WO2022244835A1 - 単量体組成物、メタクリル系樹脂組成物及び樹脂成形体 - Google Patents
単量体組成物、メタクリル系樹脂組成物及び樹脂成形体 Download PDFInfo
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- WO2022244835A1 WO2022244835A1 PCT/JP2022/020784 JP2022020784W WO2022244835A1 WO 2022244835 A1 WO2022244835 A1 WO 2022244835A1 JP 2022020784 W JP2022020784 W JP 2022020784W WO 2022244835 A1 WO2022244835 A1 WO 2022244835A1
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- Prior art keywords
- methyl
- mass
- resin composition
- methacrylic resin
- methacrylic
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 263
- 239000000178 monomer Substances 0.000 title claims abstract description 119
- 239000000113 methacrylic resin Substances 0.000 title claims description 128
- 239000011347 resin Substances 0.000 title claims description 56
- 229920005989 resin Polymers 0.000 title claims description 56
- OCWLYWIFNDCWRZ-UHFFFAOYSA-N Methyl (S)-2-Methylbutanoate Chemical compound CCC(C)C(=O)OC OCWLYWIFNDCWRZ-UHFFFAOYSA-N 0.000 claims abstract description 141
- 150000001875 compounds Chemical class 0.000 claims abstract description 67
- 229920000642 polymer Polymers 0.000 claims description 77
- CWKLZLBVOJRSOM-UHFFFAOYSA-N methyl pyruvate Chemical compound COC(=O)C(C)=O CWKLZLBVOJRSOM-UHFFFAOYSA-N 0.000 claims description 71
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 70
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 51
- BHIWKHZACMWKOJ-UHFFFAOYSA-N methyl isobutyrate Chemical compound COC(=O)C(C)C BHIWKHZACMWKOJ-UHFFFAOYSA-N 0.000 claims description 40
- 238000000465 moulding Methods 0.000 claims description 30
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- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 21
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 claims description 20
- WDAXFOBOLVPGLV-UHFFFAOYSA-N isobutyric acid ethyl ester Natural products CCOC(=O)C(C)C WDAXFOBOLVPGLV-UHFFFAOYSA-N 0.000 claims description 20
- 229940017219 methyl propionate Drugs 0.000 claims description 20
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 16
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- -1 n-ethyl acrylate Chemical compound 0.000 claims description 12
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- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 10
- 238000010526 radical polymerization reaction Methods 0.000 claims description 5
- TYEYBOSBBBHJIV-UHFFFAOYSA-N 2-oxobutanoic acid Chemical compound CCC(=O)C(O)=O TYEYBOSBBBHJIV-UHFFFAOYSA-N 0.000 abstract 1
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- UIERETOOQGIECD-ONEGZZNKSA-N tiglic acid Chemical compound C\C=C(/C)C(O)=O UIERETOOQGIECD-ONEGZZNKSA-N 0.000 abstract 1
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- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
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- OSWPMRLSEDHDFF-UHFFFAOYSA-N methyl salicylate Chemical compound COC(=O)C1=CC=CC=C1O OSWPMRLSEDHDFF-UHFFFAOYSA-N 0.000 description 4
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- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 3
- 241001465754 Metazoa Species 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
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- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 description 2
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
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- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- QTECDUFMBMSHKR-UHFFFAOYSA-N prop-2-enyl prop-2-enoate Chemical compound C=CCOC(=O)C=C QTECDUFMBMSHKR-UHFFFAOYSA-N 0.000 description 1
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 229940107700 pyruvic acid Drugs 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
- C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
- C07C69/54—Acrylic acid esters; Methacrylic acid esters
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- 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
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/12—Esters of monohydric alcohols or phenols
- C08F20/14—Methyl esters, e.g. methyl (meth)acrylate
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
- C08L33/12—Homopolymers or copolymers of methyl methacrylate
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/14—Organic medium
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
Definitions
- the present invention relates to a monomer composition, a methacrylic resin composition and a resin molding.
- This application claims priority based on Japanese Patent Application No. 2021-085291 filed in Japan on May 20, 2021, the content of which is incorporated herein.
- Methacrylic resins are excellent in transparency, heat resistance, and weather resistance, and have well-balanced performance in resin physical properties such as mechanical strength, thermal properties, and moldability.
- methacrylic resin plates made of plate-shaped methacrylic resins are used for tanning beds, lighting equipment, skin therapy equipment, medical equipment, UV irradiation devices, equipment for growing animals and plants, skylights, HID lamps, and the like. It is used for translucent members.
- the methacrylic resin plate when the methacrylic resin plate is installed in an environment where it is exposed to UV such as direct sunlight or a UV lamp, the methacrylic resin plate has a yellowish color (yellowish, yellowish). was there. Therefore, there has been a demand for a methacrylic resin that does not develop a yellowish color even when exposed to UV for a long period of time, that is, a methacrylic resin that has excellent photostability.
- Patent Document 1 discloses that a monomer such as methyl methacrylate is polymerized in the presence of a hindered amine compound (HALS) having a specific structure, which is one of the photostabilizers.
- HALS hindered amine compound
- the present invention provides a methacrylic resin composition that has excellent light stability and suppressed yellowing while ensuring the excellent heat resistance of methacrylic resins;
- An object of the present invention is to provide a resin molded product; and a monomer composition for obtaining the methacrylic resin composition.
- the present invention has the following features. That is, the gist of the present invention is as follows.
- a monomer composition comprising methyl methacrylate and at least one compound of methyl pyruvate and methyl 2-methylbutyrate.
- a monomer composition comprising methyl methacrylate and at least one compound selected from methyl pyruvate and methyl 2-methylbutyrate, A monomer composition, wherein the total content of at least one compound selected from methyl pyruvate and methyl 2-methylbutyrate is 5 mass ppm or more relative to the total mass of the monomer composition.
- a monomer composition comprising methyl methacrylate and at least one compound selected from methyl pyruvate and methyl 2-methylbutyrate, A monomer composition, wherein the total content of at least one compound selected from methyl pyruvate and methyl 2-methylbutyrate is 50 mass ppm or more relative to the total mass of the monomer composition.
- a monomer composition comprising methyl methacrylate and at least one compound selected from methyl pyruvate and methyl 2-methylbutyrate, A monomer composition, wherein the total content of at least one compound selected from methyl pyruvate and methyl 2-methylbutyrate is 100 mass ppm or more relative to the total mass of the monomer composition.
- a methacrylic resin composition comprising a methacrylic polymer (P) and at least one compound selected from methyl pyruvate and methyl 2-methylbutyrate.
- a methacrylic resin composition containing a methacrylic polymer (P) and at least one compound selected from methyl pyruvate and methyl 2-methylbutyrate A methacrylic resin composition, wherein the total content of at least one compound selected from methyl pyruvate and methyl 2-methylbutyrate is 5 ppm by mass or more relative to the total mass of the methacrylic resin composition.
- a methacrylic resin composition containing a methacrylic polymer (P) and at least one compound selected from methyl pyruvate and methyl 2-methylbutyrate A methacrylic resin composition, wherein the total content of at least one compound selected from methyl pyruvate and methyl 2-methylbutyrate is 50 ppm by mass or more relative to the total mass of the methacrylic resin composition.
- a methacrylic resin composition containing a methacrylic polymer (P) and at least one compound selected from methyl pyruvate and methyl 2-methylbutyrate A methacrylic resin composition, wherein the total content of at least one compound selected from methyl pyruvate and methyl 2-methylbutyrate is 100 ppm by mass or more relative to the total mass of the methacrylic resin composition.
- the methacrylic polymer (P) contains 70 to 100% by mass of repeating units derived from methyl methacrylate and 0 to 30% by mass of repeating units derived from an acrylic ester.
- the methacrylic resin composition according to 1.
- a methacrylic resin composition having excellent light stability and suppressed yellowing while ensuring the excellent heat resistance of the methacrylic resin; a resin molded article containing the methacrylic resin composition; and a monomer composition for obtaining the methacrylic resin composition;
- (meth)acrylate means at least one selected from “acrylate” and “methacrylate”
- “(meth)acrylic” is selected from “methacrylic” and “acrylic”.
- the "methacrylic polymer” may contain repeating units derived from acrylic monomers in addition to repeating units derived from methacrylic monomers.
- “monomer” means an unpolymerized compound
- “repeating unit” means a unit derived from the monomer formed by polymerizing the monomer.
- the repeating unit may be a unit directly formed by a polymerization reaction, or may be a unit in which some of the units are converted to another structure by treating the polymer.
- “% by mass” indicates the content of a specific component contained in 100% by mass of the total amount.
- UV means light mainly including light in a wavelength range of 295 nm or more and 430 nm or less, that is, light in a wavelength range of 380 nm or less.
- a monomer composition according to a first embodiment of the present invention comprises methyl methacrylate and at least one compound of methyl pyruvate and methyl 2-methylbutyrate. Further, other components may be contained within a range that does not impair the effects of the present invention.
- Methyl methacrylate Since the monomer composition according to the present embodiment contains methyl methacrylate, it is possible to provide a methacrylic resin composition having good photostability and suppressed yellowing.
- the lower limit of the content of methyl methacrylate with respect to the total mass of the monomer composition according to the present embodiment is not particularly limited, but is preferably 85% by mass or more, more preferably 90% by mass or more, It is more preferably 95% by mass or more, and particularly preferably 97% by mass or more.
- the upper limit of the content of methyl methacrylate is usually 99.9995% by mass or less, and may be 99.9950% by mass or less, or 99.9900% by mass or less.
- the content of methyl methacrylate is, for example, 85% by mass or more and 99.9995% by mass or less, 90% by mass or more and 99.9995% by mass or less, 95% by mass or more and 99.9950% by mass or less, and 97% by mass or more.
- a range of 99.9900% by mass or less can be mentioned.
- the total content of methyl methacrylate, methyl pyruvate, and methyl 2-methylbutyrate with respect to the total mass of the monomer composition according to the present embodiment is not particularly limited, and is usually 100% by mass or less.
- the monomer composition according to the present embodiment is a methacrylic resin composition having good photostability and suppressed yellowing by containing at least one compound selected from methyl pyruvate and methyl 2-methylbutyrate. can be provided.
- the lower limit of the total content of methyl pyruvate and methyl 2-methylbutyrate with respect to the total mass of the monomer composition according to the present embodiment is not particularly limited, but provides a methacrylic resin composition with better photostability. In that respect, it is usually 5 mass ppm or more, preferably 50 mass ppm or more, more preferably 100 mass ppm or more, still more preferably 200 mass ppm or more, and particularly preferably 300 mass ppm or more.
- the upper limit of the total content of methyl pyruvate and methyl 2-methylbutyrate with respect to the total mass of the monomer composition according to the present embodiment is not particularly limited, but the monomer composition is converted to a methacrylic resin composition. In this case, it is usually 50,000 mass ppm or less, preferably 25,000 mass ppm or less, and more preferably 20,000 mass ppm or less, in that the heat resistance of the methacrylic resin is not impaired. , is more preferably 15,000 mass ppm or less, and particularly preferably 10,000 mass ppm or less.
- the total content of methyl pyruvate and methyl 2-methylbutyrate with respect to the total mass of the monomer composition according to the present embodiment is preferably 5 mass ppm or more and 50,000 mass ppm or less, It is more preferably 50 mass ppm or more and 25,000 mass ppm or less, further preferably 100 mass ppm or more and 20,000 mass ppm or less, and particularly preferably 200 mass ppm or more and 15,000 mass ppm or less. , 300 mass ppm or more and 10,000 mass ppm or less.
- the monomer composition according to the present embodiment may contain methyl methacrylate and monomers other than methyl methacrylate.
- monomers other than methyl methacrylate include the following monomers 1) to 16).
- the following monomers 1) to 16) can be used singly or in combination of two or more at any ratio.
- Methacrylic acid ester For example, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate, phenyl methacrylate or benzyl methacrylate.
- Acrylic acid ester For example, methyl acrylate, ethyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, or 2-ethylhexyl acrylate.
- unsaturated carboxylic acid For example acrylic acid, methacrylic acid, maleic acid or itaconic acid.
- Unsaturated carboxylic acid anhydride For example, maleic anhydride or itaconic anhydride.
- Maleimide For example, N-phenylmaleimide or N-cyclohexylmaleimide.
- hydroxy group-containing vinyl monomer For example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, or 2-hydroxypropyl methacrylate.
- Vinyl ester For example vinyl acetate or vinyl benzoate.
- Nitrogen-containing vinyl monomer For example, methacrylamide, or acrylonitrile.
- Epoxy group-containing monomer For example, glycidyl acrylate or glycidyl methacrylate.
- Aromatic vinyl monomer For example, styrene or ⁇ -methylstyrene.
- Alkanediol di(meth)acrylates For example, ethylene glycol di(meth)acrylate, 1,2-propylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate or 1,6-hexanediol di(meth)acrylate.
- Polyoxyalkylene glycol di(meth)acrylate For example, diethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, triethylene glycol (meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, or neopentyl glycol di(meth) ) acrylates.
- Vinyl monomer having two or more ethylenically unsaturated bonds in the molecule For example, divinylbenzene.
- the monomer is selected from the group consisting of methyl acrylate, ethyl acrylate, and n-butyl acrylate from the viewpoint of excellent balance of transparency, heat resistance, and moldability of the methacrylic resin composition.
- the content of the acrylic acid ester is preferably 0% by mass or more and 30% by mass or less with respect to the total mass of the monomer composition.
- the monomer composition according to this embodiment may further contain at least one compound selected from methyl isobutyrate and methyl propionate.
- a methacrylic resin composition having better photostability and more suppressed yellowing by the monomer composition containing the above compound in addition to at least one compound selected from methyl pyruvate and methyl 2-methylbutyrate. can provide things.
- the lower limit of the total content of methyl isobutyrate and methyl propionate with respect to the total mass of the monomer composition according to the present embodiment is 20 ppm by mass in that a methacrylic resin composition with better photostability can be provided. It is preferably 100 mass ppm or more, more preferably 200 mass ppm or more, particularly preferably 500 mass ppm or more, and most preferably 1000 mass ppm or more. .
- the upper limit of the total content of methyl isobutyrate and methyl propionate with respect to the total mass of the monomer composition according to the present embodiment is not particularly limited, but when the monomer composition is converted to a methacrylic resin composition, , from the point that the heat resistance of the methacrylic resin is not impaired, it is usually 50,000 mass ppm or less, preferably 25,000 mass ppm or less, more preferably 10,000 mass ppm or less, 7 ,000 mass ppm or less, and particularly preferably 5,000 mass ppm or less.
- the total content of methyl isobutyrate and methyl propionate is 20 mass ppm or more and 50,000 mass ppm or less, 100 mass ppm or more and 25,000 mass ppm or less, 200 mass ppm or more and 10,000 mass ppm.
- the range of 200 mass ppm or more and 7,000 mass ppm or less, 500 mass ppm or more and 7,000 mass ppm or less, and 1,000 mass ppm or more and 5,000 mass ppm or less are mentioned.
- the total content of methyl isobutyrate and methyl propionate is more preferably 100 mass ppm or more and 25,000 mass ppm or less, and further preferably 200 mass ppm or more and 7,000 mass ppm or less. .
- the monomer composition contains at least one of methyl isobutyrate and methyl propionate, methyl isobutyrate, methyl propionate, methyl pyruvate, and 2-methyl relative to the total mass of the monomer composition
- the total content of methyl butyrate is preferably within the range of the total content of methyl pyruvate and methyl 2-methylbutyrate described above.
- methyl pyruvate and methyl 2-methylbutyrate are believed to exhibit excellent photostability due to a mechanism of action different from that of commonly known UV absorbers and radical scavengers (HALS). . Therefore, it is also possible to use at least one compound of methyl pyruvate and methyl 2-methylbutyrate in combination with additives such as UV absorbers and HALS.
- a methacrylic resin composition and a resin molded article in which the photostability is increased at a lower cost by the monomer composition containing at least one compound selected from methyl pyruvate and 2-methylbutyrate and the additive. can be provided.
- additives examples include release agents, lubricants, plasticizers, antioxidants, antistatic agents, light stabilizers other than methyl pyruvate and methyl 2-methylbutyrate, ultraviolet absorbers, flame retardants, flame retardant aids, Known additives such as polymerization inhibitors, fillers, pigments, dyes, silane coupling agents, leveling agents, antifoaming agents, and fluorescent agents can be used.
- the said additive can be used individually by 1 type or in combination of arbitrary 2 or more types.
- the monomer composition according to the present embodiment may contain compounds such as methacrolein and methanol that are unavoidably mixed with methyl methacrylate.
- the polymerizable composition (X2) according to the second embodiment of the present invention is one aspect of raw materials for obtaining the methacrylic resin composition according to the third embodiment of the present invention, which will be described later.
- the polymerizable composition (X2) according to the present embodiment contains, for example, a raw material composition (X1) described later, at least one compound selected from methyl pyruvate and methyl 2-methylbutyrate, and a known radical polymerization initiator.
- polymerizable composition (X2-1); or polymerizable composition (X2-2) containing the monomer composition according to the first embodiment of the present invention and a known radical polymerization initiator.
- the raw material composition (X1) is a component of the polymerizable composition (X2-1), and is the methacrylic polymer (P) contained in the methacrylic resin composition according to the third embodiment of the present invention. It is also a raw material component.
- the methacrylic polymer (P) includes repeating units derived from methyl methacrylate (hereinafter also referred to as "MMA") (hereinafter also referred to as "MMA units”) and repeating units derived from acrylic acid esters.
- the raw material composition (X1) used for the production of the methacrylic polymer (P1) containing the unit (hereinafter also referred to as "acrylic acid ester unit") is mainly described, but the acrylic acid ester is changed to styrene. Therefore, it can also be applied to the production of a methacrylic polymer (P2) containing MMA units and styrene-derived repeating units (hereinafter also referred to as "styrene units"). At this time, the content of styrene is ⁇ 3-1. Methacrylic polymer (P)> can be applied to the styrene unit content.
- Examples of the raw material composition (X1) include a composition containing only MMA and a composition containing the MMA and an acrylic acid ester. ⁇ 1-3. other monomers> or ⁇ 3-1. Methacrylic Polymer (P)> can be used the same monomer as the acrylic acid ester described.
- the raw material composition (X1) contains MMA and an acrylic ester, the photostability of the methacrylic resin composition is improved, and the resin molding containing the methacrylic resin composition is exposed to UV for a long time. It is possible to suppress the occurrence of yellowish color and deterioration of photostability.
- the content of MMA in the raw material composition (X1) is not particularly limited, and can improve the photostability of the methacrylic resin composition.
- a ratio similar to the content ratio of MMA units in the methacrylic polymer (P1) or the methacrylic polymer (P2) described in Methacrylic Polymer (P)> can be suitably applied.
- ⁇ 3-1 "With respect to the total mass of the methacrylic polymer (P1)” and “with respect to the total mass of the methacrylic polymer (P2)" in the methacrylic polymer (P)>, "raw material composition (X1) shall be read as "for the total mass of
- the content of the acrylic acid ester (M2) in the raw material composition (X1) is not particularly limited, and the light stability of the methacrylic resin composition can be improved, so ⁇ 3-1.
- a ratio similar to the content ratio of the acrylic acid ester unit contained in the methacrylic polymer (P1) or the methacrylic polymer (P2) described in Methacrylic Polymer (P)> can be suitably applied.
- ⁇ 3-1 A ratio similar to the content ratio of the acrylic acid ester unit contained in the methacrylic polymer (P1) or the methacrylic polymer (P2) described in Methacrylic Polymer (P)> can be suitably applied.
- ⁇ 3-1 is ⁇ 3-1.
- raw material composition (X1) shall be read as "for the total mass of From the viewpoint of excellent photostability of the methacrylic resin composition, ⁇ 1-3. other monomers> or ⁇ 3-1.
- Methacrylic Polymer (P)> can be applied to the same compound as the acrylic acid ester described in the section.
- the raw material composition (X1) may previously contain a polymer containing MMA units.
- the raw material composition (X1) can contain in advance the polymer (a) described later.
- the polymerizable composition (X2-1) becomes a viscous liquid (referred to as “syrup”), so that the polymerization time can be shortened and productivity can be improved. can be improved.
- a method for obtaining the above-mentioned syrup for example, a method of dissolving a polymer in the raw material composition (X1), or a known radical polymerization initiator is added to the raw material composition (X1), and a part thereof is polymerized. methods and the like.
- the polymerizable composition (X2-1) when the polymerizable composition (X2-1) is a syrup, it includes a composition containing the following polymer (a) and monomer composition (m).
- Monomer composition (m) a monomer composition containing 70.0% by mass or more of MMA and 30.0% by mass or less of an acrylic ester, or MMA50, based on the total mass of the monomer composition (m) A monomer composition containing 0% by mass or more and 50.0% by mass or less of styrene, or a monomer composition comprising 100% by mass of MMA.
- the content (unit: mass %) of the raw material composition (X1) contained in the polymerizable composition (X2-1) is not particularly limited, and the total amount of the polymerizable composition (X2-1) It can be in the range of 97.5% by mass or more and 99.99% by mass or less with respect to the mass.
- the monomer composition which is a component of the polymerizable composition (X2-2), is the monomer composition according to the first embodiment of the present invention, and according to the third embodiment of the present invention. It is a composition containing the raw material component of the methacrylic polymer (P) contained in the methacrylic resin composition.
- the content of the monomer composition according to the first embodiment of the present invention is 60% by mass or more and less than 100% by mass with respect to the total mass of the polymerizable composition (X2-2).
- the polymerizable composition (X2-2) contains other monomers copolymerizable with the monomers in the monomer composition (also simply referred to as "other monomers"). You can When the polymerizable composition (X2-2) contains another monomer, the content of the other monomer is 0% by mass with respect to the total mass of the polymerizable composition (X2-2) It is more than 40% by mass and less than 40% by mass.
- Other monomers> include the monomers 1) to 16) listed above.
- the above monomers 1) to 16) can be used singly or in combination of two or more at any ratio.
- a monomer selected from ethylene glycol dimethacrylate and neopentyl glycol dimethacrylate from the viewpoint of providing a methacrylic resin composition having an excellent balance between heat resistance and transparency. is preferred.
- radical polymerization initiators include known azo compounds such as 2,2′-azobis(isobutyronitrile) and 2,2′-azobis(2,4-dimethylvaleronitrile); benzoyl peroxide and lauroyl peroxide; well-known organic peroxides such as oxide; These can be used alone or in combination of two or more in any ratio.
- known polymerization accelerators such as amines and mercaptans can be used together with the radical polymerization initiator.
- the content of the radical polymerization initiator in the polymerizable composition (X2) is not particularly limited, and can be appropriately determined by those skilled in the art according to well-known techniques. Specifically, the content of the radical polymerization agent may be 0.005 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the total mass of the polymerizable composition (X2), and 0.01 mass parts parts or more and 1.0 parts by mass or less.
- the polymerizable composition (X2) optionally contains a release agent, a heat stabilizer, a lubricant, a plasticizer, an antioxidant, an antistatic agent, and a photostabilizer other than methyl pyruvate and methyl 2-methylbutyrate.
- the methacrylic resin composition according to the third embodiment of the present invention (hereinafter also simply referred to as "methacrylic resin composition”) comprises a methacrylic polymer (P), methyl pyruvate and methyl 2-methylbutyrate.
- a methacrylic resin composition containing at least one compound of The methacrylic resin composition according to this embodiment may be a composition obtained by radically polymerizing the polymerizable composition (X2) according to the second embodiment of the invention. Since the methacrylic resin composition according to the present embodiment contains the methacrylic polymer (P), it is possible to provide a resin molding having good transparency.
- the methacrylic resin composition contains at least one compound selected from methyl pyruvate and methyl 2-methylbutyrate, thereby suppressing the generation of yellowish color even when exposed to UV for a long time, and further improving photostability. It is possible to provide a resin molding in which a decrease in the is suppressed. Moreover, although the form of the methacrylic resin composition is not particularly limited, it is usually solid.
- the content of the methacrylic polymer (P) with respect to the total mass of the methacrylic resin composition is not particularly limited, but from the viewpoint of good heat resistance, it is usually 95% by mass or more, and 97.5% by mass. It is preferably at least 98% by mass, more preferably at least 99.0% by mass. On the other hand, from the viewpoint of obtaining excellent photostability, this content is usually 99.9995% by mass or less, preferably 99.9950% by mass or less, 99.99% by mass or less, 99.9850% by mass or less, 99.98% by mass or less, 99.97% by mass or less, 99.95% by mass or less, or 99.90% by mass or less.
- the above upper limit and lower limit can be combined arbitrarily.
- the preferred content of the methacrylic polymer (P) is 95% by mass or more and 99.9995% by mass or less, 95% by mass or more and 99.9950% by mass or less, 97.5% by mass or more and 99.99% by mass or less. , 98% by mass or more and 99.9850% by mass or less, 99.0% by mass or more and 99.98% by mass or less, 99.0% by mass or more and 99.97% by mass or less, 99.0% by mass or more and 99.95% by mass or less , and a range of 99.0% by mass or more and 99.90% by mass or less.
- the methacrylic resin composition contains two or more methacrylic polymers (P)
- the above content is the total content of the two or more methacrylic polymers (P).
- the total content of at least one of methyl pyruvate and methyl 2-methylbutyrate relative to the total mass of the methacrylic resin composition is not particularly limited. From the viewpoint of obtaining excellent photostability, the total content of at least one compound selected from methyl pyruvate and methyl 2-methylbutyrate is usually 5 mass ppm or more with respect to the total mass of the methacrylic resin composition. , preferably 50 mass ppm or more, more preferably 100 mass ppm or more, even more preferably 150 mass ppm or more, particularly preferably 200 mass ppm or more, and 300 mass ppm or more Most preferably there is.
- the upper limit of the total content of at least one of methyl pyruvate and methyl 2-methylbutyrate contained in the methacrylic resin composition according to the present embodiment is not particularly limited, but the heat resistance of the resin molded product is good. From this point of view, it is usually 50,000 mass ppm or less, preferably 25,000 mass ppm or less, more preferably 20,000 mass ppm or less, and further preferably 15,000 mass ppm or less. Preferably, it is particularly preferably 10,000 mass ppm or less.
- the above upper limit and lower limit can be combined arbitrarily.
- the preferred total content of at least one compound of methyl pyruvate and methyl 2-methylbutyrate is 5 ppm by mass or more and 50,000 mass ppm or less, 50 mass ppm or more and 25,000 mass ppm or less, 100 mass ppm. 20,000 mass ppm or less, 150 mass ppm or more and 15,000 mass ppm or less, 200 mass ppm or more and 15,000 mass ppm or less, and 300 mass ppm or more and 10,000 mass ppm or less.
- the total content of at least one compound selected from methyl pyruvate and methyl 2-methylbutyrate is more preferably 50 mass ppm or more and 25,000 mass ppm or less, and still more preferably 150 mass ppm or more. 000 mass ppm or less.
- At least one compound of methyl pyruvate and methyl 2-methylbutyrate exhibits excellent photostability due to a different mechanism of action than commonly known UV absorbers and radical scavengers (HALS). It is thought that it expresses sexuality. Therefore, it is also possible to use at least one compound of methyl pyruvate and methyl 2-methylbutyrate in combination with additives such as UV absorbers and HALS. By using at least one compound selected from methyl pyruvate and methyl 2-methylbutyrate in combination with the additive, it is possible to provide a methacrylic resin composition and a resin molding with increased photostability at a lower cost. becomes.
- the methacrylic resin composition may contain a component other than at least one compound selected from the methacrylic polymer (P) and methyl pyruvate and methyl 2-methylbutyrate to the extent that the effects of the present invention can be obtained.
- a component other than at least one compound selected from the methacrylic polymer (P) and methyl pyruvate and methyl 2-methylbutyrate to the extent that the effects of the present invention can be obtained.
- additives selected from release agents, heat stabilizers, antioxidants, UV absorbers, and light stabilizers other than methyl pyruvate and methyl 2-methylbutyrate may be included.
- the methacrylic polymer (P) is one of the components contained in the methacrylic resin composition according to this embodiment.
- the methacrylic resin composition can improve transparency, suppress decomposition by heat and light, and improve heat moldability, heat resistance, and mechanical strength. can be made better.
- the methacrylic polymer (P) is a copolymer containing MMA units and acrylic acid ester units (hereinafter also referred to as a methacrylic polymer (P1)), or a copolymer containing MMA units and styrene units ( Hereinafter, it is also referred to as a methacrylic polymer (P2).).
- the arrangement of these copolymers is not particularly limited, and may be, for example, random copolymers, block copolymers, alternating copolymers, etc., but random copolymers are preferred.
- the repeating unit derived from the acrylic acid ester is a repeating unit derived from the acrylic acid ester having an alkyl group having 1 to 6 carbon atoms in the side chain.
- the monomer constituting this unit is not particularly limited as long as it is a monomer copolymerizable with MMA. Examples thereof include acrylic esters such as methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, and t-butyl acrylate. These may be used individually by 1 type, and may use 2 or more types together by arbitrary ratios and combinations.
- acrylic At least one acrylate ester selected from the group consisting of methyl acid, n-ethyl acrylate, and n-butyl acrylate is preferred, and n-butyl acrylate is more preferred.
- the content of MMA units in the methacrylic polymer (P1) is not particularly limited. From the viewpoint of good heat resistance, the total mass of the methacrylic polymer (P1) is preferably 70.0% by mass or more, more preferably 80.0% by mass or more, and 90% by mass or more. It is more preferably at least 0.0% by mass, and usually at most 100% by mass.
- the content of the acrylate unit in the methacrylic polymer (P1) is not particularly limited, but from the viewpoint of good heat resistance and light stability, it is preferably 30% by mass or less. It is more preferably 10% by mass or less, more preferably 10% by mass or less, and usually 0% by mass or more.
- the above content ratio is the total content ratio of two or more kinds of acrylic acid ester units.
- the content ratio of the MMA unit in the methacrylic polymer (P2) is not particularly limited, but from the viewpoint of good heat resistance, it is 50.5% with respect to the total mass of the methacrylic polymer (P2). It is preferably 0% by mass or more, more preferably 60.0% by mass or more, still more preferably 70.0% by mass or more, and usually 100% by mass or less.
- the content of styrene units in the methacrylic polymer (P2) is not particularly limited, but from the viewpoint of good transparency, it is preferably 50% by mass or less, and 40% by mass or less. is more preferable, more preferably 30% by mass or less, and usually 0% by mass or more.
- the methacrylic polymer (P) in the present embodiment is a structural unit derived from a polyfunctional monomer containing two or more radically polymerizable functional groups in one molecule (hereinafter referred to as , referred to as “polyfunctional monomer units”).
- polyfunctional monomer units a polyfunctional monomer containing two or more radically polymerizable functional groups in one molecule
- the term "radical polymerizable functional group” as used herein refers to any group having a carbon-carbon double bond and capable of being radically polymerized. Specific examples include a vinyl group, an allyl group, a (meth)acryloyl group, A (meth)acryloyloxy group and the like can be mentioned.
- a (meth)acryloyl group is preferable from the viewpoint that the compound having a radically polymerizable functional group has excellent storage stability and that the polymerizability of the compound can be easily controlled.
- “(meth)acryloyl” indicates one or both of "acryloyl” and "methacryloyl”.
- Each radically polymerizable functional group in the monomer having two radically polymerizable functional groups may be the same or different.
- the methacrylic polymer (P) contains polyfunctional monomer units, solvent resistance, chemical resistance, etc. can be improved.
- Polyfunctional monomers include allyl methacrylate, allyl acrylate, ethylene glycol di(meth)acrylate, ethylene glycol tri(meth)acrylate, neopentyl glycol di(meth)acrylate, and trimethylolpropane tri(meth) Examples include acrylates, but are not particularly limited to these. These may be used individually by 1 type, and may use 2 or more types together by arbitrary ratios and combinations. Among these, the polyfunctional monomer is selected from ethylene glycol di (meth) acrylate and neopentyl glycol di (meth) acrylate from the viewpoint of better solvent resistance and chemical resistance. is more preferred, and ethylene glycol di(meth)acrylate is even more preferred.
- the weight average molecular weight (Mw) of the methacrylic polymer (P) measured by gel permeation chromatography (GPC) is not particularly limited. do not have.
- the weight average molecular weight (Mw) can be appropriately set according to the intended use of the resin molding. For example, the may be 4,000,000 or less.
- the weight average molecular weight is a value measured by gel permeation chromatography using standard polystyrene as a standard sample. Solvent resistance and chemical resistance can be improved by appropriately increasing the weight average molecular weight.
- the weight average molecular weight (Mw) of the methacrylic polymer (P) can be controlled by adjusting the polymerization temperature, polymerization time, amount of polymerization initiator added, or type and amount of serial transfer agent.
- Methyl pyruvate and methyl 2-methylbutyrate At least one compound of methyl pyruvate and methyl 2-methylbutyrate is one of the components contained in the methacrylic resin composition according to this embodiment.
- the methacrylic resin composition can suppress yellowish discoloration upon long-term UV exposure. Furthermore, it is less expensive than conventional ultraviolet absorbers and the like, and can also suppress a decrease in photostability.
- the methacrylic resin composition according to this embodiment may further contain at least one compound selected from methyl isobutyrate and methyl propionate.
- the lower limit of the total content of methyl isobutyrate and methyl propionate with respect to the total mass of the methacrylic resin composition according to the present embodiment is 20 ppm by mass in that a methacrylic resin composition with better photostability can be provided. It is preferably 100 mass ppm or more, more preferably 200 mass ppm or more, particularly preferably 500 mass ppm or more, and 1,000 mass ppm or more. Most preferred.
- the upper limit of the total content of methyl isobutyrate and methyl propionate with respect to the total mass of the methacrylic resin composition according to the present embodiment is not particularly limited. 000 mass ppm or less, preferably 25,000 mass ppm or less, more preferably 10,000 mass ppm or less, further preferably 7,000 mass ppm or less, 5,000 mass ppm The following are particularly preferred.
- the total content of methyl isobutyrate and methyl propionate is 20 mass ppm or more and 50,000 mass ppm or less, 100 mass ppm or more and 25,000 mass ppm or less, 200 mass ppm or more and 10,000 mass ppm.
- the range of 200 mass ppm or more and 7,000 mass ppm or less, 500 mass ppm or more and 7,000 mass ppm or less, and 1,000 mass ppm or more and 5,000 mass ppm or less are mentioned.
- the total content of methyl isobutyrate and methyl propionate is more preferably 100 mass ppm or more and 25,000 mass ppm or less, and further preferably 200 mass ppm or more and 7,000 mass ppm or less. .
- the methacrylic resin composition contains at least one compound of methyl isobutyrate and methyl propionate, methyl isobutyrate, methyl propionate, methyl pyruvate, and 2-
- the total content of methyl methylbutyrate is preferably within the range of the total content of methyl pyruvate and methyl 2-methylbutyrate described above.
- the methacrylic resin composition according to the present embodiment contains the methacrylic polymer (P) and at least one compound selected from methyl pyruvate and methyl 2-methylbutyrate, it has excellent photostability. there is
- a test piece made of a methacrylic resin composition (50 mm long x 50 mm wide, 3 mm thick) was subjected to the UV exposure test described below.
- the yellowness index (YI) measured according to ASTM D1925 obtained from before the start of the test to 200 hours after the start of the UV exposure test is 7.1 or less, preferably 6.0 or less, more preferably 4.5 or less. , and more preferably 4.0 or less.
- the test piece preferably has a light transmittance of 15.0% or more at a wavelength of 295 nm or a light transmittance of 35.0% or more at a wavelength of 315 nm.
- the test piece has a light transmittance of 15.0% or more at a wavelength of 295 nm and a light transmittance of 35.0% or more at a wavelength of 315 nm.
- the light transmittance is measured using a haze meter (for example, "NDH4000” manufactured by Nippon Denshoku Industries Co., Ltd.) in accordance with JIS K 7361-1: 1997, and the total light transmission in the thickness direction of the test piece. means rate (Tt).
- a resin molded article (also referred to simply as a "resin molded article") according to the fourth embodiment of the present invention is a resin molded article containing the methacrylic resin composition according to the third embodiment of the present invention.
- the resin molded article is not particularly limited as long as it is a molded article containing the above methacrylic resin composition, and a molded article consisting only of a methacrylic resin composition is substantially a methacrylic resin composition. and resin moldings.
- the shape of the resin molded body examples include a plate-shaped resin molded body (resin plate) and a sheet-shaped resin molded body (resin sheet).
- the thickness of the resin molding can be adjusted to any desired thickness from a thick plate to a thin film.
- the thickness can be 1 mm or more and 30 mm or less.
- the resin molding contains the methacrylic resin composition described above, it has excellent light stability. That is, a test piece of the resin molding (50 mm long ⁇ 50 mm wide, 3 mm thick) is obtained from before the start of the UV exposure test to 200 hours after the start of the UV exposure test, according to ASTM D1925.
- the yellowness index (YI) as measured by immersion is 7.1 or less, preferably 6.0 or less, more preferably 4.5 or less, and even more preferably 4.0 or less.
- the test strips preferably exhibit high photostability, such as a light transmission of 15.0% or greater at a wavelength of 295 nm, or a light transmission of 35.0% or greater at a wavelength of 315 nm.
- the test piece has a light transmittance of 15.0% or more at a wavelength of 295 nm and a light transmittance of 35.0% or more at a wavelength of 315 nm.
- the light transmittance is the total light transmission in the thickness direction of the test piece measured using a haze meter (for example, "NDH4000” manufactured by Nippon Denshoku Industries Co., Ltd.) in accordance with JIS K 7361-1: 1997. means rate (Tt).
- Method for producing methacrylic resin composition or resin molding> A method for producing a methacrylic resin composition or a resin molded article containing the resin composition (hereinafter, the methacrylic resin composition and the resin molded article are also collectively referred to as "resin composition etc.”), No special restrictions.
- the polymerizable composition (X2) according to the second embodiment of the present invention preferably the monomer composition according to the first embodiment of the present invention.
- the radical polymerization step may include a syrup preparation step of polymerizing a portion of the polymerizable composition (X2) to prepare a syrup, and a polymerization step of polymerizing the polymerizable components in the syrup.
- "polymerizing a part of the polymerizable composition (X2)" in the syrup preparation step means that the content of the methacrylic polymer in the obtained syrup is 10% by mass or more and 80% by mass or less, preferably 10% by mass. It means that the polymerization is carried out so that the content is 60% by mass or more, more preferably 10% by mass or more and 40% by mass or less.
- the polymerization temperature for polymerizing the polymerizable composition (X2) is not particularly limited, and can be appropriately determined by those skilled in the art according to well-known techniques. Generally, the temperature is appropriately set in the range of preferably 40° C. or higher and 180° C. or lower, more preferably 50° C. or higher and 150° C. or lower, depending on the type of radical polymerization initiator to be used. In addition, the polymerizable composition (X2) can be polymerized under multistage temperature conditions as necessary. The polymerization time may be appropriately determined according to the progress of polymerization and curing.
- Polymerization methods for the polymerizable composition (X2) include, for example, a bulk polymerization method, a suspension polymerization method, an emulsion polymerization method and a dispersion polymerization method. Legal is preferred.
- the method for producing the resin composition or the like specifically includes, for example, a method of obtaining a resin composition or the like by a bulk polymerization method using a known cast polymerization method such as a cell casting method or a continuous casting method, or Moreover, the method of shape
- a cast polymerization method for example, when obtaining a resin composition having a plate-like shape, two glass plates or metal plates (SUS plates) facing each other and a soft resin tube or the like arranged at the edge thereof are used. Using the space formed by the gasket as a mold, the polymerizable composition (X2) or a syrup obtained by polymerizing a part of the polymerizable composition (X2) is injected into the mold and subjected to heat polymerization treatment to complete the polymerization. , a cell casting method in which a resin composition or the like is taken out from a mold.
- a space formed by two stainless steel endless belts running in the same direction at the same speed and facing each other at a predetermined interval and gaskets such as soft resin tubes arranged on both sides of the belt is used as a mold.
- the polymerizable composition (X2) or a syrup obtained by polymerizing a part of the polymerizable composition (X2) is continuously injected into the mold from one end of the endless belt, and the polymerization is completed by heat polymerization treatment,
- a continuous casting method, in which the resin composition or the like is continuously taken out from the other end of the endless belt, can be mentioned.
- a resin composition or the like having a desired thickness can be obtained by appropriately adjusting the spacing of the voids in the mold by adjusting the thickness (diameter) of the gasket.
- the thickness of the plate-shaped resin composition or the like is usually set in the range of 1 mm or more and 30 mm or less.
- resin composition, etc. are not particularly limited, but include tanning beds, lighting equipment, skin therapy equipment, medical equipment, UV irradiation devices, equipment for growing animals and plants, and skylights. , and HID lamps. More specifically, a lighting member which is a member for the purpose of daylighting used in any of tanning beds and skylights, or a lighting device, a skin therapy device, a medical device, a UV irradiation device, and for growing animals and plants It is preferably used as a translucent member which is a member intended to transmit light used in any of equipment, HID lamps, and the like.
- the monomer composition according to the first embodiment of the present invention contains at least one compound selected from methyl pyruvate and methyl 2-methylbutyrate, and a polymerizable composition (X2) containing the monomer composition
- the methacrylic resin composition obtained by radical polymerization of is excellent in light stability while ensuring excellent heat resistance, and yellowing is suppressed.
- the monomer composition according to the first embodiment of the present invention contains at least one compound of methyl pyruvate and 2-methylbutyrate, thereby ensuring excellent heat resistance and excellent photostability. The reason why a methacrylic resin composition with suppressed yellowing can be obtained is presumed as follows.
- Polymers containing units based on methyl methacrylate generate radical species when the main chain or side chains are cleaved by light.
- the generated radical species usually causes yellowing of the methacrylic resin and reduction in mechanical strength due to reduction in molecular weight.
- methyl pyruvate and methyl 2-methylbutyrate contained in the monomer composition according to the first embodiment of the present invention remains in the methacrylic resin composition, resulting in pyruvic acid
- At least one compound of methyl and methyl 2-methylbutyrate is believed to function as a radical scavenger.
- the methacrylic resin composition is considered to exhibit excellent heat resistance and good light stability.
- ⁇ Photo stability ( ⁇ YI)> A metal weather super-accelerated photostability tester (Daipla ⁇ Using Wintes Co., Ltd., model name: KU-R5CI-A), a UV exposure test was performed, and according to the method described later, the change in yellowness from before the start of the UV exposure test to 200 hours after the start ( ⁇ YI) was measured.
- a test piece square shape of 50 mm long x 50 mm wide, thickness 5 mm
- the irradiation intensity of ultraviolet rays (UV) irradiated from the metal halide lamp to the test piece was measured with an ultraviolet illuminometer (manufactured by Ushio Inc., model name: UIT-101), and the irradiation intensity at a wavelength of 330 to 390 nm was 80 mW/ Corrected to be cm 2 .
- the evaluation chamber of the metal weather ultra-accelerated photostability tester is set to an environment with a temperature of 63° C.
- a spectroscopic color difference meter manufactured by Nippon Denshoku Industries Co., Ltd., model name: SE-7700 was used to measure the yellowness (yellow index: YI) of the test piece in accordance with ASTM D1925. It was measured. Using one test piece before the start of the UV exposure test and one test piece after 200 hours after the start, measurement was performed once for each test piece, and the change in the measured value was the change in yellowness ( ⁇ YI).
- Example 1 Production of syrup A reactor (polymerization kettle) equipped with a condenser, a thermometer and a stirrer is charged with methyl 2-methylbutyrate at a concentration of 300 ppm, and further supplied with 98.0 parts of MMA and 2.0 parts of BA, After bubbling nitrogen gas while stirring, heating was started. When the internal temperature of the reactor reached 80 ° C., 0.12 parts of 2,2'-azobis-(2,4-dimethylvaleronitrile) as a radical polymerization initiator and 1-dodecanethiol as a chain transfer agent were added to 0.
- Table 1 shows the evaluation results of the properties of the obtained resin moldings.
- "-" means that no measurement was performed.
- Example 2 (1) Production of Syrup Methyl 2-methylbutyrate was added to a reactor (polymerization vessel) equipped with a cooling pipe, a thermometer and a stirrer at a concentration of 300 ppm, and 100 parts of MMA was supplied and nitrogen gas was bubbled while stirring. After that, heating was started. When the internal temperature of the reactor reached 80°C, 0.12 parts of 2,2'-azobis-(2,4-dimethylvaleronitrile) was added as a radical polymerization initiator, and further the internal temperature of the reactor increased. After heating to 100° C., it was held for 9 minutes. Then, the reactor was cooled until the internal temperature reached room temperature to obtain a syrup. The polymer content in the syrup was 20% by weight relative to the total weight of the syrup.
- Table 1 shows the evaluation results of the properties of the obtained resin moldings.
- "-" means that no measurement was performed.
- Examples 3 to 6 A methacrylic resin composition and a resin molding were produced in the same manner as in Example 2, except that the composition of the monomer composition was changed as shown in Table 1.
- Table 1 shows the composition of the obtained methacrylic resin composition.
- Table 1 shows the evaluation results of the properties of the obtained resin moldings.
- Example 3 A methacrylic resin composition and a resin molding were obtained in the same manner as in Example 2, except that the composition of the monomer composition was as shown in Table 1.
- Table 1 shows the composition of the obtained methacrylic resin composition.
- Table 1 shows the evaluation results of the properties of the obtained resin moldings.
- Example 1 and Comparative Example 1 From the comparison of Example 1 and Comparative Example 1, in the system in which the methacrylic polymer contains units derived from acrylic acid ester, by containing at least one compound of methyl pyruvate and methyl 2-methylbutyrate, photostability It has been found that the performance can be improved. From the comparison of Example 1 and Comparative Example 2, if the methacrylic polymer contains at least one compound selected from methyl pyruvate and methyl 2-methylbutyrate, the resin composition does not contain a hindered amine compound. It was found that, even if there was a hindered amine compound, better photostability could be achieved than in an embodiment containing a hindered amine compound.
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Abstract
Description
本願は、2021年5月20日に、日本に出願された特願2021-085291号に基づき優先権を主張し、その内容をここに援用する。
また、HALSの添加量が増えることで、重合効率が低下しメタクリル系樹脂中の残存モノマーが増加してしまい、メタクリル系樹脂の光安定性を低下させるという問題があった。
メタクリル酸メチルと、ピルビン酸メチル及び2-メチル酪酸メチルのうち少なくとも1つの化合物とを含む、単量体組成物。
〔2〕
メタクリル酸メチルと、ピルビン酸メチル及び2-メチル酪酸メチルのうち少なくとも1つの化合物とを含む単量体組成物であって、
ピルビン酸メチル及び2-メチル酪酸メチルのうち少なくとも1つの化合物の合計含有量が、前記単量体組成物の総質量に対して、5質量ppm以上である、単量体組成物。
〔3〕
メタクリル酸メチルと、ピルビン酸メチル及び2-メチル酪酸メチルのうち少なくとも1つの化合物とを含む単量体組成物であって、
ピルビン酸メチル及び2-メチル酪酸メチルのうち少なくとも1つの化合物の合計含有量が、前記単量体組成物の総質量に対して、50質量ppm以上である、単量体組成物。
〔4〕
メタクリル酸メチルと、ピルビン酸メチル及び2-メチル酪酸メチルのうち少なくとも1つの化合物とを含む単量体組成物であって、
ピルビン酸メチル及び2-メチル酪酸メチルのうち少なくとも1つの化合物の合計含有量が、前記単量体組成物の総質量に対して、100質量ppm以上である、単量体組成物。
〔5〕
アクリル酸エステルをさらに含有する、〔1〕~〔4〕のいずれかに記載の単量体組成物。
〔6〕
前記アクリル酸エステルが、アクリル酸メチル、アクリル酸n-エチル、及びアクリル酸n-ブチルからなる群より選択される少なくとも1つの化合物である、〔5〕に記載の単量体組成物。
〔7〕
前記アクリル酸エステルが、アクリル酸n-ブチルである、〔5〕に記載の単量体組成物。
〔8〕
イソ酪酸メチル及びプロピオン酸メチルのうち少なくとも1つの化合物をさらに含有する、〔1〕~〔7〕のいずれかに記載の単量体組成物。
〔9〕
〔1〕~〔8〕のいずれかに記載の単量体組成物を含む重合性組成物(X2)をラジカル重合してなる、メタクリル系樹脂組成物。
〔10〕
メタクリル系重合体(P)と、ピルビン酸メチル及び2-メチル酪酸メチルのうち少なくとも1つの化合物とを含む、メタクリル系樹脂組成物。
〔11〕
メタクリル系重合体(P)と、ピルビン酸メチル及び2-メチル酪酸メチルのうち少なくとも1つの化合物とを含むメタクリル系樹脂組成物であって、
ピルビン酸メチル及び2-メチル酪酸メチルのうち少なくとも1つの化合物の合計含有量が、前記メタクリル系樹脂組成物の総質量に対して、5質量ppm以上である、メタクリル系樹脂組成物。
〔12〕
メタクリル系重合体(P)と、ピルビン酸メチル及び2-メチル酪酸メチルのうち少なくとも1つの化合物とを含むメタクリル系樹脂組成物であって、
ピルビン酸メチル及び2-メチル酪酸メチルのうち少なくとも1つの化合物の合計含有量が、前記メタクリル系樹脂組成物の総質量に対して、50質量ppm以上である、メタクリル系樹脂組成物。
〔13〕
メタクリル系重合体(P)と、ピルビン酸メチル及び2-メチル酪酸メチルのうち少なくとも1つの化合物とを含むメタクリル系樹脂組成物であって、
ピルビン酸メチル及び2-メチル酪酸メチルのうち少なくとも1つの化合物の合計含有量が、前記メタクリル系樹脂組成物の総質量に対して、100質量ppm以上である、メタクリル系樹脂組成物。
〔14〕
前記メタクリル系重合体(P)が、メタクリル酸メチル由来の繰り返し単位を70~100質量%、及びアクリル酸エステル由来の繰り返し単位を0~30質量%で含む、〔10〕~〔13〕のいずれかに記載のメタクリル系樹脂組成物。
〔15〕
前記メタクリル系重合体(P)が、メタクリル酸メチル由来の繰り返し単位を50~100質量%、及びスチレン由来の繰り返し単位を0~50質量%で含む、〔10〕~〔13〕のいずれかに記載のメタクリル系樹脂組成物。
〔16〕
〔9〕~〔15〕のいずれかに記載のメタクリル系樹脂組成物を含む、樹脂成形体。
〔17〕
〔1〕~〔8〕のいずれかに記載の単量体組成物を含む重合性組成物(X2)をラジカル重合するラジカル重合工程を含む、メタクリル系樹脂組成物の製造方法。
本明細書において、「単量体」は未重合の化合物を意味し、「繰り返し単位」は単量体が重合することによって形成された前記単量体に由来する単位を意味する。繰り返し単位は、重合反応によって直接形成された単位であってもよく、ポリマーを処理することによって前記単位の一部が別の構造に変換された単位であってもよい。
本明細書において、「質量%」は全体量100質量%中に含まれる特定の成分の含有量を示す。
本明細書において、UVとは、波長範囲として295nm以上430nm以下の光、即ち、波長380nm以下の波長領域の光を主として含む光を意味する。
本発明の第1の実施形態に係る単量体組成物は、メタクリル酸メチルと、ピルビン酸メチル及び2-メチル酪酸メチルのうち少なくとも1つの化合物とを含む。また、本発明の効果を損ねない範囲で、その他の成分を含んでいてもよい。
本実施形態に係る単量体組成物は、メタクリル酸メチルを含むことで、光安定性が良好で、黄変が抑制されたメタクリル系樹脂組成物を提供することができる。
本実施形態に係る単量体組成物は、ピルビン酸メチル及び2-メチル酪酸メチルのうち少なくとも1つの化合物を含むことで、光安定性が良好で、黄変が抑制されたメタクリル系樹脂組成物を提供することができる。
具体的には、本実施形態に係る単量体組成物の総質量に対するピルビン酸メチル及び2-メチル酪酸メチルの合計含有量は、5質量ppm以上50,000質量ppm以下であることが好ましく、50質量ppm以上25,000質量ppm以下であることがより好ましく、100質量ppm以上20,000質量ppm以下であることがさらに好ましく、200質量ppm以上15,000質量ppm以下であることが特に好ましく、300質量ppm以上10,000質量ppm以下であることが最も好ましい。
本実施形態に係る単量体組成物は、メタクリル酸メチルとともに、メタクリル酸メチル以外の単量体を含んでいてもよい。メタクリル酸メチル以外の単量体としては、例えば、下記1)~16)の単量体が挙げられる。下記1)~16)の単量体は、1種を単独で又は2種以上を任意の比率及び組み合わせて使用することができる。
例えば、メタクリル酸エチル、メタクリル酸イソプロピル、メタクリル酸n-ブチル、メタクリル酸iso-ブチル、メタクリル酸tert-ブチル、メタクリル酸2-エチルヘキシル、メタクリル酸フェニル、又はメタクリル酸ベンジル。
2)アクリル酸エステル:
例えば、アクリル酸メチル、アクリル酸エチル、アクリル酸n-ブチル、アクリル酸iso-ブチル、アクリル酸tert-ブチル、又はアクリル酸2-エチルヘキシル。
3)不飽和カルボン酸:
例えば、アクリル酸、メタクリル酸、マレイン酸、又はイタコン酸。
4)不飽和カルボン酸無水物:
例えば、無水マレイン酸、又は無水イタコン酸。
5)マレイミド:
例えば、N-フェニルマレイミド、又はN-シクロヘキシルマレイミド。
6)ヒドロキシ基含有ビニル単量体:
例えば、アクリル酸2-ヒドロキシエチル、メタクリル酸2-ヒドロキシエチル、又はメタクリル酸2-ヒドロキシプロピル。
7)ビニルエステル:
例えば、酢酸ビニル、又は安息香酸ビニル。
8)塩化ビニル、塩化ビニリデン、又はそれらの誘導体。
9)窒素含有ビニル単量体:
例えば、メタクリルアミド、又はアクリロニトリル。
10)エポキシ基含有単量体:
例えば、アクリル酸グリシジル、又はメタクリル酸グリシジル。
11)芳香族ビニル単量体:
例えば、スチレン、又はα-メチルスチレン。
例えば、エチレングリコールジ(メタ)アクリレート、1,2-プロピレングリコールジ(メタ)アクリレート、1,3-ブチレングリコールジ(メタ)アクリレート、又は1,6-ヘキサンジオールジ(メタ)アクリレート。
13)ポリオキシアルキレングリコールジ(メタ)アクリレート:
例えば、ジエチレングリコールジ(メタ)アクリレート、ジプロピレングリコールジ(メタ)アクリレート、トリエチレングリコール(メタ)アクリレート、テトラエチレングリコールジ(メタ)アクリレート、ポリエチレングリコールジ(メタ)アクリレート、又はネオペンチルグリコールジ(メタ)アクリレート。
14)分子中に2個以上のエチレン性不飽和結合を有するビニル単量体:
例えば、ジビニルベンゼン。
15)エチレン性不飽和ポリカルボン酸を含む少なくとも1種の多価カルボン酸と少なくとも1種のジオールから得られる不飽和ポリエステルプレポリマー。
16)エポキシ基の末端をアクリル変性することにより得られるビニルエステルプレポリマー。
本実施形態に係る単量体組成物は、イソ酪酸メチル及びプロピオン酸メチルのうち少なくとも1つの化合物をさらに含有していてもよい。単量体組成物がピルビン酸メチル及び2-メチル酪酸メチルのうち少なくとも1つの化合物に加えて上記化合物を含むことで、光安定性がより良好で、黄変がより抑制されたメタクリル系樹脂組成物を提供することができる。
具体的には、イソ酪酸メチル及びプロピオン酸メチルの合計含有量としては、20質量ppm以上50,000質量ppm以下、100質量ppm以上25,000質量ppm以下、200質量ppm以上10,000質量ppm以下、200質量ppm以上7,000質量ppm以下、500質量ppm以上7,000質量ppm以下、及び1,000質量ppm以上5,000質量ppm以下の範囲が挙げられる。これらのうち、イソ酪酸メチル及びプロピオン酸メチルの合計含有量は、100質量ppm以上25,000質量ppm以下であることがより好ましく、200質量ppm以上7,000質量ppm以下であることがさらに好ましい。
本実施形態において、ピルビン酸メチル及び2-メチル酪酸メチルは、一般的に知られているUV吸収剤及びラジカル捕捉剤(HALS)とは異なる作用機序により優れた光安定性を発現すると考えられる。よって、ピルビン酸メチル及び2-メチル酪酸メチルのうち少なくとも1つの化合物をUV吸収剤及びHALS等の添加剤と併用することも可能である。単量体組成物が、ピルビン酸メチル及び2-メチル酪酸メチルのうち少なくとも1つの化合物と該添加剤とを含むことにより、より安価に光安定性が増したメタクリル系樹脂組成物や樹脂成形体を提供することが可能となる。
本発明の第2の実施形態に係る重合性組成物(X2)は、後述する本発明の第3の実施形態に係るメタクリル系樹脂組成物を得るための原料の一態様である。本実施形態に係る重合性組成物(X2)は、例えば、後述する原料組成物(X1)、ピルビン酸メチル及び2-メチル酪酸メチルのうち少なくとも1つの化合物、及び公知のラジカル重合開始剤を含有する重合性組成物(X2-1);又は本発明の第1の実施形態に係る単量体組成物及び公知のラジカル重合開始剤を含有する重合性組成物(X2-2);である。
原料組成物(X1)は、前記重合性組成物(X2-1)の構成成分であり、本発明の第3の実施形態に係るメタクリル系樹脂組成物に含まれるメタクリル系重合体(P)の原料成分でもある。なお、以下の説明では、メタクリル系重合体(P)として、メタクリル酸メチル(以下、「MMA」とも称する。)由来の繰り返し単位(以下「MMA単位」とも称する。)及びアクリル酸エステル由来の繰り返し単位(以下、「アクリル酸エステル単位」とも称する。)を含有するメタクリル系重合体(P1)の製造に用いられる原料組成物(X1)の説明を主として行うが、アクリル酸エステルをスチレンに変更することで、MMA単位及びスチレン由来の繰り返し単位(以下、「スチレン単位」とも称する。)を含有するメタクリル系重合体(P2)の製造にも適用することができる。この際、スチレンの含有量は、<3-1.メタクリル系重合体(P)>で述べるスチレン単位の含有割合を適用することができる。
原料組成物(X1)が、MMAとアクリル酸エステルを含むことにより、メタクリル系樹脂組成物の光安定性が向上し、メタクリル系樹脂組成物を含む樹脂成形体がUVに長時間曝露された際の黄帯色の発生及び光安定性の低下を抑制することができる。
アクリル酸エステルの種類としては、メタクリル系樹脂組成物の光安定性に優れる観点から、<1-3.その他の単量体>で述べたアクリル酸エステル、又は<3-1.メタクリル系重合体(P)>で述べるアクリル酸エステルと同様の化合物を適用することができる。
上述したシラップを得る方法としては、例えば、原料組成物(X1)に重合体を溶解させる方法、或いは原料組成物(X1)に公知のラジカル重合開始剤を添加して、その一部を重合させる方法等が挙げられる。
重合体(a):重合体(a)の総質量に対して、MMA単位70.0質量%以上と前記アクリル酸エステル単位30.0質量%以下を含む重合体、又はMMA単位50.0質量%以上と前記スチレン単位50.0質量%以下を含む重合体、又はMMA単位100質量%からなる重合体。
単量体組成物(m):単量体組成物(m)の総質量に対して、MMA70.0質量%以上、アクリル酸エステル30.0質量%以下を含む単量体組成物、又はMMA50.0質量%以上とスチレン50.0質量%以下を含む単量体組成物、又はMMA100質量%からなる単量体組成物。
前記重合性組成物(X2-2)の構成成分である単量体組成物は、本発明の第1の実施形態に係る単量体組成物であり、本発明の第3の実施形態に係るメタクリル系樹脂組成物に含まれるメタクリル系重合体(P)の原料成分を含む組成物である。
また、重合性組成物(X2-2)は、該単量体組成物中の単量体と共重合可能な他の単量体(単に「他の単量体」とも記す。)を含んでいてもよい。重合性組成物(X2-2)が他の単量体を含む場合、前記他の単量体の含有量は、前記重合性組成物(X2-2)の総質量に対して、0質量%超40質量%未満である。
上記1)~16)の単量体は、1種を単独で又は2種以上を任意の比率及び組み合わせて使用することができる。
ラジカル重合開始剤としては、例えば、2,2’-アゾビス(イソブチロニトリル)及び2,2’-アゾビス(2,4-ジメチルバレロニトリル)等の公知のアゾ化合物;ベンゾイルパーオキサイド及びラウロイルパーオキサイド等の公知の有機過酸化物;等が挙げられる。これらは単独で又は2種以上を任意の比率及び組み合わせで使用することができる。また、必要に応じて、ラジカル重合開始剤と共にアミン、及びメルカプタン等の公知の重合促進剤を併用することができる。
前記重合性組成物(X2)は、必要に応じて、離型剤、熱安定化剤、滑剤、可塑剤、酸化防止剤、帯電防止剤、ピルビン酸メチル及び2-メチル酪酸メチル以外の光安定剤、紫外線吸収剤、難燃剤、難燃助剤、重合禁止剤、充填剤、顔料、染料、シランカップリング剤、レベリング剤、消泡剤、蛍光剤、及び連鎖移動剤等から選択される添加剤を含有していてもよい。
本発明の第3の実施形態に係るメタクリル系樹脂組成物(以下、単に「メタクリル系樹脂組成物」とも称する。)は、メタクリル系重合体(P)と、ピルビン酸メチル及び2-メチル酪酸メチルのうち少なくとも1つの化合物とを少なくとも含有するメタクリル系樹脂組成物である。本実施形態に係るメタクリル系樹脂組成物は、本発明の第2の実施形態に係る重合性組成物(X2)をラジカル重合してなる組成物であってもよい。
本実施形態に係るメタクリル系樹脂組成物は、メタクリル系重合体(P)を含むことで、透明性の良好な樹脂成形体を提供することができる。
メタクリル系樹脂組成物は、ピルビン酸メチル及び2-メチル酪酸メチルのうち少なくとも1つの化合物を含むことで、UVに長時間曝露されても、黄帯色の発生が抑制され、さらに、光安定性の低下が抑制された樹脂成形体を提供することができる。
また、メタクリル系樹脂組成物の形態は特段制限されないが、通常、固体である。
上記の上限値及び下限値は任意に組み合わせることができる。例えば、ピルビン酸メチル及び2-メチル酪酸メチルのうち少なくとも1つの化合物の好ましい合計含有量としては、5質量ppm以上50,000質量ppm以下、50質量ppm以上25,000質量ppm以下、100質量ppm以上20,000質量ppm以下、150質量ppm以上15,000質量ppm以下、200質量ppm以上15,000質量ppm以下、及び300質量ppm以上10,000質量ppm以下の範囲が挙げられる。これらのうち、ピルビン酸メチル及び2-メチル酪酸メチルのうち少なくとも1つの化合物の合計含有量は、より好ましくは50質量ppm以上25,000質量ppm以下であり、さらに好ましくは150質量ppm以上15,000質量ppm以下である。
メタクリル系重合体(P)は、本実施形態に係るメタクリル系樹脂組成物に含まれる成分の一つである。
メタクリル系樹脂組成物は、メタクリル系重合体(P)を含むことにより、透明性を向上させることができるとともに、熱や光による分解が抑制され、加熱成形性、耐熱性、及び機械的強度を良好にすることができる。さらに、メタクリル系重合体(P)が本来有している耐熱性と、ピルビン酸メチル及び2-メチル酪酸メチルのうち少なくとも1つの化合物との相乗効果により、UVに長時間曝露されたときに、黄帯色の発生が抑制され、光安定性が高く、耐熱性が維持されたメタクリル系樹脂成形体を得ることが可能となる。
ここでいうラジカル重合性官能基とは、炭素-炭素二重結合を有し、ラジカル重合可能な基であれば何れでもよく、具体的には、ビニル基、アリル基、(メタ)アクリロイル基、(メタ)アクリロイルオキシ基などが挙げられる。特に(メタ)アクリロイル基は、ラジカル重合性官能基を有する化合物の貯蔵安定性が優れている観点や、当該化合物の重合性を制御することが容易である観点から好ましい。なお、「(メタ)アクリロイル」は「アクリロイル」と「メタクリロイル」の一方あるいは両方を示す。なお、ラジカル重合性官能基を2個有する単量体中の各ラジカル重合性官能基は、同一であっても異なっていてもよい。
メタクリル系重合体(P)が、多官能性単量体単位を含むことにより、耐溶剤性又は耐薬品性等を向上させることができる。
メタクリル系重合体(P)の重量平均分子量(Mw)は、重合温度、重合時間、重合開始剤の添加量、又は連載移動剤の種類や添加量等を調整することにより制御できる。
ピルビン酸メチル及び2-メチル酪酸メチルのうち少なくとも1つの化合物は、本実施形態に係るメタクリル系樹脂組成物に含まれる成分の一つである。メタクリル系樹脂組成物は、ピルビン酸メチル及び2-メチル酪酸メチルのうち少なくとも1つの化合物を含有することにより、UVに長時間曝露された際の黄帯色の発生を抑制することができる。さらに、従来の紫外線吸収剤等よりも安価であり、さらに光安定性の低下を抑制することもできる。
本実施形態に係るメタクリル系樹脂組成物は、イソ酪酸メチル及びプロピオン酸メチルのうち少なくとも1つの化合物をさらに含有していてもよい。
具体的には、イソ酪酸メチル及びプロピオン酸メチルの合計含有量としては、20質量ppm以上50,000質量ppm以下、100質量ppm以上25,000質量ppm以下、200質量ppm以上10,000質量ppm以下、200質量ppm以上7,000質量ppm以下、500質量ppm以上7,000質量ppm以下、及び1,000質量ppm以上5,000質量ppm以下の範囲が挙げられる。これらのうち、イソ酪酸メチル及びプロピオン酸メチルの合計含有量は、100質量ppm以上25,000質量ppm以下であることがより好ましく、200質量ppm以上7,000質量ppm以下であることがさらに好ましい。
本実施形態に係るメタクリル系樹脂組成物は、前記メタクリル系重合体(P)、及びピルビン酸メチル及び2-メチル酪酸メチルのうち少なくとも1つの化合物を含有しているので、光安定性に優れている。
メタルハライドランプ(例えば、ダイプラ・ウィンテス(株)製「MW-60W」)と光カットフィルタ(例えば、ダイプラ・ウィンテス(株)製、「KF-1」)を備えたメタルウェザー超促進光安定性試験機(例えば、ダイプラ・ウィンテス(株)製「KU-R5CI-A」)の評価室内に、メタクリル系樹脂組成物からなる試験片(縦50mm×横50mmの正方形状、厚さ5mm)を設置し、温度63℃湿度50RH%の条件下で、メタルハライドランプの紫外線光(照射強度80mW/cm2)を試験片に照射する。
本発明の第4の実施形態に係る樹脂成形体(単に「樹脂成形体」とも称する。)は、本発明の第3の実施形態に係るメタクリル系樹脂組成物を含む樹脂成形体である。該メタクリル系樹脂組成物を成形することにより、優れた光安定性を有する樹脂成形体を得ることができる。本明細書において、樹脂成形体とは、上記のメタクリル系樹脂組成物を含む成形体であれば特段制限されず、メタクリル系樹脂組成物のみからなる成形体は、実質的にメタクリル系樹脂組成物及び樹脂成形体のいずれにも該当する。
すなわち、樹脂成形体の試験片(縦50mm×横50mmの正方形状、厚さ3mm)は、上述したUV曝露試験の開始前からUV曝露試験開始後200時間の間に得られる、ASTM D1925に準拠して測定した黄色度(YI)が7.1以下、好ましくは6.0以下、より好ましくは4.5以下、さらに好ましくは4.0以下となるような、優れた光安定性を示す。加えて、試験片は、好適には、波長295nmにおける光線透過率が15.0%以上、又は波長315nmにおける光線透過率が35.0%以上となるような、高い光安定性を示す。さらに好適には、試験片は、波長295nmにおける光線透過率が15.0%以上、かつ波長315nmにおける光線透過率が35.0%以上である。なお、光線透過率は、JIS K 7361-1:1997に準拠して、ヘーズメーター(例えば、日本電色工業社製「NDH4000」)を用いて測定された、試験片の厚み方向の全光線透過率(Tt)を意味する。
メタクリル系樹脂組成物、又は該樹脂組成物を含む樹脂成形体(以下、該メタクリル系樹脂組成物及び該樹脂成形体を総称して「樹脂組成物等」とも称する。)を製造する方法は、特段制限されない。樹脂組成物等の具体的な製造方法としては、例えば本発明の第2の実施形態に係る重合性組成物(X2)、好ましくは本発明の第1の実施形態に係る単量体組成物を含む重合性組成物(X2-2)をラジカル重合するラジカル重合工程を含む方法が挙げられる。ラジカル重合工程は、重合性組成物(X2)の一部を重合してシラップを調製するシラップ調製工程、及び前記シラップ中の重合性成分を重合する重合工程を含んでいてもよい。なお、シラップ調製工程における「重合性組成物(X2)の一部を重合」とは、得られるシラップ中のメタクリル系重合体の含有量が10質量%以上80質量%以下、好ましくは10質量%以上60質量%以下、より好ましくは10質量%以上40質量%以下となるよう重合することを意味する。
鋳型の空隙の間隔を、ガスケットの太さ(直径)で適宜調整して、所望の厚さの樹脂組成物等を得ることができる。板状の樹脂組成物等の厚さは、通常は1mm以上、30mm以下の範囲に設定される。
上述したメタクリル系樹脂組成物及び樹脂成形体(「樹脂組成物等」)の用途は特段制限されないが、日焼けベッド、照明機器、スキンセラピー機器、医療機器、UV照射デバイス、動植物育成用機器、天窓、及びHIDランプ等のいずれかに使用される透光性を有する部材、特に透明部材として好ましく用いられる。より具体的には、日焼けベッド、及び天窓等のいずれかに使用される採光することを目的とする部材である採光部材、又は照明機器、スキンセラピー機器、医療機器、UV照射デバイス、動植物育成用機器、及びHIDランプ等のいずれかに使用される透光することを目的とする部材である透光部材として好ましく用いられる。
本発明の第1の実施形態に係る単量体組成物は、ピルビン酸メチル及び2-メチル酪酸メチルのうち少なくとも1つの化合物を含み、該単量体組成物を含む重合性組成物(X2)をラジカル重合して得られるメタクリル系樹脂組成物は、優れた耐熱性を担保しつつ、光安定性に優れ、黄変が抑制される。
本発明の第1の実施形態に係る単量体組成物がピルビン酸メチル及び2-メチル酪酸メチルのうち少なくとも1つの化合物を含むことで、優れた耐熱性を担保しつつ、光安定性に優れ、黄変が抑制されたメタクリル系樹脂組成物が得られる理由は、以下のように推測される。
・MMA:メタクリル酸メチル(三菱ケミカル(株)製)
・BA:アクリル酸n-ブチル(三菱ケミカル(株)製)
・イソ酪酸メチル(東京化成工業(株)製)
・プロピオン酸メチル(東京化成工業(株)製)
・ピルビン酸メチル(東京化成工業(株)製)
・2-メチル酪酸メチル(東京化成工業(株)製)
・LA-57:1,2,3,4-ブタンテトラカルボン酸テトラキス(2,2,6,6-テトラメチル-4-ピペリジニル)(ADEKA(株)製)
なお、MMA(三菱ケミカル(株)製)中には、MMA総質量に対し、イソ酪酸メチルを260質量ppmの濃度で、プロピオン酸メチルを8質量ppmの濃度で、ピルビン酸メチルを8質量ppmの濃度で、2-メチル酪酸メチルを8質量ppmの濃度で含有していた。
<メタクリル系樹脂中の目的物質の残存量測定方法>
(1)試料と検液の調製手順
実施例及び比較例で得られた樹脂成形体を細かく破砕し、破砕した樹脂0.2gを10mLの残留農薬試験用アセトン(以下、単に「アセトン」と記す。)に溶解させた。樹脂が溶解した後、内部標準液をホールピペットで1mL添加した。内部標準液には0.1体積%サリチル酸メチル/アセトン溶液を用いた。対象の標準試薬をアセトンで希釈することで濃度の異なる3種類の検液を調製し、後述するガスクロマトグラフィー質量分析(GC/MS)測定により、3点検量線を作成し、サンプル中の各ターゲット物質の濃度を定量した。内部標準液には、0.1体積%サリチル酸メチル/アセトン溶液を用いた。
装置:GC HP6890/MS HP5973(アジレント社製)
イオン化法:EI(電子イオン化、Electron Ionization)法
カラム:DB-WAX 60m×250μm×0.5μm(アジレント社製)
昇温条件:70℃(5min)→200℃(5min) Rate=10℃/min
注入口温度:220℃
AUX温度:230℃
イオン源温度:230℃
スプリット比:10:1
流量:2.0mL/min
平均線速度:37cm/sec
注入量:1μL
測定モード:SIM
実施例及び比較例で得られたメタクリル系樹脂組成物の耐熱性の指標として、実施例及び比較例で得られた樹脂成形体の試験片(長さ127mm×幅12.7mm×厚さ3mm)について、JIS K 7191に準拠して、荷重たわみ温度(以下、「HDT」と示す)(℃)を測定した。
メタルハライドランプ(ダイプラ・ウィンテス(株)製、型式:MW-60W)と光カットフィルタ(ダイプラ・ウィンテス(株)製、型式:KF-1)を備えたメタルウェザー超促進光安定性試験機(ダイプラ・ウィンテス(株)製、機種名:KU-R5CI-A)を用いて、UV曝露試験を行い、後述する方法に従って、UV曝露試験の開始前から開始後200時間の間の黄色度の変化(ΔYI)を測定した。
前記メタルハライドランプから試験片に照射される紫外線(UV)の照射強度は、紫外線照度計(ウシオ電機(株)製、機種名:UIT-101)で測定した波長330~390nmにおける照射強度が80mW/cm2となるように補正した。メタルウェザー超促進光安定性試験機の評価室内は、温度63℃湿度50RH%の環境下となるように設定して、メタルハライドランプの紫外線光(照射強度80mW/cm2)を、前記試験片に照射した。
光安定性の指標として、分光式色差計(日本電色工業(株)製、機種名:SE-7700)を用い、ASTM D1925に準拠して前記試験片の黄色度(イエローインデックス:YI)を測定した。UV曝露試験の開始前の試験片1点と、開始後200時間後の試験片1点を用いて、各試験片につき1回測定を行い、その測定値の変化を黄色度の変化(ΔYI)とした。
[実施例1]
(1)シラップの製造
冷却管、温度計及び攪拌機を備えた反応器(重合釜)に2-メチル酪酸メチルを300ppmの濃度で添加し、さらにMMA98.0部及びBA2.0部を供給し、撹拌しながら窒素ガスでバブリングした後、加熱を開始した。反応器の内温が80℃になった時点で、ラジカル重合開始剤として2,2’-アゾビス-(2,4-ジメチルバレロニトリル)0.12部及び連鎖移動剤として1-ドデカンチオールを0.075部添加し、更に反応器の内温が100℃になるまで加熱した後、9分間保持した。次いで、反応器の内温が室温になるまで冷却してシラップを得た。シラップの総質量に対し、シラップ中の重合体の含有量は25質量%であった。
上記のシラップ100部に対しラジカル重合開始剤としてt-ヘキシルペルオキシピバレード0.15部を添加して、重合性組成物(X2)を得た。次いで、重合性組成物(X2)を、対向する2枚のSUS板の間のSUS板端部に軟質樹脂製ガスケットを配置して設けられた、空隙間隔6.5mmの空間に流し込み、80℃で30分、次いで130℃で30分加熱して、重合性組成物(X2)を硬化させてメタクリル系樹脂組成物を得た。メタクリル系樹脂組成物の組成を表1に示す。次いでSUS板ごと(メタ)アクリル樹脂組成物を冷却した後に、SUS板を取り除き、厚さ5mmの板状の樹脂成形体を得た。得られた樹脂成形体の特性の評価結果を表1に示す。なお、表1中、「-」は測定を行わなかったことを意味する。
(1)シラップの製造
冷却管、温度計及び攪拌機を備えた反応器(重合釜)に2-メチル酪酸メチルを300ppmの濃度で添加し、さらにMMA100部を供給し、撹拌しながら窒素ガスでバブリングした後、加熱を開始した。反応器の内温が80℃になった時点で、ラジカル重合開始剤として2,2’-アゾビス-(2,4-ジメチルバレロニトリル)を0.12部添加し、更に反応器の内温が100℃になるまで加熱した後、9分間保持した。次いで、反応器の内温が室温になるまで冷却してシラップを得た。シラップの総質量に対し、シラップ中の重合体の含有量は20質量%であった。
上記のシラップ100部に対しラジカル重合開始剤としてt-ヘキシルペルオキシピバレード0.15部を添加して、重合性組成物(X2)を得た。次いで、重合性組成物(X2)を、対向する2枚のSUS板の間のSUS板端部に軟質樹脂製ガスケットを配置して設けられた、空隙間隔4.1mmの空間に流し込み、80℃で30分、次いで130℃で30分加熱して、重合性組成物(X2)を硬化させてメタクリル系樹脂組成物を得た。メタクリル系樹脂組成物の組成を表1に示す。次いでSUS板ごとメタクリル系樹脂組成物を冷却した後に、SUS板を取り除き、厚さ3mmの板状の樹脂成形体を得た。得られた樹脂成形体の特性の評価結果を表1に示す。なお、表1中、「-」は測定を行わなかったことを意味する。
単量体組成物の組成を表1に記載のとおりに変更した以外は、実施例2と同様の方法でメタクリル系樹脂組成物、及び樹脂成形体を製造した。得られたメタクリル系樹脂組成物の組成を表1に示す。得られた樹脂成形体の特性の評価結果を表1に示す。
単量体組成物の組成を表1に記載のとおりとした以外は、実施例1と同様の方法でメタクリル系樹脂組成物、及び樹脂成形体を得た。得られたメタクリル系樹脂組成物の組成を表1に示す。得られた樹脂成形体の特性の評価結果を表1に示す。
単量体組成物の組成を表1に記載のとおりとした以外は、実施例2と同様の方法でメタクリル系樹脂組成物、及び樹脂成形体を得た。得られたメタクリル系樹脂組成物の組成を表1に示す。得られた樹脂成形体の特性の評価結果を表1に示す。
実施例1及び比較例2の比較から、メタクリル系重合体がピルビン酸メチル及び2-メチル酪酸メチルのうち少なくとも1つの化合物を含む態様であれば、樹脂組成物がヒンダードアミン系化合物を含まない態様であっても、ヒンダードアミン系化合物を含む態様よりも、良好な光安定性を実現できることが分かった。
実施例2~6及び比較例3の比較から、メタクリル系重合体がアクリル酸エステル由来の単位を含まない系において、ピルビン酸メチル及び2-メチル酪酸メチルのうち少なくとも1つの化合物を含有させることで、光安定性を向上させることができることが分かった。
Claims (17)
- メタクリル酸メチルと、ピルビン酸メチル及び2-メチル酪酸メチルのうち少なくとも1つの化合物とを含む、単量体組成物。
- メタクリル酸メチルと、ピルビン酸メチル及び2-メチル酪酸メチルのうち少なくとも1つの化合物とを含む単量体組成物であって、
ピルビン酸メチル及び2-メチル酪酸メチルのうち少なくとも1つの化合物の合計含有量が、前記単量体組成物の総質量に対して、5質量ppm以上である、単量体組成物。 - メタクリル酸メチルと、ピルビン酸メチル及び2-メチル酪酸メチルのうち少なくとも1つの化合物とを含む単量体組成物であって、
ピルビン酸メチル及び2-メチル酪酸メチルのうち少なくとも1つの化合物の合計含有量が、前記単量体組成物の総質量に対して、50質量ppm以上である、単量体組成物。 - メタクリル酸メチルと、ピルビン酸メチル及び2-メチル酪酸メチルのうち少なくとも1つの化合物とを含む単量体組成物であって、
ピルビン酸メチル及び2-メチル酪酸メチルのうち少なくとも1つの化合物の合計含有量が、前記単量体組成物の総質量に対して、100質量ppm以上である、単量体組成物。 - アクリル酸エステルをさらに含有する、請求項1~4のいずれか1項に記載の単量体組成物。
- 前記アクリル酸エステルが、アクリル酸メチル、アクリル酸n-エチル、及びアクリル酸n-ブチルからなる群より選択される少なくとも1つの化合物である、請求項5に記載の単量体組成物。
- 前記アクリル酸エステルが、アクリル酸n-ブチルである、請求項5に記載の単量体組成物。
- イソ酪酸メチル及びプロピオン酸メチルのうち少なくとも1つの化合物をさらに含有する、請求項1~7のいずれか1項に記載の単量体組成物。
- 請求項1~8のいずれか1項に記載の単量体組成物を含む重合性組成物(X2)をラジカル重合してなる、メタクリル系樹脂組成物。
- メタクリル系重合体(P)と、ピルビン酸メチル及び2-メチル酪酸メチルのうち少なくとも1つの化合物とを含む、メタクリル系樹脂組成物。
- メタクリル系重合体(P)と、ピルビン酸メチル及び2-メチル酪酸メチルのうち少なくとも1つの化合物とを含むメタクリル系樹脂組成物であって、
ピルビン酸メチル及び2-メチル酪酸メチルのうち少なくとも1つの化合物の合計含有量が、前記メタクリル系樹脂組成物の総質量に対して、5質量ppm以上である、メタクリル系樹脂組成物。 - メタクリル系重合体(P)と、ピルビン酸メチル及び2-メチル酪酸メチルのうち少なくとも1つの化合物とを含むメタクリル系樹脂組成物であって、
ピルビン酸メチル及び2-メチル酪酸メチルのうち少なくとも1つの化合物の合計含有量が、前記メタクリル系樹脂組成物の総質量に対して、50質量ppm以上である、メタクリル系樹脂組成物。 - メタクリル系重合体(P)と、ピルビン酸メチル及び2-メチル酪酸メチルのうち少なくとも1つの化合物とを含むメタクリル系樹脂組成物であって、
ピルビン酸メチル及び2-メチル酪酸メチルのうち少なくとも1つの化合物の合計含有量が、前記メタクリル系樹脂組成物の総質量に対して、100質量ppm以上である、メタクリル系樹脂組成物。 - 前記メタクリル系重合体(P)が、メタクリル酸メチル由来の繰り返し単位を70~100質量%、及びアクリル酸エステル由来の繰り返し単位を0~30質量%で含む、請求項10~13のいずれか1項に記載のメタクリル系樹脂組成物。
- 前記メタクリル系重合体(P)が、メタクリル酸メチル由来の繰り返し単位を50~100質量%、及びスチレン由来の繰り返し単位を0~50質量%で含む、請求項10~13のいずれか1項に記載のメタクリル系樹脂組成物。
- 請求項9~15のいずれか1項に記載のメタクリル系樹脂組成物を含む、樹脂成形体。
- 請求項1~8のいずれか1項に記載の単量体組成物を含む重合性組成物(X2)をラジカル重合するラジカル重合工程を含む、メタクリル系樹脂組成物の製造方法。
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CN202280036147.9A CN117321138A (zh) | 2021-05-20 | 2022-05-19 | 单体组合物、甲基丙烯酸系树脂组合物及树脂成形体 |
EP22804744.5A EP4353775A1 (en) | 2021-05-20 | 2022-05-19 | Monomer composition, methacrylic resin composition and resin molded body |
KR1020237043048A KR20240007270A (ko) | 2021-05-20 | 2022-05-19 | 단량체 조성물, 메타크릴계 수지 조성물 및 수지 성형체 |
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- 2022-05-19 WO PCT/JP2022/020782 patent/WO2022244833A1/ja active Application Filing
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- 2023-04-18 JP JP2023068032A patent/JP2023089218A/ja active Pending
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- 2023-05-17 JP JP2023081307A patent/JP2023096058A/ja active Pending
- 2023-11-17 US US18/512,500 patent/US20240158552A1/en active Pending
- 2023-11-17 US US18/512,517 patent/US20240083835A1/en active Pending
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JPS62123150A (ja) * | 1985-11-25 | 1987-06-04 | Mitsui Toatsu Chem Inc | メタクリル酸メチルの精製法 |
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KR20240033122A (ko) | 2024-03-12 |
KR20240008349A (ko) | 2024-01-18 |
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CN117412996A (zh) | 2024-01-16 |
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JPWO2022244834A1 (ja) | 2022-11-24 |
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WO2022244833A1 (ja) | 2022-11-24 |
KR20240007271A (ko) | 2024-01-16 |
TW202302519A (zh) | 2023-01-16 |
EP4353775A1 (en) | 2024-04-17 |
JPWO2022244835A1 (ja) | 2022-11-24 |
EP4353779A1 (en) | 2024-04-17 |
US20240158552A1 (en) | 2024-05-16 |
US20240084055A1 (en) | 2024-03-14 |
WO2022244834A1 (ja) | 2022-11-24 |
KR20240007270A (ko) | 2024-01-16 |
CN117321138A (zh) | 2023-12-29 |
JPWO2022244833A1 (ja) | 2022-11-24 |
CN117321137A (zh) | 2023-12-29 |
EP4353754A1 (en) | 2024-04-17 |
JP7318828B2 (ja) | 2023-08-01 |
JP7338797B2 (ja) | 2023-09-05 |
US20240083835A1 (en) | 2024-03-14 |
TW202302517A (zh) | 2023-01-16 |
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