C causes the oxetanyl groups and carboxyl groups to react, resulting in a stronger crosslinked product with improved scratch hardness and solvent resistance compared to before heating.

[0134] <Properties of Polymer: Stretching Trackability> [Example 5-1] A heat-resistant acrylic film with a protective film on one side (a 140 μm-thick film made by a melt extruder using pellets obtained by the method described in Production Example 7 of JP 2019-179124 A, and a polyethylene protective film attached to one side of the film) was cut to 15 cm x 7 cm, and the protective film side was attached to an iron plate (15 cm x 7 cm) with weak adhesive spray glue, and then cellophane tape (50 μm thick) was attached in a U-shape to the heat-resistant acrylic film. A polymerizable composition prepared in the same manner as in Example 4-1 was placed on the part where the cellophane tape was not attached, and the film was sandwiched between glass plates (15 cm x 7 cm) with a 2 mm-thick polypropylene plate attached, with the polypropylene plate facing inward, and secured in place with clips while removing air bubbles. A belt conveyor-type UV irradiation device (high-pressure mercury lamp, illuminance 200 mW / cm ２ ) from the glass plate side with an integrated light intensity of 2 J / cm ２After irradiating with UV light to achieve a thickness of 100 mm, the glass plate and iron plate were removed, and the cellophane tape portion was cut off along with the heat-resistant acrylic film to obtain a strip-shaped heat-resistant acrylic film coated on one side with the polymer of the present invention. Using a tensile tester equipped with an oven, the strip-shaped test specimen was pulled at a gripper distance of 60 mm, a pulling speed of 300 mm / min, and an oven temperature of 130°C. Pulling was stopped when the elongation reached 100% (i.e., 2x stretching), the oven was removed, and the test specimen was returned to room temperature and then removed from the gripper. The obtained test specimen was transparent, and no peeling was observed between the polymerized layer and the heat-resistant acrylic film substrate. The compositional ratios of the polymerizable compositions are summarized in Table 5.

[0135] Example 5-2: 0.007 g of a fluorine-based surfactant (Ftergent 215M, Neos Co., Ltd.), 0.14 g of zinc oxide, 1.99 g of phenoxyethyl acrylate, and 1.00 g of 2-allyloxymethylacrylic acid were added to a screw tube containing a stirrer, and the mixture was stirred at 50°C for 30 minutes to obtain a homogeneous solution. 0.25 g of N,N'-bis(2-hydroxyethyl)ethylenediamine was added and stirred to obtain a homogeneous solution, which was then returned to room temperature. Finally, 0.10 g of 1-hydroxycyclohexyl phenyl ketone was added, and the mixture was stirred and mixed to obtain a polymerizable composition as a homogeneous, transparent liquid. A heat-resistant acrylic film with a protective film on one side (a film of 140 μm thickness made by a melt extruder from pellets obtained by the method described in Production Example 7 of JP 2019-179124 A, with a polyethylene protective film attached to one side) was cut to 15 cm × 7 cm, and the protective film side was attached to a glass plate (15 cm × 7 cm) with weak adhesive spray glue. After that, a polymerizable composition was applied to the heat-resistant acrylic film using a bar coater No. 4, and the polymerizable composition was then applied to a belt conveyor-type UV irradiation device (high-pressure mercury lamp, illuminance 150 mW / cm ２ ) under a nitrogen atmosphere with an integrated light dose of 1 J / cm ２The coated film was irradiated with UV light until the film was tackless and hard. The coated film was removed from the glass plate and both ends were cut to obtain a strip-shaped heat-resistant acrylic film (10 cm x 5 cm) coated on one side with the polymer of the present invention. Using a tensile tester equipped with an oven (same as above), the strip-shaped test specimen was pulled at a gripper distance of 60 mm, a pulling speed of 300 mm / min, and an oven temperature of 130°C. When the elongation reached 100% (i.e., 2x stretching), the pulling was stopped, the oven was removed, and the test specimen was returned to room temperature. The test specimen was then removed from the gripper. The obtained test specimen was transparent, and no peeling was observed between the polymer layer and the heat-resistant acrylic film substrate. The compositional ratios of the polymerizable compositions are summarized in Table 5.

[0136] Example 5-3 To a screw tube containing a stirrer, 0.009 g of a fluorine-based surfactant (Ftergent 215M, Neos Co., Ltd.), 0.22 g of zinc oxide, 2.80 g of phenoxyethyl acrylate, 0.80 g of 2-allyloxymethylacrylic acid, and 0.39 g of acrylic acid were added, and the mixture was stirred at 50° C. for 30 minutes to obtain a homogeneous solution. After returning the mixture to room temperature, 0.53 g of diallylamine was added and stirred, and finally 0.14 g of 1-hydroxycyclohexyl phenyl ketone was added and mixed by stirring to obtain a polymerizable composition as a homogeneous, transparent liquid. A heat-resistant acrylic film with a protective film on one side (a film of 140 μm thickness made by a melt extruder from pellets obtained by the method described in Production Example 7 of JP 2019-179124 A, with a polyethylene protective film attached to one side) was cut to 15 cm × 7 cm, and the protective film side was attached to a glass plate (15 cm × 7 cm) with weak adhesive spray glue. After that, a polymerizable composition was applied to the heat-resistant acrylic film using a bar coater No. 4, and the polymerizable composition was then applied to a belt conveyor-type UV irradiation device (high-pressure mercury lamp, illuminance 150 mW / cm ２ ) under a nitrogen atmosphere with an integrated light dose of 1 J / cm ２The coated film was irradiated with UV light until the film was tackless and hard. The coated film was removed from the glass plate and both ends were cut to obtain a strip-shaped heat-resistant acrylic film (10 cm x 5 cm) coated on one side with the polymer of the present invention. Using a tensile tester equipped with an oven (same as above), the strip-shaped test specimen was pulled at a gripper distance of 60 mm, a pulling speed of 300 mm / min, and an oven temperature of 130°C. When the elongation reached 100% (i.e., 2x stretching), the pulling was stopped, the oven was removed, and the test specimen was returned to room temperature. The test specimen was then removed from the gripper. The obtained test specimen was transparent, and no peeling was observed between the polymer layer and the heat-resistant acrylic film substrate. The compositional ratios of the polymerizable compositions are summarized in Table 5.

[0137]

[0138] The stretching compliance of Examples 5-1 to 5-3 utilizes the adhesion of the polymer of the present invention, which is evident from Examples 2-1 to 2-3, and the thermoplasticity of the polymer of the present invention, which is evident from Examples 4-1 to 4-6. In other words, this demonstrates that the coating layer laminated on the substrate can be thermoformed integrally with the substrate, even though it is a crosslinked body. Therefore, the polymerizable composition of the present invention can be used, for example, as a crack prevention coating for brittle raw film, a protective coating for decorative film, a retardation adjustment coating, etc.

Claims

1. A radically polymerizable compound (A) that is immiscible with water, represented by the following formula (1): 【Chemistry 1】 (In the formula, R represents a saturated or unsaturated hydrocarbon group having 10 or less carbon atoms.) A radical polymerizable composition comprising an anion represented by the formula: the cation includes at least one selected from the group consisting of a typical metal element, a metal or metal oxide ion belonging to Group 3 or Group 4 of the periodic table, a protonated amine, a quaternary ammonium ion, a phosphonium ion, and a protonated phosphine; the content of the anion is 1 to 120 parts by mass per 100 parts by mass of the radically polymerizable compound (A) that is immiscible with water.

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

3. 3. The radical polymerizable composition according to claim 1, wherein the cation comprises one or more cations selected from the group consisting of metal or metal oxide ions of lithium, sodium, potassium, magnesium, calcium, zinc, or aluminum, protonated amines, and quaternary ammonium ions.

4. A polymer of the radically polymerizable composition according to claim 1 or 2.

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