WO2023167187A1 - 重合性組成物 - Google Patents

重合性組成物 Download PDF

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Publication number
WO2023167187A1
WO2023167187A1 PCT/JP2023/007318 JP2023007318W WO2023167187A1 WO 2023167187 A1 WO2023167187 A1 WO 2023167187A1 JP 2023007318 W JP2023007318 W JP 2023007318W WO 2023167187 A1 WO2023167187 A1 WO 2023167187A1
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Prior art keywords
meth
acrylate
polymerizable composition
allyloxymethyl
acid
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English (en)
French (fr)
Japanese (ja)
Inventor
知正 金子
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Nippon Shokubai Co Ltd
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Nippon Shokubai Co Ltd
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Priority to JP2024504696A priority Critical patent/JP7756785B2/ja
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F36/20—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds unconjugated

Definitions

  • the present invention relates to a polymerizable composition containing a cyclization polymerizable compound.
  • Non-Patent Document 1 In the radical polymerization of vinyl compounds, it is known that ordinary allyl ether groups and allyl ester groups tend to undergo degenerative chain transfer (for example, Non-Patent Document 1), and as a result, polymers with a high degree of polymerization can be obtained. There are effects such as low monomer conversion rate. In addition, ⁇ -substituted methyl acrylates have a low polymerization termination rate, so that a polymer with high hardness may be obtained in some cases, but it is known that the polymerization rate is low, that is, the polymerization activity is low (e.g., non-patent literature 2, Non-Patent Document 3).
  • 2-allyloxymethylacrylic acid and 2-allyloxymethylacrylic acid metal salts which are compounds having an allyl ether group and also have an ⁇ -substituted methylacrylic acid structure, have cyclic polymerizability ( It is known to have radical polymerizability similar to that of meth)acrylic acid and its metal salts (for example, Patent Documents 1 and 2).
  • 2-allyloxymethyl acrylic acid and 2-allyloxymethyl acrylic acid metal salts can be synthesized via base hydrolysis of 2-allyloxymethyl acrylic acid ester. No known side reactions or by-products occurred.
  • the present invention includes 2-allyloxymethyl acrylic acid and/or a salt thereof that is hydrophilic, water-soluble, and has reduced low-molecular-weight compounds that adversely affect radical polymerization. , to provide a polymerizable composition.
  • the present inventors conducted various studies to achieve the above object, and found that ⁇ -oxy having a specific partial structure was found in producing 2-allyloxymethyl acrylic acid or 2-allyloxymethyl acrylate It has been found that carboxylic acid and/or its salt is generated as a by-product, and that the amount of such ⁇ -oxycarboxylic acid and/or its salt can be quantified by measuring the amount of a specific partial structure.
  • 2-allyloxymethylacrylic acid and/or 2-allyloxymethylacrylic acid which have a low content of the by-product have good radical polymerizability, and are suitable as raw materials for polymers used in various applications
  • the present inventors have found a polymerizable composition containing a salt and arrived at the present invention. That is, the present invention is described in [1] to [5] below. [1] Formula (1) below;
  • R and R ' each independently represent a hydrogen atom or a saturated hydrocarbon group having 4 or less carbon atoms.
  • B / or a salt thereof
  • a polymerizable composition comprising a radically polymerizable compound (C) other than the cyclopolymerizable carboxylic acid and/or its salt (A) and the ⁇ -oxycarboxylic acid and/or its salt (B)
  • C radically polymerizable compound
  • A cyclopolymerizable carboxylic acid and/or its salt
  • A ⁇ -oxycarboxylic acid and/or its salt
  • the molar ratio of the partial structure contained in the polymerizable composition in the largest molar amount is represented by the formula (1).
  • the polymerizable composition is 1.5 or less per 100 molar amounts of the partial structure.
  • the radically polymerizable compound (C) contains a compound having a (meth)acryloyl group, and a 2-(meth)allyloxymethyl acryloyl group other than the cyclization-polymerizable carboxylic acid and/or salt thereof (A).
  • R and R' in the above formulas (2) to (4) are each independently a hydrogen atom, a methyl group, or an ethyl group. Polymerizable composition.
  • the total molar amount of the partial structure represented by any one of the above formulas (2) to (4) is 4 or less per 100 molar amount of the partial structure represented by the above formula (1).
  • the polymerizable composition of the present invention has reduced hydrophilic, water-soluble low-molecular-weight compounds that are likely to be released into the environment.
  • low-molecular-weight compounds that adversely affect radical polymerization are reduced, it has good radical polymerizability. It can be suitably used for various purposes such as coalesced raw materials.
  • FIG. 2 is a diagram showing peaks of carboxylate ions having partial structures (1) to (4) in an electropherogram obtained by analyzing the polymerizable composition of Comparative Example 3 with a capillary electrophoresis system.
  • (Meth)acryl means acryl or methacryl.
  • (Meth)allyl means allyl or methallyl.
  • the polymerizable composition of the present invention has the following formula (1);
  • R and R ' each independently represent a hydrogen atom or a saturated hydrocarbon group having 4 or less carbon atoms.
  • B / or a salt thereof
  • C a radically polymerizable compound other than the cyclization-polymerizable carboxylic acid and/or salt thereof (A) and the ⁇ -oxycarboxylic acid and/or salt thereof (B)
  • the molar ratio of the partial structure contained in the polymerizable composition in the highest molar amount is It is characterized by being 1.5 or less per 100 molar amounts of the partial structure represented by the formula (1).
  • the polymerizable composition of the present invention is hydrophilic and water-soluble, which is easily released into the environment, and has reduced low-molecular-weight compounds that have an adverse effect on radical polymerization, thereby reducing the risk of adverse effects on living organisms. and has excellent radical polymerizability.
  • the present invention will be described in detail below.
  • the polymerizable composition of the present disclosure includes a cyclization polymerizable carboxylic acid having a partial structure represented by the following formula (1) (hereinafter also referred to as partial structure (1)) and/or a salt thereof (A) (hereinafter , may be simply referred to as a cyclization-polymerizable carboxylic acid compound (A)).
  • partial structure (1) a partial structure represented by the following formula (1)
  • A a salt thereof
  • A may be simply referred to as a cyclization-polymerizable carboxylic acid compound (A)).
  • the above-mentioned partial structure refers to a structure that is a part of the structure of a compound and can be combined with other parts to form a compound.
  • the above bond may be an ionic bond, a covalent bond, or the like.
  • the cyclopolymerizable carboxylic acid compound (A) is a carboxylic acid
  • the cyclopolymerizable carboxylic acid compound (A) is 2-allyloxymethyl acrylic acid.
  • the cyclization-polymerizable carboxylic acid-based compound (A) is a carboxylate
  • the cation constituting the carboxylate may be an inorganic cation or an organic cation, and may be appropriately selected according to the purpose and application. Just do it.
  • inorganic cations include metal ions and metal oxide ions.
  • element names or metal oxide names include Group 1 elements of the periodic table such as lithium, sodium, and potassium; magnesium, calcium, and barium.
  • Periodic table group 2 elements such as; lanthanum, zirconium oxide, iron, cobalt, nickel, transition metal elements or transition metal oxides such as copper; periodic table group 12-15 such as zinc, aluminum, tin, lead, bismuth Typical metal elements; etc., but not limited to these examples, and combinations of ions of two or more metals or metal oxides may be used.
  • the metal ion portion of the metal carboxylate includes ions of typical metal elements, metals belonging to Groups 3 and 4 of the periodic table, or metal oxides. Lithium, sodium, potassium, magnesium, calcium, zinc, and aluminum are more preferred in terms of availability and toxicity.
  • organic cations include cations containing non-metallic elements of Group 15 of the periodic table. Nitrogen, phosphorus, and arsenic are mentioned as a nonmetallic element of periodic table 15 group.
  • nitrogen atom is positively ionized (ammonium ion, protonated amine, quaternary ammonium ion)
  • phosphorus atom is positively ionized (phosphonium ion, protonated phosphine, quaternary phosphonium ion).
  • ions in which a nitrogen atom is positively ionized are more preferable from the viewpoint of biosafety and availability.
  • protonated amines are methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, ethanolamine, diethanolamine, triethanolamine, tris(2- aminoethyl)amine, hexamethylenediamine, iminobispropylamine, methyliminobispropylamine, 3,6,9,12-tetraoxa-tetradecane-1,14diamine, N,N'-bis(2-hydroxyethyl)ethylenediamine , 1,3-bisaminomethylcyclohexane, 1,4-bisaminomethylcyclohexane, 3-aminomethyl-3,5,6-trimethylcyclohexylamine, isophoronediamine, 2,5 (or 2,6)-bis(amino methyl)bicyclo[2,2,1]heptane, 2,6 (or 2,7)-bis(aminomethyl)bicyclo[3,2,1]octane, 2,5
  • quaternary ammonium ions include tetramethylammonium ion, tetraethylammonium ion, tetrabutylammonium ion, benzyltrimethylammonium ion, hexadecyltrimethylammonium ion and the like, but the present disclosure is only such examples. is not limited to
  • the anion constituting the carboxylate is a carboxylate ion having the above partial structure (1), that is, a 2-allyloxymethylacrylate ion. It may contain only anions, but may also contain other anions. Such anions may be inorganic anions or organic anions, but from the viewpoint of solubility in organic substances, organic anions are preferable, and from the viewpoint of radical polymerization, a double bond conjugated with a carboxyl group is used.
  • carboxylic acid ion having, for example, (meth) acrylic acid ion, 2-methallyloxymethyl acrylate ion, hydroxyl group-containing (meth) having a structure in which a polybasic acid anhydride is added to an acrylic acid ester ( Meth)acrylic acid-based polymerizable carboxylic acid ions (2-(meth)acryloyloxyethylsuccinate ion, etc.) can be mentioned, and can be appropriately selected according to the purpose and application.
  • the carboxylate may be a compound consisting of one kind of cation and one kind of anion. and a compound or the like consisting of two or more anions.
  • Examples of the form of the carboxylic acid salt of the cyclization-polymerizable carboxylic acid compound (A) that may be present in the polymerizable composition of the present disclosure include, for example, a salt formed from the partial structure (1) and a cation; Salts formed from partial structure (1) and other anions and cations are included.
  • the polymerizable composition of the present invention may contain one cyclization-polymerizable carboxylic acid compound (A), or may contain two or more cyclization-polymerizable carboxylic acid compounds (A). You can stay.
  • the content of the partial structure (1) of the cyclization polymerizable carboxylic acid compound (A) contained in the polymerizable composition of the present disclosure is 3 parts by mass or more with respect to 100 parts by mass of the polymerizable composition of the present disclosure, It is preferably 90 parts by mass or less, more preferably 5 parts by mass or more and 85 parts by mass or less, and even more preferably 10 parts by mass or more and 80 parts by mass or less.
  • Ion chromatography and capillary electrophoresis are preferable from the viewpoint of being able to directly detect the partial structure (1) and the content of cations as ions, and 1 H-NMR is preferable from the viewpoint of performing measurement in a short time.
  • measurement is performed by capillary electrophoresis from the viewpoint of sensitivity and maintainability of the apparatus.
  • the polymerizable composition of the present disclosure is a ⁇ -oxycarboxylic acid having a partial structure represented by any of the following formulas (2) to (4) and/or a salt thereof (B) (hereinafter simply referred to as ⁇ -oxycarboxylic acid may be referred to as an acid-based compound (B)).
  • R and R' each independently represent a hydrogen atom or a saturated hydrocarbon group having 4 or less carbon atoms.
  • the ⁇ -oxycarboxylic acid compound (B) is usually a non-polymerizable or low-polymerizable compound in radical polymerization of a vinyl compound.
  • a compound having a partial structure represented by the above formula (2) corresponds to an allyl ether compound that is known to easily undergo degenerative chain transfer.
  • a compound having a partial structure represented by the above formula (3) does not have a vinyl group and is non-polymerizable.
  • a compound having a partial structure represented by the above formula (4) (hereinafter also referred to as partial structure (4)) has a low polymerization termination rate, so that a high-grade polymer may be obtained, but the polymerization rate is low. It is a compound structurally in the same category as ⁇ -substituted methyl acrylate, which is known to be small, that is, to have low polymerization activity.
  • the cyclization polymerizable carboxylic acid compound (A) is preferably produced via a step of hydrolyzing a lower ester of 2-allyloxymethyl acrylic acid with a base, and 2- As lower esters of allyloxymethyl acrylic acid, esters of saturated hydrocarbons having 4 or less carbon atoms are preferable, and methyl 2-allyloxymethyl acrylate and ethyl 2-allyloxymethyl acrylate are particularly preferable.
  • the ⁇ -oxycarboxylic acid compound (B) is mainly produced by a side reaction in the hydrolysis step, and the alkoxide moiety (RO-, R'-O-) in the structure is water or 2-allyloxymethyl acrylic acid.
  • R and R' in formulas (2) to (4) are hydrogen atoms, or 4 or less saturated hydrocarbon group, and when methyl 2-allyloxymethyl acrylate and ethyl 2-allyloxymethyl acrylate are used as raw materials, R and R' in formulas (2) to (4) are It becomes a hydrogen atom, a methyl group, or an ethyl group.
  • the content of the ⁇ -oxycarboxylic acid compound (B) in the polymerizable composition of the present disclosure is expressed as the content of the partial structure represented by any one of the above formulas (2) to (4), Of the partial structures represented by any one of formulas (2) to (4), the molar ratio of the partial structure contained in the polymerizable composition in the largest molar amount is represented by the above formula (1). The amount is 1.5 or less with respect to 100 molar amount of the partial structure.
  • the content of the partial structure of the ⁇ -oxycarboxylic acid compound (B), which is the most contained in the polymerizable composition is The molar amount is 1.5 or less, preferably 1.2 or less, more preferably 0.9 or less per 100 molar amounts of the partial structure (1).
  • the lower limit of the content of the partial structure of the ⁇ -oxycarboxylic acid compound (B) that is the most contained in the polymerizable composition it is preferably lower and is not particularly limited, but the molar amount of the partial structure (1) With respect to 100, the molar amount may be 0 or more, 0.01 or more, or 0.1 or more.
  • the content of the partial structure of the ⁇ -oxycarboxylic acid compound (B), which is the most contained in the polymerizable composition, is the cyclization polymerizable carboxylic acid compound represented by the formula (1) ( A) preferably has a molar amount of 0 or more and 1.5 or less, more preferably 0.01 or more and 1.2 or less, still more preferably 0.1 or more, relative to 100 molar amounts of the partial structure (1) of A); 0.9 or less.
  • the total molar amount of the partial structures (2) to (4) of the ⁇ -oxycarboxylic acid compound (B) contained in the polymerizable composition is the partial structure of the cyclization polymerizable carboxylic acid compound (A) It is preferably 4 or less, more preferably 3.5 or less, still more preferably 3 or less, and most preferably 2.5 or less per 100 molar amounts of (1). Further, regarding the lower limit of the total amount of the partial structure of the ⁇ -oxycarboxylic acid compound (B) contained in the polymerizable composition, it is preferably lower and is not particularly limited. On the other hand, the molar amount may be 0 or more, 0.01 or more, or 0.1 or more.
  • the total molar amount of the partial structure represented by any one of the formulas (2) to (4) contained in the polymerizable composition is the total molar amount of the partial structure (1) represented by the formula (1).
  • 2-allyloxymethyl acrylic acid and 2-allyloxymethyl acrylic acid metal salt can be synthesized, for example, via base hydrolysis of 2-allyloxymethyl acrylic acid ester, but by-products
  • the ⁇ -oxycarboxylic acid compound (B) presumed to have a tendency to inhibit radical polymerization. Furthermore, from the viewpoint of safety, the content of the ⁇ -oxycarboxylic acid compound (B) is required to be small since the content in the polymerizable composition is strictly restricted.
  • Ion chromatography and capillary electrophoresis are preferable from the viewpoint of being able to directly detect the above partial structures (2) to (4) and the content of cations as ions, and 1 H-NMR is preferable from the viewpoint of being able to perform measurements in a short time. preferable.
  • measurement is performed by capillary electrophoresis from the viewpoint of sensitivity and maintainability of the apparatus.
  • the polymerizable composition of the present disclosure contains a radically polymerizable compound (C) other than the above-described cyclization-polymerizable carboxylic acid and/or salt thereof (A) and ⁇ -oxycarboxylic acid and/or salt thereof (B).
  • the radically polymerizable compound (C) includes a monofunctional radically polymerizable monomer, which is a compound having one radically polymerizable group in the same molecule, and a compound having two or more radically polymerizable groups in the same molecule. It can be classified as a certain polyfunctional radically polymerizable compound.
  • the radically polymerizable groups are preferably carbon-carbon double bonds, more preferably carbon-carbon double bonds flanked by functional groups that activate the carbon-carbon double bonds.
  • the functional group that activates the carbon-carbon double bond includes preferably a carbonyl group, an amide group, a cyano group, an aromatic ring, an alkoxy group, an acyloxy group, a carbon-carbon double bond, and a halogen. Only one may be adjacent to the double bond, or two or more of two or more may be adjacent to each other.
  • Functional groups that activate carbon-carbon double bonds and corresponding compound groups are exemplified below, but the present disclosure is not limited to such exemplifications.
  • Examples of compounds having only one functional group that activates a carbon-carbon double bond and which is a carbonyl group include (meth)acrylic acid, (meth)acrylic acid ester, (meth)acrylamide, and the like ( meth) compounds having an acryloyl group; 2-hydroxymethyl acrylic acid, compounds having a 2-hydroxymethyl acryloyl group such as 2-hydroxymethyl acrylate; 2-(meth) allyloxymethyl acrylic acid, 2-(meth) compounds having a 2-(meth)allyloxymethylacryloyl group such as allyloxymethyl acrylate; and the like.
  • Compounds having only one carbon-carbon double bond activating functional group, which is an amide group include, for example, N-vinylamides.
  • Compounds having only one carbon-carbon double bond activating functional group, which is a cyano group include, for example, (meth)acrylonitrile.
  • Compounds having only one functional group that activates a carbon-carbon double bond, which is an aromatic ring include, for example, aromatic vinyls.
  • Compounds having only one carbon-carbon double bond activating functional group, which is an alkoxy group include, for example, vinyl ethers.
  • Examples of compounds having only one functional group that activates a carbon-carbon double bond, which is an acyloxy group, include vinyl esters.
  • Compounds having one or more carbon-carbon double bond-activating functional groups, one of which is a carbon-carbon double bond include, for example, conjugated dienes.
  • Examples of compounds having one or more halogen atoms as functional groups that activate carbon-carbon double bonds include halogenated vinyls.
  • Examples of compounds having two or more carbonyl groups as functional groups that activate carbon-carbon double bonds include unsaturated polycarboxylic acids, unsaturated polycarboxylic acid esters, anhydrides of unsaturated polycarboxylic acids, Examples include N-substituted maleimides, methylene malonic acid esters, and the like.
  • Compounds having one cyano group and one carbonyl group as functional groups that activate carbon-carbon double bonds include 2-cyanoacrylates.
  • the radically polymerizable compound (C) may be appropriately selected according to the purpose and application.
  • Compounds having a (meth)acryloyl group, compounds having a 2-(meth)allyloxymethylacryloyl group other than the cyclization-polymerizable carboxylic acid compound (A), N-vinylamides, (meth)acrylonitrile, aromatic vinyls , vinyl ethers, and vinyl esters are preferable, and these may be monofunctional radically polymerizable monomers that are compounds having one radically polymerizable group in the same molecule, and two or more radically polymerizable groups in the same molecule. It may be a polyfunctional radically polymerizable compound that is a compound having These can use 1 type(s) or 2 or more types.
  • the radically polymerizable compound (C ) is more preferably 1000 mPa ⁇ s or less, still more preferably 500 mPa ⁇ s or less, and most preferably 200 mPa ⁇ s or less.
  • the content of the radically polymerizable compound (C) may be appropriately selected according to the purpose and application. It is preferably 1 to 3000 parts by mass, more preferably 2 to 2000 parts by mass, still more preferably 3 to 1000 parts by mass, most preferably 4 to 700 parts by mass with respect to 100 parts by mass of the system compound (A) is.
  • the monofunctional radically polymerizable compound is a compound having one radically polymerizable group in the same molecule, and the radically polymerizable group is preferably a carbon-carbon double bond, more preferably a carbon-carbon double bond. It is a carbon-carbon double bond that is adjacent to the functional group to be modified.
  • specific compound groups include compounds having a (meth)acryloyl group and compounds having a 2-(meth)allyloxymethylacryloyl group (excluding the cyclization-polymerizable carboxylic acid compound (A). ), N-vinylamides, (meth)acrylonitrile, aromatic vinyls, vinyl ethers, and vinyl esters are preferred, but the present disclosure is not limited to only such examples.
  • (meth)acrylic esters include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, n-amyl (meth)acrylate, sec-amyl (meth)acrylate, tert-amyl (meth)acrylate, (meth)acrylic acid n-hexyl, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, tridecyl (meth)acrylate, cyclohexyl (meth)acrylate, cyclohexylmethyl (meth)acrylate, octyl (meth)acrylate, ( Lauryl (meth)acrylate, Stearyl (meth)acrylate, Benz
  • (Meth)acrylamides include, for example, N,N-dimethyl(meth)acrylamide, N-methylol(meth)acrylamide, acryloylmorpholine and the like, but the present disclosure is not limited to such examples. These (meth)acrylamides may be used alone or in combination of two or more.
  • 2-(meth)allyloxymethyl acrylic esters examples include methyl 2-(meth)allyloxymethyl acrylate, ethyl 2-(meth)allyloxymethyl acrylate, and 2-(meth)allyloxymethyl acrylic acid.
  • N-vinylamides examples include N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylformamide, N-vinylacetamide, etc., but the present disclosure is not limited to such examples. Each of these N-vinylamides may be used alone, or two or more of them may be used in combination.
  • aromatic vinyls examples include styrene, ⁇ -methylstyrene, vinyltoluene, methoxystyrene, N-vinylimidazole, cinnamic acid, vinylbenzoic acid, etc., but the present disclosure is limited only to such examples. not something. These aromatic vinyls may be used alone or in combination of two or more.
  • vinyl ethers examples include methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, methoxyethoxyethyl vinyl ether, methoxypolyethylene.
  • examples include glycol vinyl ether, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, etc., but the present disclosure is not limited to such examples only. These vinyl ethers may be used alone or in combination of two or more.
  • Vinyl esters include, for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, etc., but the present disclosure is not limited to such examples. These vinyl esters may be used alone or in combination of two or more.
  • Conjugated dienes include, for example, 1,3-butadiene, isoprene, chloroprene, and the like, but the present disclosure is not limited to such examples. These conjugated dienes may be used alone or in combination of two or more.
  • Examples of unsaturated polycarboxylic acids, unsaturated polycarboxylic acid esters, and anhydrides of unsaturated polycarboxylic acids include maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, their alkyl esters, and anhydrides. and the like, but the present disclosure is not limited only to such examples.
  • These unsaturated polyvalent carboxylic acid esters and unsaturated polyvalent carboxylic acid anhydrides may be used alone, or two or more of them may be used in combination.
  • N-substituted maleimides examples include methylmaleimide, ethylmaleimide, isopropylmaleimide, cyclohexylmaleimide, phenylmaleimide, benzylmaleimide, naphthylmaleimide, etc., but the present disclosure is not limited to such examples.
  • Each of these N-substituted maleimides may be used alone, or two or more of them may be used in combination.
  • a polyfunctional radically polymerizable compound is a compound having two or more radically polymerizable groups in the same molecule.
  • the radically polymerizable group is preferably a carbon-carbon double bond, more preferably a carbon-carbon double bond flanked by a functional group that activates the carbon-carbon double bond.
  • specific compound groups include compounds having a (meth)acryloyl group and compounds having a 2-(meth)allyloxymethylacryloyl group (excluding the cyclization-polymerizable carboxylic acid compound (A). ), N-vinylamides, (meth)acrylonitrile, aromatic vinyls, vinyl ethers, and vinyl esters are preferred, but the present disclosure is not limited to only such examples.
  • Examples of general-purpose polyfunctional radically polymerizable compounds include polyfunctional (meth)acrylic acid esters, vinyl ether group-containing (meth)acrylic acid esters, allyl group-containing (meth)acrylic acid esters, polyfunctional (meth)acryloyl group-containing Polyfunctional (meth)acrylic compounds such as isocyanurate and polyfunctional urethane (meth)acrylate; Polyfunctional 2-(meth)allyloxymethyl acrylate; Multifunctional maleimide compounds; Multifunctional vinyl ethers; Polyfunctional allyl compounds and polyfunctional aromatic vinyls, but the present disclosure is not limited to such examples. These polyfunctional radically polymerizable compounds may be used alone or in combination of two or more.
  • Polyfunctional (meth)acrylic esters include, for example, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butylene glycol di(meth) Acrylates, hexanediol di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, bisphenol A alkylene oxide di(meth)acrylate, bisphenol F alkylene oxide di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylol Propane tetra(meth)acrylate, glycerin tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethylene oxide added tri
  • Vinyl ether group-containing (meth)acrylic esters include, for example, 2-vinyloxyethyl (meth)acrylate, 3-vinyloxypropyl (meth)acrylate, 1-methyl-2-vinyloxyethyl (meth)acrylate, (meth)acrylate, 2-vinyloxypropyl acrylate, 4-vinyloxybutyl (meth)acrylate, 4-vinyloxycyclohexyl (meth)acrylate, 5-vinyloxypentyl (meth)acrylate, 6-vinyloxyhexyl (meth)acrylate, 4-vinyloxymethylcyclohexylmethyl (meth)acrylate, p-vinyloxymethylphenylmethyl (meth)acrylate, 2-(vinyloxyethoxy)ethyl (meth)acrylate, 2-(vinyloxy)acrylate (meth) ethoxyethoxyethoxy)ethyl and the like, but the present disclosure is not limited only to
  • vinyl ether group-containing (meth)acrylic acid esters may be used alone or in combination of two or more.
  • allyl group-containing (meth)acrylic acid esters include allyl (meth)acrylate and the like, but the present disclosure is not limited to such examples.
  • Polyfunctional (meth)acryloyl group-containing isocyanurates include, for example, tri(acryloyloxyethyl) isocyanurate, tri(methacryloyloxyethyl) isocyanurate, alkylene oxide-added tri(acryloyloxyethyl) isocyanurate, alkylene oxide-added tri( methacryloyloxyethyl)isocyanurate, etc., but the present disclosure is not limited to such examples only.
  • These polyfunctional (meth)acryloyl group-containing isocyanurates may be used alone or in combination of two or more.
  • polyfunctional urethane (meth)acrylates examples include polyfunctional isocyanates such as tolylene diisocyanate, isophorone diisocyanate, and xylylene diisocyanate, and hydroxyl groups such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate.
  • polyfunctional urethane (meth)acrylate obtained by reaction with contained (meth)acrylic acid ester may be mentioned, but the present disclosure is not limited only to such examples.
  • polyfunctional 2-(meth)allyloxymethyl acrylates examples include polyfunctional 2-(meth)allyloxymethyl acrylates described in Japanese Patent No. 05689628, and the like. The examples are not intended to be limiting. Each of these polyfunctional 2-(meth)allyloxymethyl acrylates may be used alone, or two or more of them may be used in combination.
  • Polyfunctional maleimide compounds include, for example, 4,4′-diphenylmethanebismaleimide, m-phenylenebismaleimide, bisphenol A diphenyletherbismaleimide, 3,3′-dimethyl-5,5′-diethyl-4,4′- diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, 1,6-bismaleimido-(2,2,4-trimethyl)hexane, phenylmethanemaleimide oligomers, and the like, although the present disclosure provides such examples. is not limited to only These polyfunctional maleimide compounds may be used alone or in combination of two or more.
  • Polyfunctional vinyl ethers include, for example, ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether, bisphenol F alkylene oxide divinyl ether.
  • trimethylolpropane trivinyl ether trimethylolpropane trivinyl ether, ditrimethylolpropane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether, ethylene oxide-added trimethylolpropane trivinyl ether, ethylene oxide-added ditrimethylolpropane tetravinyl ether, Examples include ethylene oxide-added pentaerythritol tetravinyl ether, ethylene oxide-added dipentaerythritol hexavinyl ether, and the like, but the present disclosure is not limited only to such examples.
  • These polyfunctional vinyl ethers may be used alone or in combination of two or more.
  • Polyfunctional allyl compounds include, for example, ethylene glycol diallyl ether, diethylene glycol diallyl ether, polyethylene glycol diallyl ether, propylene glycol diallyl ether, butylene glycol diallyl ether, hexanediol diallyl ether, bisphenol A alkylene oxide diallyl ether, bisphenol F alkylene oxide.
  • diallyl ether trimethylolpropane triallyl ether, ditrimethylolpropane tetraallyl ether, glycerin triallyl ether, pentaerythritol tetraallyl ether, dipentaerythritol pentaallyl ether, dipentaerythritol hexaallyl ether, ethylene oxide-added trimethylolpropane triallyl ether , ethylene oxide-added ditrimethylolpropane tetraallyl ether, ethylene oxide-added pentaerythritol tetraallyl ether, ethylene oxide-added dipentaerythritol hexaallyl ether and other polyfunctional allyl ethers; polyfunctional allyl group-containing isocyanurates such as triallyl isocyanurate; diallyl phthalate , polyfunctional allyl esters such as diallyl diphenate; bisallyl na
  • Polyfunctional aromatic vinyls include, for example, divinylbenzene and the like, but the present disclosure is not limited to such examples.
  • the polyfunctional radically polymerizable compound may be an oligomer or polymer in which the backbone portion other than the radically polymerizable group has repeating units based on monomers.
  • the molecular weight of the polyfunctional radical polymerizable compound is less than 1000, it can be classified as an oligomer, and when the molecular weight is 1000 or more, it can be classified as a polymer.
  • Examples of the oligomer or polymer skeleton of the multifunctional radically polymerizable compound include polyester skeletons, polyether skeletons, polyurethane skeletons, conjugated diene polymer skeletons such as polybutadiene and polyisoprene, poly(meth)acrylate skeletons, Examples include a phenol resin skeleton, an aniline resin skeleton, a polyolefin skeleton, a polyamide skeleton, a cycloolefin polymer skeleton, and a polysiloxane skeleton, but the present disclosure is not limited to these examples.
  • a polyester skeleton, a polyether skeleton, a polyurethane skeleton, a conjugated diene polymer skeleton, a poly(meth)acrylate skeleton, a phenolic resin skeleton and an aniline resin skeleton are preferred.
  • the skeleton portion and the radically polymerizable group may be bonded by a covalent bond, but are preferably bonded via an ester bond and/or a urethane bond.
  • oligomers or polymers of polyfunctional radically polymerizable compounds include urethane (meth)acrylate polymerizable oligomers in which (meth)acryloyl groups are bonded to the skeleton via urethane bonds, and (meth)acryloyl groups as the skeleton.
  • Polyfunctional radically polymerizable compounds are readily commercially available.
  • Commercially readily available polyfunctional radically polymerizable compounds include, for example, products manufactured by Kyoeisha Chemical Co., Ltd., trade names: Light Acrylate 3EG-A, Light Acrylate 4EG-A, Light Acrylate 9EG-A, Light Acrylate 14EG-A, light acrylate NP-A, light acrylate 1,6-HX-A, light acrylate 1,9ND-A, light acrylate DCP-A, light acrylate BP-4EA, light acrylate BP-4PA, light acrylate TMP -A, light acrylate TMP-3EO-A, light acrylate TMP-6EO-3A, light acrylate PE-3A, light acrylate PE-4A, light acrylate DPE-6A, light acrylate BA-134, light acrylate HPP-A, light Acrylate PTMGA-250, Light acrylate DTMP-4A, Light ester EG, Light ester 2EG,
  • Aronix M-208 trade names: Aronix M-208, Aronix M-211B, Aronix M-215, Aronix M-220, Aronix M-225, Aronix M-270, Aronix M-240, Aronix M-309, Aronix M-310, Aronix M-321, Aronix M-350, Aronix M-360, Aronix M-313, Aronix M-315, Aronix M-306, Aronix M-305, Aronix M-303, Aronix M-452, Aronix M-450, Aronix M-408, Aronix M-403, Aronix M-400, Aronix M-402, Aronix M-404, Aronix M-406, Aronix M-405, Aronix M-460, Aronix M-510, Aronix M-520, Aronix M-1100, Aronix M-1200, Aronix M-6100, Aronix M-6200, Aronix M-6250, Aronix M-6500, A
  • the polymerizable composition of the present disclosure can contain ingredients other than Such components include radical polymerization inhibitors, radical polymerization initiators, compounds having reactive groups other than radical polymerizability, organic solvents, thermoplastic resins, organic or inorganic fine particles, fillers, quantum dots, dyes, and pigments.
  • the polymerizable composition of the present disclosure contains a primary antioxidant and/or excess A suitable amount of a secondary antioxidant having oxide-decomposability may be used.
  • Primary antioxidants include, for example, hydroquinones, benzoquinones, phenols, aromatic amines, phenothiazines, dithiocarbamate metal salts, nitroso compounds, etc., but the present disclosure is limited only to such examples. not something.
  • secondary antioxidants include phosphorus compounds such as phosphine and phosphite, sulfur compounds such as thioether, mercaptobenzimidazole, and thiourea, but the present disclosure is limited only to such examples. isn't it. Although the primary antioxidant and the secondary antioxidant may be used alone, it is more preferable to use them together.
  • phenols are preferred from the viewpoint of suppressing coloring
  • thioethers are preferred from the viewpoint of acid resistance and hydrolysis resistance.
  • Phenols include, for example, monoetherified hydroquinones, hindered phenols and their multimers (including dimers) or multimer derivatives, semi-hindered phenols and their multimers (including dimers) or derivatives of multimers, etc., but the present disclosure is not limited only to such examples. These phenols may be used alone or in combination of two or more.
  • Monoetherified hydroquinones include, for example, hydroquinone monomethyl ether, hydroquinone mono n-butyl ether, hydroquinone monobenzyl ether, hydroquinone monocyclohexyl ether, 4-methoxy-1-naphthol, etc., but the present disclosure provides only such examples. is not limited to These mono-etherified hydroquinones may be used alone or in combination of two or more.
  • hindered phenols examples include 2,6-bis(tert-butyl)-4-methylphenol, octadecyl-3-(3,5-ditert-butyl-4-hydroxyphenyl)propionate, isooctyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylanilino)-1,3, 5-triazine, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate-diethyl ester and the like, but the present disclosure is not limited to only such exemplification.
  • Hindered phenol multimers or multimer derivatives include, for example, pentaerythrityl tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,2-thio-diethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamamide), 1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-isocyanurate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene and the like, but the present disclosure is not limited only to such examples. do not have.
  • semi-hindered phenols include 6-tert-butyl-o-cresol, 6-tert-butyl-2,4-xylenol, 2,4,8,10-tetra-tert-butyl-6-[3 -(3-methyl-4-hydroxy-5-t-butylphenyl)propoxy]dibenzo[d,f][1,3,2]dioxaphosphepin, 2,4-dimethyl-6-(1-methyl pentadecyl)phenol, 2,4-bis(octylthiomethyl)-o-cresol, 2,4-bis(dodecylthiomethyl)-o-cresol, 2-tert-butylphenol, 2,4-ditert-butylphenol, 2-tert-amylphenol, 2,4-di-tert-amylphenol, etc., but the present disclosure is not limited to such examples.
  • Semi-hindered phenol multimers or multimer derivatives include, for example, methylenebis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate], triethylene glycol bis[ ⁇ -(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 4,4′-thiobis(2-methyl-6-tert-butylphenol), bis(3-methyl-4-hydroxy-5- tert-butylbenzyl)sulfide, terephthaloyl-di(2,6-dimethyl-4-tert-butyl-3-hydroxybenzylsulfide), 3,9-bis[2-[3-(3-tert-butyl-4-hydroxy -5-methylphenyl)propionic acid]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, 4,4′-butylidenebis(6-tert-but
  • Phosphines include, for example, triethylphosphine, tributylphosphine, tris(2-ethylhexyl)phosphine, triphenylphosphine, and the like, but the present disclosure is not limited to such examples. These phosphines may be used alone or in combination of two or more.
  • phosphites include diethyl hydrogen phosphite, bis(2-ethylhexyl) hydrogen phosphite, dilauryl hydrogen phosphite, dioleyl hydrogen phosphite, diphenyl hydrogen phosphite, triethyl phosphite, tributyl phosphite, tris(2 -ethylhexyl)phosphite, triisodecylphosphite, trilaurylphosphite, tris(tridecylphosphite), trioleylphosphite, tristearylphosphite, phenyldiisodecylphosphite, diphenylmethylphosphite, 2-ethylhexyldiphenylphosphite Phyto, isodecyldiphenylphosphite, tridecyldiphenylphosphi
  • Thioethers include, for example, 2,2′-thiodiglycolic acid, (ethylenedithio)diacetic acid, 2,2′-(ethylenedithio)diethanol, 3,3′-thiodipropionic acid, 3,3′-thio Dimethyl dipropionate, 3-laurylthiopropionic acid, methyl 3-laurylthiopropionate, (3-octylthiopropionic acid) pentaerythritol tetraester, (3-decylthiopropionic acid) pentaerythritol tetraester, (3-lauryl) thiopropionic acid) pentaerythritol tetraester, (3-oleylthiopropionic acid) pentaerythritol tetraester, (3-stearylthiopropionic acid) pentaerythritol tetraester, (3-laurylthiopropionic acid
  • the amount of the radical polymerization inhibitor is determined from the viewpoint of suppressing undesired radical polymerization during various operations such as storage, transportation, composition preparation and treatment, and ensuring the radical polymerizability according to the application. It is preferably 0.005 to 2 parts by mass, more preferably 0.01 to 1 part by mass, and still more preferably 0.02 to 0.5 parts by mass with respect to the total 100 parts by mass.
  • the term "radical polymerizable component” refers to two components of the cyclization polymerizable carboxylic acid compound (A) and the radical polymerizable compound (C).
  • Radical polymerization initiators can be classified into photoradical initiators that generate radicals by irradiation with active energy rays and thermal radical initiators that generate radicals by heating. An initiator and a thermal radical initiator may be used in combination.
  • photoradical initiators include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether; acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy-2 -phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl ]-Acetophenone compounds such as 2-morpholinopropan-1-one; Anthraquinone compounds such as 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-chloroanthraquinone, and 2-amylanthraquinone; 2,4-diethylthioxanthone, 2- Thio
  • organic peroxide initiators and azo initiators are suitable, and specific examples thereof include the following. methyl ethyl ketone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide, methyl acetoacetate peroxide, acetyl acetate peroxide, 1,1-bis(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1- bis(t-hexylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)-2-methylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)cyclododecane, 1,1-bis(t-butylperoxy)butane, 2,2-bis(4 ,4-
  • 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile 1-[(1-cyano-1-methylethyl)azo]formamide, 1,1′-azobis(cyclohexane-1-carbonitrile), 2, 2-azobis(2-methylbutyronitrile), 2,2′-azobisisobutyronitrile, 2,2′-azobis(2,4-dimethylvaleronitrile), 2,2′-azobis(2,4 -dimethyl-4-methoxyvaleronitrile), 2,2′-azobis(2-methylpropionamidine) dihydrochloride, 2,2′-azobis(2-methyl-N-phenylpropionamidine) dihydrochloride, 2,2′ -azobis[N-(4-chlorophenyl)-2-methylpropionamidine]dihydrochloride, 2,2'-azobis[N-(4-hydrophenyl)-2-methylpropionamidine]dihydrochloride, 2,2'- Azobis[
  • the content of the radical polymerization initiator 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.
  • Examples of such compounds include compounds having cationic polymerizable groups such as epoxy groups, oxetanyl groups, and vinyl ether groups; compounds having functional groups that react with carboxyl groups such as epoxy groups, oxazoline groups, carbodiimide groups, and aziridine groups; isocyanates; a compound having a group, a compound having a functional group that reacts with a hydroxyl group such as an amino resin; a compound having a silane coupling group;
  • the content of the compound having a reactive group other than radically polymerizable may be adjusted according to the application and purpose, and may not be contained, but when used, the total amount of the radically polymerizable component is 100 parts by mass. , preferably 1 to 300 parts by mass, more preferably 2 to 200 parts by mass, still more preferably 3 to 100 parts by mass.
  • organic solvent An appropriate amount of an organic solvent may be contained from the viewpoints of adjusting the viscosity, adjusting the thickness of the coating film, and dissolving the resin in the composition.
  • organic solvents include monoalcohols such as methanol, ethanol, isopropanol, n-butanol and sec-butanol; glycols such as ethylene glycol and propylene glycol; cyclic ethers such as tetrahydrofuran and dioxane; Glycol monoethers such as ethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, 3-methoxybutanol; ethylene glycol dimethyl ether , ethylene glycol diethyl ether, ethylene
  • the content of the organic solvent may be adjusted according to the application and purpose, and may not be included. More preferably 2 to 700 parts by mass, still more preferably 3 to 500 parts by mass.
  • the content of other components other than the components described above may be adjusted according to the application and purpose, and may not be included. It is preferably 1 to 300 parts by mass, more preferably 2 to 200 parts by mass, still more preferably 3 to 100 parts by mass.
  • the method for producing a polymerizable composition of the present disclosure includes a step of hydrolyzing 2-allyloxymethyl acrylic acid ester to produce a cyclization polymerizable carboxylic acid compound (A) (hereinafter simply referred to as a hydrolysis step and a step of combining the radically polymerizable compound (C) with the cyclization-polymerizable carboxylic acid compound (A) (hereinafter sometimes simply referred to as a combining step).
  • the hydrolysis step is a step including a step of hydrolyzing the 2-allyloxymethyl acrylate with a strong acid or a medium to strong base, and from the viewpoint of suppressing polymerization during the hydrolysis reaction, hydrolysis with a medium to strong base. method is preferred.
  • the compounding step is a step in which the cyclization polymerizable carboxylic acid compound (A) and the radically polymerizable compound (C) are uniformly mixed in the composition.
  • the hydrolysis step and the compounding step can be performed together or independently. Either the hydrolysis step or the compounding step may be performed first.
  • the method of integrally performing the reaction can be broadly classified into two types, one of which is a method of partially hydrolyzing the 2-allyloxymethyl acrylate. In this case, at least the raw material 2-allyloxymethyl acrylate is included as the radically polymerizable compound (C) together with the cyclization polymerizable carboxylic acid compound (A) produced through hydrolysis.
  • Another is a method including a step of hydrolyzing 2-allyloxymethyl acrylate in the presence of a radically polymerizable compound (C) other than 2-allyloxymethyl acrylate.
  • the radically polymerizable compound (C) a compound that is resistant to structural change under hydrolysis conditions.
  • the independent method means a method of adding the radically polymerizable compound (C) after the hydrolysis step.
  • the hydrolysis step and the composite step are preferably performed integrally from the viewpoint of efficiency, but preferably performed independently from the viewpoint that various compounds can be used as the radically polymerizable compound (C).
  • steps other than the hydrolysis step and the compounding step may be included in order to obtain the desired composition structure.
  • Other steps include, for example, a step of adding a strong acid to convert the salt of 2-allyloxymethylacrylic acid into 2-allyloxymethylacrylic acid (strong acid treatment); A step of cation exchange by adding a strong acid salt of a metal species (metathesis), a step of extracting a cyclization polymerizable carboxylic acid compound (A) with an organic solvent that separates into two layers with water, a water-soluble inorganic salt or Examples include a step of removing by-products by washing with water, a step of distilling off water and organic solvents, and a step of removing polymers, but are not limited to these examples.
  • steps may be performed simultaneously with or after the hydrolysis step, and may be performed before, at the same time, or after the conjugation step. Two or more other steps may be combined, two or more may be performed simultaneously or independently, the order is arbitrary, and the steps may be repeated two or more times.
  • the polymerizable composition of the present disclosure is characterized in that the amount of the ⁇ -oxycarboxylic acid compound (B) is reduced, and the following has a large impact on the reduction of the ⁇ -oxycarboxylic acid compound (B). Describe the process and operation in detail. It also details the steps and operations that have the greatest impact on controlling the formation of undesirable polymer (by-products).
  • ⁇ Hydrolysis step> 2-Allyloxymethyl acrylate can be hydrolyzed with a strong acid or a medium to strong base, but from the viewpoint of suppressing polymerization during hydrolysis, a medium to strong base that exhibits a pH of 9.5 or higher when made into an aqueous solution is used. is preferable, and an inorganic base is preferable from the viewpoint of not bringing in excess organic components. Considering that it can be colorless, the metal content of the inorganic base (may be two or more) is preferably a typical metal element, a metal belonging to Group 3 or Group 4 of the periodic table, and has no toxicity.
  • any one of lithium, sodium, potassium, magnesium, calcium, zinc, and aluminum is more preferable, and considering the solubility and availability of the inorganic base in water, lithium, sodium, and potassium are further preferred. preferable.
  • Specific examples of such inorganic bases include lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, trisodium phosphate, tripotassium phosphate, sodium aluminate, potassium aluminate, and the like.
  • Sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate are particularly preferred in consideration of ease of post-treatment and waste liquid treatment, but are not limited to these examples.
  • 2-allyloxymethyl acrylate ester from the viewpoint of availability and hydrolysis under mild conditions, a lower ester having a small number of carbon atoms is preferable, and an ester of a saturated hydrocarbon having 4 or less carbon atoms is preferable. More preferred are methyl 2-allyloxymethyl acrylate and ethyl 2-allyloxymethyl acrylate.
  • the main reaction is the hydrolysis of the ester moiety, and the important products are the inorganic salt of 2-allyloxymethyl acrylate and alcohol.
  • the main reaction is sodium 2-allyloxymethyl acrylate and methanol is produced. (See the reaction formula below).
  • the main side reactions are the Michael addition of hydroxide ions derived from water or alkoxide ions derived from alcohol generated in the main reaction to the double bond conjugated with the carbonyl group, hydrogen abstraction and elimination, It is speculated that the ⁇ -oxycarboxylic acid compound (B) is produced through hydrolysis of the ester moiety.
  • the main side reactions and by-products are specifically shown below when the 2-allyloxymethyl acrylate is methyl 2-allyloxymethyl acrylate and the inorganic base is sodium hydroxide. Become.
  • Methods for suppressing the Michael addition include using an aqueous solution of a low-concentration inorganic base, lowering the reaction temperature, removing the alcohol produced by hydrolysis of the ester moiety during the reaction out of the reaction system (e.g., by distillation), Hydrolyzing a portion of the 2-allyloxymethyl acrylate using a moderate inorganic base (stopping the reaction, using less than the chemical equivalent of the base, etc.), but examples include It is not limited.
  • These methods for suppressing Michael addition may be performed in combination of two or more, may be performed simultaneously or independently, may be performed in any order, and may be repeated two or more times.
  • Methods (1) to (3) are exemplified below as particularly preferred examples of methods for suppressing Michael addition.
  • a method of combining two or more of the methods (1) to (3) is more preferable.
  • the ⁇ -oxycarboxylic acid compound (B) can be further effectively reduced by combining the methods (1) to (3) with the water washing treatment described below as a purification treatment after hydrolysis.
  • metal hydroxides of Groups 1 and 2 of the periodic table are preferred, among which lithium hydroxide, sodium hydroxide and potassium hydroxide are preferred, and sodium hydroxide and potassium hydroxide are particularly preferred.
  • the concentration of the strong alkaline aqueous solution is preferably 0.1 to 1.6 mmol/g, more preferably 0.2 to 1.3 mmol/g, still more preferably 0.3 to 1.0 mmol/g.
  • the reaction temperature is preferably 0 to 60°C, more preferably 0 to 50°C, even more preferably 0 to 40°C, most preferably 0 to 35°C.
  • the molar ratio of strong alkali/2-allyloxymethyl acrylate used for this purpose is preferably 0.98 to 1.10. , more preferably 0.99 to 1.09, more preferably 1.0 to 1.08.
  • the hydrolysis it is preferable to mix and stir only the medium-strength alkali aqueous solution and 2-allyloxymethyl acrylate without using an organic solvent.
  • 2-allyloxymethyl acrylate to be used, methyl 2-allyloxymethyl acrylate and ethyl 2-allyloxymethyl acrylate are preferable.
  • the concentration of the carbonate aqueous solution is preferably 5 to 30% by mass, more preferably 7 to 25% by mass, and more preferably 9 to 20% by mass.
  • the reaction temperature is preferably 50 to 100°C, more preferably 60 to 95°C, still more preferably 65 to 90°C.
  • the molar ratio of carbonate/2-allyloxymethyl acrylate used for this purpose is preferably 0.8 to 2.0. , more preferably 0.9 to 1.6, more preferably 0.95 to 1.2.
  • the consumption rate of 2-allyloxymethyl acrylate as a starting material is preferably 10 to 80%, more preferably 20 to 70%, still more preferably 30 to 60%.
  • the hydrolysis it is preferable to mix and stir only the inorganic alkali aqueous solution and the 2-allyloxymethyl acrylate without using an organic solvent.
  • the inorganic alkali to be used the aforementioned strong alkali and moderate alkali are preferred.
  • 2-allyloxymethyl acrylate to be used methyl 2-allyloxymethyl acrylate and ethyl 2-allyloxymethyl acrylate are preferable.
  • the amount of the inorganic alkali used is preferably 0.1 to 0.8, more preferably 0.2 to 0.7, and still more preferably 0.3 to 0.3 as the molar ratio of inorganic alkali/2-allyloxymethyl acrylate. 0.6.
  • a high-concentration aqueous solution can be used, preferably 5 to 30% by mass, more preferably 7 to 25% by mass, more preferably 9%. ⁇ 20% by mass.
  • the reaction temperature may be set according to the type of alkali used, and in the case of a strong alkali, it is preferably 0 to 60°C, more preferably 0 to 50°C, still more preferably 0 to 40°C, and most preferably 0. ⁇ 35°C.
  • the temperature is preferably 50 to 100°C, more preferably 60 to 95°C, still more preferably 65 to 90°C.
  • a polymer When hydrolyzing 2-allyloxymethyl acrylate, especially when the reaction is carried out under heating or under reduced pressure, a polymer may be generated by a radical polymerization mechanism.
  • a method for suppressing it there is a method of hydrolyzing with the addition of the above-described primary antioxidant and/or secondary antioxidant. Phenols are preferred among the primary antioxidants, and thioethers are preferred among the secondary antioxidants, from the viewpoints of easily exhibiting the effect of inhibiting polymerization even under hydrolysis conditions and preventing coloration.
  • the purification treatment after hydrolysis is preferably carried out after all the carboxylates present in the reaction system are treated with a strong acid to convert them to carboxylic acids, or after the metathesis treatment described later.
  • Specific reduction operations include distillation and removal of the aqueous layer containing the ⁇ -oxycarboxylic acid compound (B) (water washing treatment).
  • a water washing treatment is preferable from the viewpoint of suppressing the generation of a polymer by a radical polymerization mechanism.
  • the strong acid treatment is a treatment of carboxylating a carboxylate by adding an acid stronger than the carboxylic acid.
  • Such acids include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid; organic acids such as methanesulfonic acid, p-toluenesulfonic acid and trifluoroacetic acid; but are limited to such examples. isn't it.
  • Hydrochloric acid and sulfuric acid are preferred from the viewpoints of water solubility of salts produced by strong acid treatment and ease of waste water treatment.
  • the strong acid and the carboxylate either one may be excessive or equivalent, and may be appropriately selected according to the purpose.
  • the strong acid treatment generates 2-allyloxymethyl acrylic acid in an amount corresponding to the added strong acid, but in the presence of a radical polymerization inhibitor, a polymer may be generated even if the treatment is performed at a low temperature. It is presumed that the strong acid serves as an initiator or a catalyst, and 2-allyloxymethylacrylic acid is polymerized by a cationic polymerization mechanism. Methods for suppressing the generation of such polymers include, for example, reducing the concentration of the strong acid to be added, adding the strong acid slowly over time, and the like.
  • 2-allyloxymethylacrylic acid itself is relatively lipophilic and separates into two layers when mixed with water. It often separates into two layers, a water layer containing mainly.
  • an organic layer mainly containing 2-allyloxymethylacrylic acid and an aqueous layer By removing the water layer, the ⁇ -oxycarboxylic acid compound (B) can be reduced. This corresponds to the water washing process described above. From the viewpoint of efficient two-layer separation, it is preferable to use water and an organic liquid that separates into two layers in combination. may be added after adding Such an organic liquid may be an organic solvent or a radically polymerizable compound (C) that separates into two layers with water, and the amount used may be appropriately selected according to the purpose.
  • the washing treatment may be repeated. That is, after washing water is added to the organic layer containing the extracted 2-allyloxymethylacrylic acid and stirred, the two layers are separated by standing still, and the aqueous layer is discarded to obtain a ⁇ -oxycarboxylic acid compound ( B) can be removed more.
  • the washing water may consist only of water, or may contain additives. Examples of additives include water-soluble inorganic salts (sodium sulfate, potassium sulfate, sodium chloride, potassium chloride, etc.) for increasing the specific gravity of the aqueous layer, but are not limited to these examples. Such water washing treatment may be performed twice or more.
  • the metathesis treatment is a treatment in which a strong acid salt of another metal species is added to an aqueous solution of a salt of 2-allyloxymethylacrylic acid to exchange cations.
  • a strong acid salt of another metal species is added to an aqueous solution of a salt of 2-allyloxymethylacrylic acid to exchange cations.
  • an aqueous solution of the salt of 2-allyloxymethylacrylic acid before the metathesis treatment an aqueous solution of an alkali metal salt is preferable, and sodium salt and potassium salt are particularly preferable.
  • an inorganic salt of a polyvalent ion of a metal or metal oxide and a strong inorganic acid is preferable from the viewpoint of efficient cation exchange.
  • metals or metal oxides constituting such inorganic salts include metals or metal oxides belonging to groups 2 to 15 of the periodic table. Metals or metal oxides belonging to Groups 12, 13, 14 and 15 are preferred, and magnesium, calcium, zirconium oxide, zinc and aluminum are preferred in consideration of toxicity and availability.
  • Preferred examples of the strong acid that constitutes the inorganic salt include hydrochloric acid, sulfuric acid, and nitric acid.
  • Salts of metals or metal oxides belonging to groups 2 to 15 of the periodic table and 2-allyloxymethylacrylic acid have relatively high lipophilicity. In some cases, it is separated into two layers, an organic layer mainly containing a metal or metal oxide belonging to Table 2 to 15 and a salt of 2-allyloxymethylacrylic acid, and an aqueous layer mainly containing an alkali metal salt of a strong acid. many.
  • an organic layer mainly containing a metal or metal oxide belonging to Table 2 to 15 and a salt of 2-allyloxymethylacrylic acid and an aqueous layer mainly containing an alkali metal salt of a strong acid.
  • metals or metal oxides belonging to groups 2 to 15 of the periodic table and salts of 2-allyloxymethyl acrylic acid are mainly used.
  • the aqueous layer can be removed to reduce the ⁇ -oxycarboxylic acid compound (B). This corresponds to the water washing process described above.
  • the organic liquid that separates into two layers with water may be an organic solvent or radically polymerizable compound (C) that separates into two layers with water, and the amount used may be appropriately selected according to the purpose.
  • C radically polymerizable compound
  • styrene is added to an aqueous solution of sodium 2-allyloxymethylacrylate and then zinc sulfate is added, zinc 2-allyloxymethylacrylate is mainly obtained as the cyclization-polymerizable carboxylic acid compound (A).
  • the washing treatment may be repeated. That is, washing water is further added to the extracted organic layer containing a metal or metal oxide belonging to groups 2 to 15 of the periodic table or a salt of 2-allyloxymethylacrylic acid, and the mixture is stirred, and then allowed to stand to separate into two layers. ⁇ -hydroxycarboxylic acid compound (B) can be further reduced by removing the aqueous layer.
  • the washing water may consist only of water, or may contain additives. Examples of additives include water-soluble inorganic salts (sodium sulfate, potassium sulfate, sodium chloride, potassium chloride, etc.) for increasing the specific gravity of the aqueous layer, but are not limited to these examples. Such water washing treatment may be performed twice or more.
  • water and the organic solvent may be distilled off from the mixture containing the cyclization-polymerizable carboxylic acid compound (A) and water and/or the organic solvent by heating and/or reducing the pressure.
  • a polymer may be generated by a radical polymerization mechanism.
  • a method of suppressing it there is a method of adding the primary antioxidant and/or secondary antioxidant described above. Phenols are preferred among the primary antioxidants, and thioethers are preferred among the secondary antioxidants, from the viewpoints that the polymerization inhibitory effect can be easily exhibited even in an aqueous system and that coloring is difficult to occur.
  • polymer When water or solvent is distilled off from a mixture containing a large amount of 2-allyloxymethyl acrylic acid, polymer may be generated even if a radical polymerization inhibitor is added, but it is assumed that this is due to the cationic polymerization mechanism. are doing.
  • a method for suppressing the generation of such a polymer a method in which a carboxylate is allowed to coexist is preferable, and 2-allyloxymethyl acrylate is particularly preferable.
  • the amount of carboxylate to be added is preferably 1% by mass or more, more preferably 3% by mass or more, and still more preferably 5% by mass or more relative to 2-allyloxymethylacrylic acid.
  • Polymerization may occur during various processes and operations. Polymers tend to be water-soluble when they contain many carboxylate-type structures, but tend to be poorly soluble in water and in organic solvents other than alcohols when they contain many carboxylic acid-type structures. Therefore, the generated polymer can be removed by filtering or centrifuging after making the polymer contain a large amount of carboxylic acid structure. Filtration is preferable from the viewpoint that it can be performed with a simple apparatus, and if a filter aid or an adsorbent is used in combination, work efficiency can be improved.
  • the present disclosure is also a polymer obtained by polymerizing the polymerizable composition of the present disclosure under radical generation conditions.
  • the method of generating radicals includes a method of heating the polymerizable composition of the present disclosure and/or a method of irradiating the polymerizable composition of the present disclosure with active energy rays. Heating or irradiation with active energy rays may be performed in one step or in two or more steps. Heating and irradiation with active energy rays may be combined, combined simultaneously, or separately.
  • the polymerizable composition of the present disclosure is more preferably in a state containing the aforementioned radical polymerization initiator.
  • the heating temperature may be appropriately selected according to the presence or absence, type, content, and application of the radical polymerization initiator. °C or higher.
  • the active energy ray one commonly used can be used, and examples thereof include electromagnetic waves such as gamma rays, X-rays, ultraviolet rays, visible rays, and infrared rays, and particle beams such as electron beams, neutron beams, and proton beams. .
  • electromagnetic waves such as gamma rays, X-rays, ultraviolet rays, visible rays, and infrared rays
  • particle beams such as electron beams, neutron beams, and proton beams.
  • gamma rays, X-rays, ultraviolet rays, visible rays, and electron beams are preferable, ultraviolet rays, visible rays, and electron beams are more preferable, and ultraviolet rays are most preferable, in terms of energy intensity, energy ray generator, and the like. .
  • active energy rays with high energy such as gamma rays, X-rays, and electron beams. Active energy rays, which are relatively weak but are easy to generate and economical, can be preferably used.
  • the polymerizable composition of the present disclosure has good radical polymerizability as described above, it can be Lenses, molding materials, various types of three-dimensional modeling (inkjet, SLA, DLP), optical film intermediate layers, negative resist resins, water-absorbing resins, quantum dot ink compositions, EUV resist compositions, materials for electronic parts (Prepregs, adhesives for electrical materials, adhesives for electrical materials, etc.), fiber treatment agents, compositions for surface treatment agents, etc., can be suitably used for various applications in which radical polymerization is performed by heating or irradiation with active energy rays. .
  • Preparation of standard sample After dissolving sodium propionate and the substance to be quantified (sodium salt of carboxylate ion) in heavy water and quantifying the molar ratio by 1 H-NMR, further dilute with ultrapure water to create a calibration curve. It was used as a standard sample for Preparation of measurement sample: A sodium propionate aqueous solution and a test sample were weighed and diluted with a 1% sodium bicarbonate aqueous solution and ultrapure water to obtain a measurement sample.
  • Example 1 5.0 g of methyl 2-allyloxymethyl acrylate (containing 0.03% of p-methoxyphenol and 0.06% of dimethyl 3,3′-thiodipropionate) was placed in a 50 ml round-bottomed flask containing a stirrer, 32.0 g of 4% sodium hydroxide aqueous solution (equivalent to methyl 2-allyloxymethyl acrylate used) was added and stirred at room temperature for 1 hour. The mixture was heated while bubbling an oxygen/nitrogen mixed gas (oxygen concentration 7%), and when the internal temperature reached 60°C, the pressure was gradually reduced to distill off water and low-boiling components.
  • an oxygen/nitrogen mixed gas oxygen concentration 7%
  • the aqueous layer (lower layer) was discarded, 9.0 g of the organic layer was taken out, and the comparative polymerizable composition (1) (2-allyl A styrene solution containing oxymethyl acrylic acid) was obtained.
  • the polymerizable composition was analyzed with a capillary electrophoresis system, and the amounts of partial structure (1) and partial structures (2) to (4) were measured as carboxylate ions. Table 1 shows the results.
  • the aqueous layer (lower layer) was discarded, 9.0 g of the organic layer was taken out, and the comparative polymerizable composition (2) (2-allyl A styrene solution containing oxymethyl acrylic acid) was obtained.
  • the polymerizable composition was analyzed with a capillary electrophoresis system, and the amounts of partial structure (1) (a1) and partial structures (2)-(4) (b1-b6) were measured as carboxylate ions. Table 1 shows the results.
  • Example 2 A stirrer was placed in a 100 ml eggplant flask, and a cooling tube and a distillation receiver were connected to the eggplant flask via a thermometer, a gas inlet tube, and a trellis tube to form a reactor. 2.9 g of potassium hydroxide, 7.1 g of potassium carbonate, and 60.0 g of ultrapure water were placed in an eggplant flask and stirred to form a uniform solution.
  • polymerizable composition (2) (methyl acrylate solution containing 2-allyloxymethyl acrylic acid) of the present disclosure.
  • the polymerizable composition was analyzed with a capillary electrophoresis system, and the amounts of partial structure (1) and partial structures (2) to (4) were measured as carboxylate ions. Table 1 shows the results.
  • Example 3 5.0 g of methyl 2-allyloxymethyl acrylate (containing 0.03% of p-methoxyphenol and 0.06% of dimethyl 3,3'-thiodipropionate) was placed in a 50 ml eggplant-shaped flask equipped with a stirrer, 32.0 g of 4% sodium hydroxide aqueous solution (equivalent to methyl 2-allyloxymethyl acrylate used) was added and stirred at room temperature for 1 hour. The mixture was heated while bubbling an oxygen/nitrogen mixed gas (oxygen concentration 7%), and when the internal temperature reached 60°C, the pressure was gradually reduced to distill off water and low-boiling components.
  • oxygen/nitrogen mixed gas oxygen concentration 7%
  • polymerizable composition (3) (methyl acrylate solution containing 2-allyloxymethyl acrylic acid) of the present disclosure.
  • the polymerizable composition was analyzed with a capillary electrophoresis system, and the amounts of partial structure (1) and partial structures (2) to (4) were measured as carboxylate ions. Table 1 shows the results.
  • Example 4 5.0 g of methyl 2-allyloxymethyl acrylate (containing 0.03% of p-methoxyphenol and 0.06% of dimethyl 3,3'-thiodipropionate) was placed in a 50 ml eggplant-shaped flask equipped with a stirrer, 6.4 g of 10% aqueous sodium hydroxide solution (0.5 equivalents relative to methyl 2-allyloxymethyl acrylate used) was added and stirred at room temperature for 1 hour. After 2.3 g of zinc sulfate heptahydrate was added and stirring was continued for 30 minutes, the stirring was stopped and the contents were transferred to a separatory funnel and allowed to stand for 30 minutes.
  • the aqueous layer (lower layer) was discarded, 5.0 g of the organic layer was taken, and the polymerizable composition (4) of the present disclosure (2- containing zinc 2-allyloxymethylacrylate and sodium 2-allyloxymethylacrylate) Allyloxymethyl acrylate solution) was obtained.
  • the polymerizable composition was analyzed with a capillary electrophoresis system, and the amounts of partial structure (1) and partial structures (2) to (4) were measured as carboxylate ions. Zinc and sodium were also quantified. Table 1 shows the results.
  • Example 5 4.0 g of the polymerizable composition (2) obtained in Example 2, 6.0 g of ethanol, and 0.04 g of 2,2′-azobis(2,4-dimethylvaleronitrile) were placed in a 50 ml test tube containing a stirring bar. was added and heating was started while stirring. After stirring for 4 hours while adjusting the heating so that the internal temperature was 66° C. ⁇ 1° C., the mixture was cooled to room temperature. After the content was mixed with 30 g of tetrahydrofuran, it was added dropwise to 100 g of n-hexane while stirring. After continuing stirring for 30 minutes, the precipitate was taken out by decantation.
  • the precipitate was placed in a 50 ml eggplant flask (precisely weighed) and vacuum-dried at 80° C. for 1 hour to obtain a polymer.
  • the weight of the resulting polymer was accurately weighed together with the eggplant flask, and the yield of the polymer relative to the weight of the charged polymerizable composition was calculated to be 95.9%. Further, the weight-average molecular weight of the reprecipitated polymer was measured by the APC system and found to be 50,000.
  • Example 6 A polymer was obtained in the same manner as in Example 5 except that the polymerizable composition obtained in Example 3 was used as the polymerizable composition. The yield was 92.9% and the weight average molecular weight was 46,000.
  • Comparative Example 4 A polymer was obtained in the same manner as in Example 5 except that the polymerizable composition obtained in Comparative Example 3 was used as the polymerizable composition. The yield was 75.9% and the weight average molecular weight was 32,000.
  • Example 7 3.0 g of the polymerizable composition obtained in Example 4, 0.09 g of 1-hydroxycyclohexylphenyl ketone, and 0.09 g of 1-[4-(2-hydroxyethoxyl)-phenyl]-2-hydroxy-methylpropanone were The mixture was mixed and stirred to obtain a uniform solution. Bar coater no. 2, the resulting liquid was applied to a cycloolefin polymer film (Zeonor (registered trademark) 1410R/Nippon Zeon Co., Ltd. made into a 100 ⁇ m thick film by a small press), and then applied by a belt conveyor.
  • a cycloolefin polymer film Zeonor (registered trademark) 1410R/Nippon Zeon Co., Ltd. made into a 100 ⁇ m thick film by a small press
  • Example 8 An isobornyl acrylate solution containing 2-allyloxymethyl acrylic acid was obtained in the same manner as in Example 3, except that 8.0 g of isobornyl acrylate was used instead of 3.0 g of methyl acrylate. Next, 0.86 g of zinc oxide powder was added and stirred at 60° C. for about 3 hours until the mixture became transparent. After confirming that it became transparent, 1.56 g of N,N'-bis(2-hydroxyethyl)ethylenediamine was added and stirred for about 30 minutes until it became transparent to obtain 2-allyloxymethyl acrylic acid.
  • the polymerizable composition of the present invention is hydrophilic, water-soluble, and has a partial structure (2) to (4) that adversely affects radical polymerization. It became clear that the content of (B) could be reduced.
  • the polymerizable composition of the present disclosure is compared with a polymerizable composition containing a large amount of ⁇ -oxycarboxylic acid-based compound (B) having partial structures (2) to (4). Furthermore, the results of Examples 7 and 8 revealed that the polymerizable composition of the present disclosure has good UV curability.

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WO2026014333A1 (ja) * 2024-07-09 2026-01-15 株式会社日本触媒 重合性組成物、及び、α－アリルオキシメチルアクリロイル基を有する重合性エステル化合物の製造方法

Citations (4)

* Cited by examiner, † Cited by third party
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JP2013216737A (ja) * 2012-04-05 2013-10-24 Nippon Shokubai Co Ltd 重合性組成物
JP2013231164A (ja) * 2012-04-05 2013-11-14 Nippon Shokubai Co Ltd 水系組成物
JP2020050832A (ja) * 2018-09-28 2020-04-02 株式会社日本触媒 変性樹脂の製造方法
JP2021024795A (ja) * 2019-08-02 2021-02-22 株式会社日本触媒 ２−（（メタ）アリルオキシメチル）アクリル酸アルカリ金属塩粉体

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013216737A (ja) * 2012-04-05 2013-10-24 Nippon Shokubai Co Ltd 重合性組成物
JP2013231164A (ja) * 2012-04-05 2013-11-14 Nippon Shokubai Co Ltd 水系組成物
JP2020050832A (ja) * 2018-09-28 2020-04-02 株式会社日本触媒 変性樹脂の製造方法
JP2021024795A (ja) * 2019-08-02 2021-02-22 株式会社日本触媒 ２−（（メタ）アリルオキシメチル）アクリル酸アルカリ金属塩粉体

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2026014333A1 (ja) * 2024-07-09 2026-01-15 株式会社日本触媒 重合性組成物、及び、α－アリルオキシメチルアクリロイル基を有する重合性エステル化合物の製造方法

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