Radical polymerizable composition and polymer 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

[Technical Field]

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

[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 1-3). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2016-079408 [Patent Document 2] Japanese Patent Application Laid-Open No. 2005-054019 [Patent Document 3] Japanese Patent Application Publication No. 11-029672 [Non-patent literature]

[0005] [Non-Patent Document 1] "Development of Ionomer and Ionic Polymer Materials", CMC Publishing, 2009 [Non-patent document 2] Journal of the Robotics Society of Japan, Vol. 24, No. 4, p. 442, 2006 Summary of the Invention [Problem to be solved by the invention]

[0006] As described above, it is known that, for ethylene-based ionomers, ethylene / unsaturated carboxylic acid is copolymerized and the resulting copolymer is ionized.

[0007] However, conventional ionomers are synthesized by synthesizing a host polymer having ionizable functional groups 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 that are carboxylates with high radical polymerizability. However, these are miscible only with water or highly polar organic substances, and 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 become 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. [Means for solving the problem]

[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 radically polymerizable compound (A) immiscible with water and a compound represented by the following formula (1):

[0012] [ka]

[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 radical polymerizable composition according to the above [1], wherein R in the formula (1) is an allyl group or a methallyl group. [3] The radical polymerizable composition according to the above [1] or [2], further comprising a cation, the cation being one or more cations selected from the group consisting of a metal ion, a metal oxide ion, and a cation containing a non-metal element of Group 15 of the periodic table. [4] A polymer of the radically polymerizable composition according to any one of [1] to [3] above. [Effects of the Invention]

[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. DETAILED DESCRIPTION OF THE INVENTION

[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 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, to obtain an ionically crosslinked polymer having an ionomer structure, a radically polymerizable compound (A) that is immiscible with water is used as the main component for forming the polymer backbone. Here, "immiscible with water" is determined by whether or not it can be homogenized when mixed with water in equal amounts. Furthermore, "homogeneous" refers to a state in which, when the radically polymerizable compound (A) and water are mixed in equal amounts, no precipitate is visually observed and the mixture is transparent. The determination can be made based on whether the mixture is uniform at the temperature and pressure at which it is polymerized, but more simply, it can be made based on whether the mixture is uniform at room temperature and normal pressure, and the temperature and pressure at which it is mixed do not have to be normal temperature and normal pressure. The temperature and pressure at which the determination is made 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 body. The radically polymerizable group may be any unsaturated bond that can be radically polymerized, 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 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, but the present invention is not limited to these examples. Among these, 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 are preferred.

[0020] Examples of compounds having a carbon-carbon double bond bonded to a carbonyl group 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 to which a cyano group is bonded include (meth)acrylonitrile and 2-cyanoacrylates. Examples of compounds having a carbon-carbon double bond to which a nitrogen atom is bonded include N-vinylamides and vinylamines. Examples of compounds having a carbon-carbon double bond to which an aromatic ring is bonded include aromatic vinyls. Examples of compounds having a carbon-carbon double bond to which an oxygen atom is bonded 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 only such examples.

[0022] Among these, from the viewpoints of polymerization activity and the diversity of synthesizable structures, 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; but 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, and 2-(meth)allyloxymethyl acrylate. Alkyl esters such as n-amyl 2-(meth)allyloxymethyl acrylate, sec-amyl 2-(meth)allyloxymethyl acrylate, tert-amyl 2-(meth)allyloxymethyl acrylate, n-hexyl 2-(meth)allyloxymethyl acrylate, 2-ethylhexyl 2-(meth)allyloxymethyl acrylate, isodecyl 2-(meth)allyloxymethyl acrylate, tridecyl 2-(meth)allyloxymethyl acrylate, lauryl 2-(meth)allyloxymethyl acrylate, and stearyl 2-(meth)allyloxymethyl acrylate; 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) oligomers / polymers, epoxy(2-(meth)allyloxymethyl acrylate) oligomers / polymers, and polyester(2-(meth)allyloxymethyl acrylate) oligomers / polymers; however, the present disclosure is not limited to these examples, and any oligomer / polymer having a 2-(meth)allyloxymethyl acrylate structure and immiscible with water may be used.

[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. 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 viewpoint of making the compound 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] 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, from the viewpoint of achieving a good balance between the viscosity of the composition and the mechanical properties of the polymer, such as toughness.

[0032] <Anion represented by formula (1)> The radical polymerizable composition of the present disclosure comprises a compound represented by the following formula (1):

[0033] [ka]

[0034] (wherein R represents a saturated or unsaturated hydrocarbon group having 10 or less carbon atoms). Conventional ionomers are synthesized by synthesizing a host polymer having ionizable functional groups and then ionizing (neutralizing) it. However, 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 with 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 widely used as radically polymerizable salts, are highly radically polymerizable but are only miscible with water or highly polar organic substances, making it difficult to dissolve them uniformly in low-polarity vinyl compounds and liquefy them. Furthermore, although polyacrylic 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, the use of the above anions allows for uniform dissolution in low-polarity vinyl compounds, resulting in a liquid polymerizable composition. Furthermore, resins with an ionomer structure can be successfully formed using simple methods such as coating and printing processes.

[0035] To obtain the radical polymerizable composition of the present invention containing the anion represented by the above formula (1), it is preferable to use a radical polymerizable carboxylate compound (B) composed of an anion component containing the anion represented by the above formula (1) and a cation component as a component for forming an ionic crosslinking structure. 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 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 per 100 parts by mass of the above 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 above 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 2-oxymethylacrylic acid ions as anions constituting the polymerizable salt compound (B), or may contain 2-oxymethylacrylic acid ions and anions other than 2-oxymethylacrylic acid ions. The anion other than the 2-oxymethylacrylic acid ion is not particularly limited, but from the viewpoint of solubility in the polymerizable compound (A) and organic solvents, anions of organic protonic acids are preferred. Specific examples of such anions, by protonic acid name, 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 radically polymerizable composition of the present invention may further contain a cation, and the cation is preferably the cation that constitutes the polymerizable salt compound (B).

[0041] Examples of inorganic cations include metal ions or metal oxide ions. Specific examples of the inorganic cations include Group 1 elements of the periodic table, such as lithium, sodium, and potassium; Group 2 elements of the periodic table, such as magnesium, calcium, and barium; transition metal elements or transition metal oxides, such as lanthanum, zirconium oxide, iron, cobalt, nickel, and copper; and typical metal elements of Groups 12 to 15 of the periodic table, such as zinc, aluminum, tin, lead, and bismuth. However, the cations are not limited to these examples, and may be a combination of ions of two or more metals or metal oxides. From the viewpoint of rendering the polymerizable composition of the present disclosure colorless, the metal ion portion of the metal carboxylate is preferably an ion of a typical metal element, a metal belonging to Groups 3 or 4 of the periodic table, or a metal oxide thereof. Taking into account availability and toxicity, lithium, sodium, potassium, magnesium, calcium, zinc, and aluminum are even 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] For protonated amines, the names of the amines before protonation are specifically listed as follows: 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, diazabicycloundecene, Examples of the amines include amines having primary to tertiary nitrogen atom moieties and monovalent and divalent or higher amine valencies, such as zabicyclononene, 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 polymerizable salt compound (B) can be prepared by reacting a compound represented by the following formula (2):

[0047] [ka]

[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 the above formula (2) include the above-mentioned organic protonic acids. 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-metal 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 ingredients> 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 radical polymerization inhibitors, radical polymerization initiators, solvents, radically polymerizable compounds miscible with water, compounds that undergo a thermal addition reaction or thermal condensation reaction with active hydrogen groups, thermoplastic resins, organic or inorganic fine particles, fillers, dyes, pigments, dispersants, UV absorbers, leveling agents, surface conditioners, antistatic agents, adhesion improvers, coupling agents, mold release agents, and viscosity modifiers, but the present disclosure is not limited to these.

[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 inhibitors] From the viewpoint of suppressing 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 radical chain inhibitory properties and / or a secondary antioxidant having peroxide decomposition properties.

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

[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 the hydroxybenzoates include 2,2'-methylenebis(6-tert-butyl-3-methylphenol), 4,4'-thiobis(6-tert-butyl-3-methylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 2,2'-thiobis(4-methyl-6-tert-butylphenol), 2-[1-(2-hydroxy-3,5-ditert-pentylphenyl)ethyl]-4,6-ditert-pentylphenyl acrylate, and 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate, but the present disclosure is not limited to these examples. The semi-hindered phenols and their polymers (including dimers) or derivatives of the polymers may be used either alone or in combination of two or more kinds.

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

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

[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.

[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 photoradical initiators and thermal radical initiators 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 thereof 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-dimethoxyphenyl)- ... Phosphine oxide compounds such as bis(benzoyl)-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 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-butyl peroxylaurate, t-butylperoxyisopropyl monocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate, t-butyl peroxyacetate, t-butylperoxy-m-toluylbenzoate, t-butyl peroxybenzoate, bis(t-butylperoxy)isophthalate, 2,5-dimethyl-2,5-bis(m-toluylperoxy)hexane, t-hexyl peroxybenzoate, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane, t-butylperoxyallyl monocarbonate, t-butyltrimethylsilyl peroxide, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, and 2,3-dimethyl-2,3-diphenylbutane.

[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-methyl-2-imidazolin-2-yl)propane]dihydrochloride 2,2'-Azobis{2-[1-(2-hydroxyethyl)-2-imidazolin-2-yl]propane}dihydrochloride, 2,2'-Azobis[2-(2-imidazolin-2-yl)propane], 2,2'-Azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide}, 2,2'-Azobis{2-methyl-N-[1,1-bis(hydroxymethyl)ethyl]propionamide}, 2,Azo initiators such as 2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], 2,2'-azobis(2-methylpropionamide), 2,2'-azobis(2,4,4-trimethylpentane), 2,2'-azobis(2-methylpropane), dimethyl-2,2-azobis(2-methylpropionate), 4,4'-azobis(4-cyanopentanoic acid), and 2,2'-azobis[2-(hydroxymethyl)propionitrile].

[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 viewpoints 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] [Radical polymerizable compound miscible with water] The radical polymerizable composition of the present invention may contain an appropriate amount of a radical polymerizable compound miscible with water depending on the purpose and use. Specific examples of the radical 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 radical polymerizable group may be used.

[0077] [Compounds that undergo thermal addition or thermal condensation reactions with active hydrogen groups] 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 thermal condensation reaction with an active hydrogen group, and may be one type or two or more types in the same molecule. Also, it may be 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 phenol 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 Epocross WS-300 (product name, Nippon Shokubai Co., Ltd.), Epocross WS-500 (product name, Nippon Shokubai Co., Ltd.), Epocross WS-700 (product name, Nippon Shokubai Co., Ltd.), and Epocross 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 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-polycondensation oligomer of tetramethoxysilane, hydrolysis-polycondensation oligomer 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 polymer compounds such as radical (co)polymers of compounds having a radical polymerizable group and an alkoxysilyl group, such as alkoxysilyl-terminated polydimethylsiloxane, 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 hexamethylolmelamine, partially or completely methyl-etherified products of hexamethylolmelamine, 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, dimethyloldihydroxyethyleneurea, and methyl-etherified products of dimethyloldihydroxyethyleneurea; 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> The polymer of the present disclosure can be obtained by reacting the radically polymerizable composition of the present disclosure, and the reaction method includes at least generating radicals in the radically polymerizable composition of the present disclosure to carry out radical polymerization. A radical polymer of the radically polymerizable composition of the present disclosure, which is a polymer obtained by polymerizing such a radically polymerizable composition of the present disclosure under radical-generating conditions, also constitutes part of the present disclosure.

[0089] Examples of radical generation methods include heating the radical polymerizable composition of the present disclosure and / or irradiating the radical polymerizable composition of the present disclosure with active energy rays. Heating or irradiating with active energy rays may be performed in one step or in two or more separate steps. Heating and irradiating with active energy rays may be combined, may be performed simultaneously, or may be performed separately. When heating or irradiating with active energy rays, it is more preferable that the 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] The active energy rays can be those that are commonly used, including electromagnetic waves such as gamma rays, X-rays, ultraviolet rays, visible light, and infrared rays, and particle rays such as electron beams, neutron beams, and proton beams. Among these, in terms of energy intensity, energy ray generator, etc., gamma rays, X-rays, ultraviolet rays, visible light, and electron beams are preferred, ultraviolet rays, visible light, and electron beams are more preferred, and ultraviolet rays are most preferred. When a photoradical initiator is not used, it is preferable to use active energy rays with high energy such as gamma rays, X-rays, and electron beams, and when a photoradical initiator is used, it is preferable to use active energy rays such as ultraviolet rays and visible light, which have relatively low energy but are easy to generate and economical.

[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 have only one type of the structural unit (a), the structural unit (b), and the structural unit (c), or may have two or more types of each.

[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 the 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 the 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) structural units in which at least one of the carbon-carbon double bonds of the polymerizable compound (A) and the 2-oxymethylacrylic acid ion is replaced with a carbon-carbon single bond, and (ii) structural units formed by cyclopolymerization of the polymerizable compound (A) and the 2-oxymethylacrylic acid ion when the polymerizable compound (A) and the 2-oxymethylacrylic acid ion are cyclopolymerizable compounds. An example of the compound containing the 2-oxymethylacrylic acid ion is the polymerizable salt compound (B).

[0099] <Uses of the radically polymerizable composition of the present disclosure> The radical polymerizable composition of the present disclosure can be made into a liquid form that can be used in various printing applications by adjusting the types and amounts of the above-mentioned polymerizable compound (A), polymerizable salt compound (B), and other components, and the polymerized product can exhibit the various excellent properties of conventional ionomers. Therefore, the composition can be used in a wide variety of applications, such as various coatings (anti-crack coatings for brittle films, protective coatings for decorative films, retardation adjustment coatings, etc.), 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. [Example]

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

[0102] <Dissolution of polymerizable salts in radically polymerizable compounds that are immiscible with water> [Example 1-1] 0.26g of zinc oxide, 2.8g of methanol, and 1.04g 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 methanol solution (90 mol% of the 2-allyloxymethylacrylic acid was neutralized with zinc). The mixture was returned to room temperature, and 2.8g of 2-ethylhexyl acrylate was added. The temperature was then reduced with a vacuum pump while 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 replaced with cyclohexyl acrylate, and a uniform, transparent liquid composition with a zinc concentration of 5.2% was obtained. The results are shown in Table 1.

[0104] [Comparative Example 1-1] 0.22g of zinc oxide, 2.8g of methanol, and 0.43g 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 mixture was returned to room temperature and 2.8g of 2-ethylhexyl acrylate was added (an amount that would result in a zinc concentration of 5.2% if the methanol was removed). The mixture was then reduced in pressure with a vacuum pump while still at room temperature to remove the methanol. However, a white precipitate formed during the removal of the methanol, and the solution was not homogeneous. The results are shown in Table 1.

[0105] [Comparative Example 1-2] The procedure was the same as in Comparative Example 1-1, except that 2-ethylhexyl acrylate was replaced with cyclohexyl acrylate. During the removal of methanol, a white precipitate was formed and a homogeneous solution was not obtained. The results are shown in Table 1.

[0106] [Table 1] EHA 2-Ethylhexyl Acrylate CHA Cyclohexyl acrylate AIO-A 2-Allyloxymethylacrylic acid AIO-Zn 2-allyloxymethyl acrylate zinc salt AA acrylic acid AA-Zn Zinc Acrylate AIO- 2-allyloxymethylacrylate ion

[0107] <Polymer characteristics: 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 the mixture was stirred at 50°C for 4 hours to obtain a uniform ethanol solution (100 mol% of the 2-allyloxymethylacrylic acid was neutralized with zinc). The mixture was then 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 polymerization components. The resulting composition was applied to a heat-resistant acrylic film (a 140 μm thick film made by melt-extruding pellets obtained by the method described in Production Example 7 of JP 2019-179124 A) using a bar coater No. 4, and then placed on a hot plate at 80°C for 5 minutes to dry. The dried coating film was then dried using a belt conveyor-type UV irradiation device (high-pressure mercury lamp, illuminance 200 mW / cm). 2 ), the cumulative light intensity was 0.6 J / cm 2 So it became tackleless. The adhesion of the polymer layer was evaluated according to JIS K 5600-5-6 (cross-cut method). That is, out of all the squares (10 × 10 squares = 100 squares), the number of squares that remained without peeling or damage was evaluated as 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 replaced with 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. 2When the adhesiveness was evaluated, the number of squares that remained 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 uniform ethanol solution (60 mol% of the 2-allyloxymethylacrylic acid was neutralized with zinc). The mixture was then 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, followed by stirring to obtain a composition in the form of an ethanol solution containing 50% of the polymerization components. Using this, a dry coating film was formed on a heat-resistant acrylic film in the same manner as in Example 2-1, and the dry coating film was then exposed to a belt conveyor-type UV irradiation device 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 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), which is an industrially readily available divalent acrylate ester, is miscible with water-immiscible radically polymerizable compounds, and has a short length between radically polymerizable groups, was used instead of zinc 2-allyloxymethylacrylate. That is, 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 by stirring, and the resulting uniform, transparent liquid composition was applied to a heat-resistant acrylic film using a bar coater No. 2. This was polymerized using a belt conveyor-type UV irradiation device in the same manner as in Example 2-1, and the cumulative light dose was 5 J / cm. 2 So it became tackleless. When the adhesion of the polymerized 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 replaced with isobornyl acrylate, and the liquid composition was applied to a heat-resistant acrylic film. The composition was polymerized using a belt conveyor-type UV irradiation device, resulting in an accumulated light dose of 5 J / cm. 2 When the adhesiveness was evaluated, the number of squares remaining without peeling or damage 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 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] [Table 2] EHA 2-Ethylhexyl Acrylate IBOA Isobornyl acrylate CHA Cyclohexyl acrylate DPHA Dipentaerythritol Hexaacrylate BDDA 1,4-Butanediol Diacrylate AIO-A 2-Allyloxymethylacrylic acid AIO-Zn 2-allyloxymethyl acrylate zinc salt AIO- 2-allyloxymethylacrylate ion

[0114] <Characteristics of polymers: 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 the mixture was 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 then returned to room temperature, and 3.57 g of 2-ethylhexyl acrylate was added. The mixture was then kept at room temperature and the pressure was reduced with a vacuum pump to remove the methanol. Then, 0.15 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 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, and a 0.5 mm thick silicon sheet cut into a U-shape 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 mold 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 with an integrated light dose of 1 J / cm. 2 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 dumbbell-shaped No. 3 specimen (compliant with JIS K 6251) using a test specimen punching machine. After measuring the thickness at the center of the test piece, the tensile strength (maximum tensile force until the test piece broke), Young's modulus, and breaking elongation 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 pieces produced during the preparation of the dumbbell-shaped test pieces were analyzed by X-ray diffraction, peaks due to ion aggregation domains specific to ionomers were observed on the low-angle side (2θ = 2 to 4°).

[0115] [Example 3-2] In a screw tube containing a stirrer, 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 and stirred to form 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 stirred to form a homogeneous, transparent liquid polymerizable composition. Using this polymerizable composition, a dumbbell-shaped No. 3 test piece was 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 (the length between acryloyloxy groups = 4 carbon atoms), which is an industrially readily available divalent acrylate ester, is miscible with water-immiscible radical polymerizable compounds, and has a short distance between radical polymerizable groups (= acryloyloxy groups), 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 and stirred 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 strength of the test piece was so weak that the portion clamped by the clamp broke when the test piece 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 this order to a recovery flask containing a stirrer, and the mixture was stirred at 50°C for 4 hours to obtain a homogeneous solution (60 mol% of the 2-allyloxymethylacrylic acid was neutralized with zinc). The mixture was returned to room temperature, and 10.44 g of 2-ethylhexyl acrylate was added. The mixture was then depressurized with a vacuum pump while still at room temperature to remove the methanol, yielding approximately 16 g of a polymerizable composition containing no initiator. 5.0 g of the mixture was taken, and 0.15 g of 1-hydroxycyclohexyl phenyl ketone was added thereto and stirred. After that, a dumbbell-shaped No. 3 test piece was 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] To the initiator-free polymerizable composition obtained in Example 3-3, 0.10 g of 1-hydroxycyclohexyl phenyl ketone and 0.05 g of t-butylperoxy-2-ethylhexanoate were added, stirred, and mixed. The mixture was poured into a casting mold in the same manner as in Example 3-1, and then irradiated from the glass plate side with a belt conveyor-type UV irradiation device at an integrated light dose of 1 J / cm. 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] [Examples 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 with 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 mold. The polymerizable composition was poured into the mold, and the mold was placed in a polypropylene bag and immersed in 60°C hot water while suspended for 2 hours. The mold was then placed in a 110°C oven and heated for 1 hour. The mold was then removed, yielding a sheet approximately 13 cm x 5 cm x 0.5 mm thick. Dumbbell-shaped No. 3 test pieces were prepared 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] [Examples 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 pressure was reduced with a vacuum pump while still at room temperature to remove the methanol. 2.04 g of a 75% ethyl acetate solution of a trimethylolpropane adduct of tolylene diisocyanate was then added, and the pressure was reduced with a vacuum pump while still at room temperature to remove the ethyl acetate. 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] [Table 3] EHA 2-Ethylhexyl Acrylate BDDA 1,4-Butanediol Diacrylate AIO-A 2-Allyloxymethylacrylic acid AIO-Zn 2-allyloxymethyl acrylate zinc salt AIO-TAEA Tris(2-aminoethyl)amine salt of 2-allyloxymethylacrylic acid AIO- 2-allyloxymethylacrylate 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 indicate that the polymers of the present invention have an ionomer structure. Furthermore, Example 3-6 indicates that solvent resistance can be improved by adding a crosslinking agent that reacts with carboxyl groups in advance, followed by UV curing and then thermal curing, i.e., by using a dual-cure system.

[0124] <Properties of polymer: Thermoplastic> [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 the mixture was 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 mixture was kept at room temperature and the pressure was reduced with a vacuum pump to remove the methanol. Then, 0.15 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 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, and a 0.5 mm thick silicon sheet cut into a U-shape 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 mold 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 with an integrated light dose of 1 J / cm. 2 The plate and silicone sheet were removed, and the resulting sheet, approximately 13 cm x 5 cm x 0.5 mm thick, was cut into 10 cm x 4 cm strips using a cutter, and the edges were polished. The pencil hardness of the remaining pieces was measured using an electric pencil hardness tester with a load of 750 g, resulting in a value of H. Using a tensile tester equipped with an oven, a 10 cm x 4 cm strip-shaped test piece was pulled at a grip distance of 60 mm, a pulling speed of 30 mm / min, and an oven temperature of 120°C. When the elongation reached 100% (i.e., 2x stretching), the pulling was stopped, the oven was removed, and the test piece was allowed to return to room temperature. The test piece was then removed from the grip. The resulting test piece was transparent. The pencil hardness of the test piece after being stretched twice was also measured (the scratch scanning direction was perpendicular to the stretching direction), and it was found to have improved to 2H. Table 4 shows the weight ratio of the polymerizable components and the thermoplasticity results (stretchable to 2 times: ○, not stretchable: ×).

[0125] [Comparative Example 4-1] 1,4-butanediol diacrylate (the length between acryloyloxy groups = 4 carbon atoms), which is an industrially readily available divalent acrylate ester, is miscible with water-immiscible radical polymerizable compounds, and has a short distance between radical polymerizable groups (= acryloyloxy groups), 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 and stirred to obtain a polymerizable composition. Using this polymerizable composition, a 10 cm × 4 cm strip test piece was prepared in the same manner as in Example 4-1. The pencil hardness of the surplus strips obtained during the preparation of the strip test piece was measured using an electric pencil hardness tester under a load of 750 g, and was found to be H. Using a tensile testing machine with an oven, a rectangular test piece was pulled at a gripping 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%. Table 4 shows the weight ratio of the polymerizable components and the thermoplasticity results (stretchable to 2 times: ○, not stretchable: ×).

[0126] [Example 4-2] A 10 cm x 4 cm strip test piece 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, strip-shaped test specimens were pulled at a grip distance of 60 mm, a pulling rate of 30 mm / min, and an oven temperature of 80°C. When the elongation reached 100% (i.e., 2x stretching), the pulling was stopped, the oven was removed, and the test specimen was allowed to return to room temperature. The test specimen was then removed from the grips. The resulting test specimen was transparent. The retardation of the test piece after 2x stretching was measured at a wavelength of 550 nm using a RETS-100 manufactured by Otsuka Electronics Co., Ltd., and was found to be a positive retardation of 210 nm per 100 μm of thickness. The weight ratio of the polymerizable components and the thermoplasticity results (stretchable to 2x: ○, not stretchable: ×) 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 testing machine with an oven, a rectangular test piece was pulled at a gripping 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%. Table 4 shows the weight ratio of the polymerizable components and the thermoplasticity results (stretchable to 2 times: ○, not stretchable: ×).

[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, and 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 3.53 g of cyclohexyl acrylate was added. The mixture was then reduced in pressure with a vacuum pump while still at room temperature to remove the methanol, after which 0.15 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. 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 speed of 30 mm / min, and an oven temperature of 120°C. When the elongation reached 100% (i.e., 2x stretching), the pulling was stopped, the oven was removed, and the test specimen was allowed to return to room temperature, after which it was removed from the gripper. The obtained test specimen was transparent. Table 4 shows the weight ratio of the polymerizable components and the thermoplasticity results (stretchable to 2 times: ○, not stretchable: ×).

[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 the mixture was stirred at 50°C for 1 hour to form a homogeneous solution. The mixture 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 vacuum dried at room temperature to obtain magnesium 2-allyloxymethylacrylate powder. A screw tube containing a stirrer was charged with 0.46 g of magnesium 2-allyloxymethylacrylate powder, 1.08 g of 2-allyloxymethylacrylic acid, and 0.19 g of ultrapure water, and the mixture was stirred while heating to 50°C until it became uniform and transparent. After the mixture was returned to room temperature, 3.50 g of cyclohexyl acrylate and 0.15 g of 1-hydroxycyclohexyl phenyl ketone were added and mixed with stirring to obtain a polymerizable composition as a uniform and 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 speed of 30 mm / min, and an oven temperature of 120°C. When the elongation reached 100% (i.e., 2x stretching), the pulling was stopped, the oven was removed, and the test specimen was allowed to return to room temperature, after which it was removed from the gripper. The obtained test specimen was transparent. Table 4 shows the weight ratio of the polymerizable components and the thermoplasticity results (stretchable to 2 times: ○, not stretchable: ×).

[0130] [Examples 4-5] To a recovery flask containing a stirrer, 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, and 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 pressure was reduced with a vacuum pump while still at room temperature to remove the methanol, and then 0.15 g of 1-hydroxycyclohexyl phenyl ketone was added and mixed by stirring to obtain a polymerizable composition as a homogeneous, 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 speed of 30 mm / min, and an oven temperature of 120°C. When the elongation reached 100% (i.e., 2x stretching), the pulling was stopped, the oven was removed, and the test specimen was allowed to return to room temperature, after which it was removed from the gripper. The obtained test specimen was transparent. Table 4 shows the weight ratio of the polymerizable components and the thermoplasticity results (stretchable to 2 times: ○, not stretchable: ×).

[0131] [Examples 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, and 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 2.52 g of cyclohexyl acrylate was added. The pressure was reduced with a vacuum pump while still at room temperature to remove the methanol, after which 1.01 g of (3-ethyloxetan-3-yl)methyl acrylate and 0.15 g of 1-hydroxycyclohexyl phenyl ketone were added, and the mixture was stirred and mixed to obtain a homogeneous, transparent liquid polymerizable composition. Using this polymerizable composition, a 10 cm x 4 cm strip-shaped test piece was prepared in the same manner as in Example 4-1. Using a tensile tester equipped with an oven, the 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. When the elongation reached 100% (i.e., 2x stretching), the pulling was stopped, the oven was removed, and the test piece was allowed to return to room temperature, after which it was removed from the gripper. The obtained test piece was transparent. The pencil hardness of the surplus pieces that were produced when cutting out the strip-shaped test pieces was measured using an electric pencil hardness tester with a load of 750 g, and the result was H. When the surface was wiped with a paper wiper soaked in acetone, the surface whitened slightly. On the other hand, when the pencil hardness of another surplus piece was measured after heating it on a hot plate at 200°C for 5 minutes, the result was 3H, and the surface did not whiten when wiped with a paper wiper soaked in acetone. Table 4 shows the weight ratio of the polymerizable components and the thermoplasticity results (stretchable to 2 times: ○, not stretchable: ×).

[0132] [Table 4] 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 2-allyloxymethyl acrylate zinc salt AIO-Ca 2-Allyloxymethylacrylate Calcium AIO-Mg 2-Allyloxymethylacrylate Magnesium AIO-Na Sodium 2-Allyloxymethylacrylate AIO- 2-allyloxymethylacrylate 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 improves upon 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 is possible at 120°C, but that 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] <Polymer properties: stretchability> [Example 5-1] A heat-resistant acrylic film with a protective film on one side (a 140 μm-thick film made by melt extruding 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 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 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 2 After irradiating with UV light to achieve a uniform elongation, the glass and iron plates were removed, and the cellophane tape was cut off along with the heat-resistant acrylic film, yielding a strip of 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 specimen was stretched at a gripper distance of 60 mm, a tension speed of 300 mm / min, and an oven temperature of 130°C. The tension was stopped when the elongation reached 100% (i.e., 2x stretching), the oven was removed, and the specimen was allowed to return to room temperature before being removed from the gripper. The resulting specimen was transparent, and no peeling was observed between the polymer layer and the heat-resistant acrylic film substrate. The composition ratios of the polymerizable compositions are summarized in Table 5.

[0135] [Example 5-2] A screw cap containing a stirrer was charged with 0.007 g of a fluorochemical 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, and 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 stirred to obtain a homogeneous, transparent liquid polymerizable composition. A heat-resistant acrylic film with a protective film on one side (a 140 μm-thick film made by melt-extruding pellets obtained by the method described in Production Example 7 of JP 2019-179124 A) was cut into a size of 15 cm x 7 cm, and the protective film side was attached to a glass plate (15 cm x 7 cm) using weakly adhesive spray glue. After that, a polymerizable composition was applied to the heat-resistant acrylic film using a bar coater No. 4, and the film was then heated in 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 2 The surface was tackless and hard. The coated film was removed from the glass plate and both ends were cut to obtain strips of heat-resistant acrylic film (10 cm x 5 cm) coated on one side with the polymer of the present invention. Using an oven-equipped tensile tester (same as above), the strip specimens were 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 specimen was allowed to return to room temperature before being removed from the grippers. The resulting specimens were transparent, and no peeling was observed between the polymer layer and the heat-resistant acrylic film substrate. The composition ratios of the polymerizable compositions are summarized in Table 5.

[0136] [Example 5-3] A screw tube containing a stirrer was charged with 0.009 g of a fluorochemical 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, and the resulting 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-hydroxycyclohexylphenyl ketone was added and mixed by stirring, yielding a polymerizable composition as a homogeneous, transparent liquid. A heat-resistant acrylic film with a protective film on one side (a 140 μm-thick film made by melt-extruding pellets obtained by the method described in Production Example 7 of JP 2019-179124 A) was cut into a size of 15 cm x 7 cm, and the protective film side was attached to a glass plate (15 cm x 7 cm) using weakly adhesive spray glue. After that, a polymerizable composition was applied to the heat-resistant acrylic film using a bar coater No. 4, and the film was then heated in 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 2 The surface was tackless and hard. The coated film was removed from the glass plate and both ends were cut to obtain strips of heat-resistant acrylic film (10 cm x 5 cm) coated on one side with the polymer of the present invention. Using an oven-equipped tensile tester (same as above), the strip specimens were 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 specimen was allowed to return to room temperature before being removed from the grippers. The resulting specimens were transparent, and no peeling was observed between the polymer layer and the heat-resistant acrylic film substrate. The composition ratios of the polymerizable compositions are summarized in Table 5.

[0137] [Table 5]

[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 shows 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, or a retardation adjustment coating.

Claims

1. A radically polymerizable compound (A) immiscible with water, represented by the following formula (1): 【Chemistry 1】 (In the formula, R represents a saturated or unsaturated hydrocarbon group having 3 to 10 carbon atoms.) A radical polymerizable composition comprising an anion represented by the formula: and a cation, The water-immiscible radical polymerizable compound (A) comprises at least one selected from the group consisting of compounds having a carbon-carbon double bond bonded to a carbonyl group, compounds having a carbon-carbon double bond bonded to a cyano group, compounds having a carbon-carbon double bond bonded to a nitrogen atom, compounds having a carbon-carbon double bond bonded to an aromatic ring, compounds having a carbon-carbon double bond bonded to an oxygen atom, compounds having a carbon-carbon double bond in which the carbon-carbon double bonds are bonded and conjugated, and compounds having a carbon-carbon double bond bonded to a halogen atom, the water-immiscible radically polymerizable compound (A) has 4 to 90 carbon atoms; 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 4 of the periodic table, a protonated amine, a quaternary ammonium ion, a phosphonium ion, and a protonated phosphine; the radically polymerizable composition having a content of the anion of 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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