JP4518372B2 - Ultrafine particle dispersed resin composition - Google Patents
Ultrafine particle dispersed resin composition Download PDFInfo
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- JP4518372B2 JP4518372B2 JP2003358615A JP2003358615A JP4518372B2 JP 4518372 B2 JP4518372 B2 JP 4518372B2 JP 2003358615 A JP2003358615 A JP 2003358615A JP 2003358615 A JP2003358615 A JP 2003358615A JP 4518372 B2 JP4518372 B2 JP 4518372B2
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- Prior art keywords
- metal
- ethylene
- oxygen
- meth
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000011882 ultra-fine particle Substances 0.000 title claims description 19
- 239000011342 resin composition Substances 0.000 title description 19
- 229910052751 metal Inorganic materials 0.000 claims description 80
- 239000002184 metal Substances 0.000 claims description 80
- 239000002253 acid Substances 0.000 claims description 40
- 229920000642 polymer Polymers 0.000 claims description 39
- 150000001875 compounds Chemical class 0.000 claims description 38
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 36
- 229910052760 oxygen Inorganic materials 0.000 claims description 36
- 239000001301 oxygen Substances 0.000 claims description 36
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 32
- 239000005977 Ethylene Substances 0.000 claims description 32
- -1 aluminum group metals Chemical class 0.000 claims description 28
- 238000004898 kneading Methods 0.000 claims description 25
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 22
- 229920002126 Acrylic acid copolymer Polymers 0.000 claims description 19
- 150000003839 salts Chemical class 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 17
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 10
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 239000011701 zinc Substances 0.000 claims description 9
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 7
- 150000001340 alkali metals Chemical class 0.000 claims description 7
- 150000007942 carboxylates Chemical class 0.000 claims description 7
- 238000002844 melting Methods 0.000 claims description 7
- 230000008018 melting Effects 0.000 claims description 7
- 150000004645 aluminates Chemical class 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 150000004703 alkoxides Chemical class 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 1
- 239000010452 phosphate Substances 0.000 claims 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 22
- 229920001577 copolymer Polymers 0.000 description 21
- 238000000034 method Methods 0.000 description 16
- 239000000463 material Substances 0.000 description 15
- 150000002736 metal compounds Chemical class 0.000 description 12
- 230000000704 physical effect Effects 0.000 description 12
- 239000011787 zinc oxide Substances 0.000 description 11
- 239000000178 monomer Substances 0.000 description 10
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 8
- 238000004736 wide-angle X-ray diffraction Methods 0.000 description 8
- 150000003751 zinc Chemical class 0.000 description 8
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 7
- 230000002378 acidificating effect Effects 0.000 description 7
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000010419 fine particle Substances 0.000 description 7
- 125000000524 functional group Chemical group 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 229920005992 thermoplastic resin Polymers 0.000 description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 239000000395 magnesium oxide Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 150000002484 inorganic compounds Chemical class 0.000 description 5
- 229910010272 inorganic material Inorganic materials 0.000 description 5
- 239000000155 melt Substances 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 4
- 239000005751 Copper oxide Substances 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- 238000004220 aggregation Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 239000002872 contrast media Substances 0.000 description 4
- 229910000431 copper oxide Inorganic materials 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000011358 absorbing material Substances 0.000 description 3
- 238000010306 acid treatment Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 3
- 229920000554 ionomer Polymers 0.000 description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 3
- 229910001510 metal chloride Inorganic materials 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 150000002927 oxygen compounds Chemical class 0.000 description 3
- 230000000737 periodic effect Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- 239000004716 Ethylene/acrylic acid copolymer Substances 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 159000000003 magnesium salts Chemical class 0.000 description 2
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 2
- 229940117841 methacrylic acid copolymer Drugs 0.000 description 2
- 239000011859 microparticle Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 229910052716 thallium Inorganic materials 0.000 description 2
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 2
- ZIKATJAYWZUJPY-UHFFFAOYSA-N thulium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Tm+3].[Tm+3] ZIKATJAYWZUJPY-UHFFFAOYSA-N 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 229920001567 vinyl ester resin Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WQXKGOOORHDGFP-UHFFFAOYSA-N 1,2,4,5-tetrafluoro-3,6-dimethoxybenzene Chemical compound COC1=C(F)C(F)=C(OC)C(F)=C1F WQXKGOOORHDGFP-UHFFFAOYSA-N 0.000 description 1
- OGMSGZZPTQNTIK-UHFFFAOYSA-N 1-methyl-2-prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1C OGMSGZZPTQNTIK-UHFFFAOYSA-N 0.000 description 1
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- WROUWQQRXUBECT-UHFFFAOYSA-N 2-ethylacrylic acid Chemical compound CCC(=C)C(O)=O WROUWQQRXUBECT-UHFFFAOYSA-N 0.000 description 1
- FRWYFWZENXDZMU-UHFFFAOYSA-N 2-iodoquinoline Chemical compound C1=CC=CC2=NC(I)=CC=C21 FRWYFWZENXDZMU-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- BYDYILQCRDXHLB-UHFFFAOYSA-N 3,5-dimethylpyridine-2-carbaldehyde Chemical compound CC1=CN=C(C=O)C(C)=C1 BYDYILQCRDXHLB-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- XLYMOEINVGRTEX-ARJAWSKDSA-N Ethyl hydrogen fumarate Chemical compound CCOC(=O)\C=C/C(O)=O XLYMOEINVGRTEX-ARJAWSKDSA-N 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052773 Promethium Inorganic materials 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 239000004280 Sodium formate Substances 0.000 description 1
- 239000005084 Strontium aluminate Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229920005603 alternating copolymer Polymers 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- LTPBRCUWZOMYOC-UHFFFAOYSA-N beryllium oxide Inorganic materials O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 1
- DVWBKCSKPCZFDE-UHFFFAOYSA-N bicyclo[2.2.1]hept-2-ene-2,3-dicarboxylic acid Chemical compound C1CC2C(C(=O)O)=C(C(O)=O)C1C2 DVWBKCSKPCZFDE-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 description 1
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 235000011132 calcium sulphate Nutrition 0.000 description 1
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- 229910003440 dysprosium oxide Inorganic materials 0.000 description 1
- NLQFUUYNQFMIJW-UHFFFAOYSA-N dysprosium(iii) oxide Chemical compound O=[Dy]O[Dy]=O NLQFUUYNQFMIJW-UHFFFAOYSA-N 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 229920005648 ethylene methacrylic acid copolymer Polymers 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 229910001940 europium oxide Inorganic materials 0.000 description 1
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 description 1
- LNYNHRRKSYMFHF-UHFFFAOYSA-K europium(3+);triacetate Chemical compound [Eu+3].CC([O-])=O.CC([O-])=O.CC([O-])=O LNYNHRRKSYMFHF-UHFFFAOYSA-K 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000010097 foam moulding Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- XLYMOEINVGRTEX-UHFFFAOYSA-N fumaric acid monoethyl ester Natural products CCOC(=O)C=CC(O)=O XLYMOEINVGRTEX-UHFFFAOYSA-N 0.000 description 1
- NKHAVTQWNUWKEO-UHFFFAOYSA-N fumaric acid monomethyl ester Natural products COC(=O)C=CC(O)=O NKHAVTQWNUWKEO-UHFFFAOYSA-N 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- NKHAVTQWNUWKEO-IHWYPQMZSA-N methyl hydrogen fumarate Chemical compound COC(=O)\C=C/C(O)=O NKHAVTQWNUWKEO-IHWYPQMZSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-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
- 230000005855 radiation Effects 0.000 description 1
- 229910052705 radium Inorganic materials 0.000 description 1
- HCWPIIXVSYCSAN-UHFFFAOYSA-N radium atom Chemical compound [Ra] HCWPIIXVSYCSAN-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001028 reflection method Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 1
- 229940071536 silver acetate Drugs 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- FNWBQFMGIFLWII-UHFFFAOYSA-N strontium aluminate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Al+3].[Sr+2].[Sr+2] FNWBQFMGIFLWII-UHFFFAOYSA-N 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- 125000000626 sulfinic acid group Chemical group 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052713 technetium Inorganic materials 0.000 description 1
- GKLVYJBZJHMRIY-UHFFFAOYSA-N technetium atom Chemical compound [Tc] GKLVYJBZJHMRIY-UHFFFAOYSA-N 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical class [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 229960000314 zinc acetate Drugs 0.000 description 1
- 235000013904 zinc acetate Nutrition 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、調製が容易で、かつ透明性、紫外線吸収性、機械的特性等に優れた超微粒子分散樹脂組成物に関する。本発明はまた酸基含有ポリマーの金属塩の経済的な製造方法に関する。 The present invention relates to an ultrafine particle dispersed resin composition that is easy to prepare and excellent in transparency, ultraviolet absorption, mechanical properties, and the like. The invention also relates to an economical process for the production of metal salts of acid group-containing polymers.
熱可塑性樹脂にナノオーダーの粒径を有するある種の無機化合物を配合した樹脂組成物は知られている。一般には、熱可塑性樹脂とナノオーダーの粒径を有する無機化合物粉末を直接混合し、溶融混練しても、無機化合物粉末の二次凝集によって樹脂中に分散する無機化合物粉末の粒径は大きくなり、所望の分散径で分散したものが得難いという問題がある。そのため、例えば界面活性剤で被覆された金属酸化物の超微粒子を熱可塑性樹脂に配合する方法が知られている（特許文献１参照）。この提案では、配合する熱可塑性樹脂として、軟質ポリ塩化ビニル、ポリエチレン、ポリエチレンテレフタレート及びポリカーボネートが好ましいとしている。 A resin composition in which a certain inorganic compound having a nano-order particle size is blended with a thermoplastic resin is known. In general, even if a thermoplastic resin and an inorganic compound powder having a nano-order particle size are directly mixed and melt-kneaded, the particle size of the inorganic compound powder dispersed in the resin increases due to secondary aggregation of the inorganic compound powder. There is a problem that it is difficult to obtain a dispersion with a desired dispersion diameter. Therefore, for example, a method of blending ultrafine particles of metal oxide coated with a surfactant into a thermoplastic resin is known (see Patent Document 1). In this proposal, soft polyvinyl chloride, polyethylene, polyethylene terephthalate and polycarbonate are preferred as the thermoplastic resin to be blended.
さらに、上記提案技術においては界面活性剤使用による弊害があるため、有機金属化合物や金属カルボニルなどを熱可塑性樹脂に配合し、溶融混練時にこれら金属化合物を分解することにより、超微粒子状金属酸化物を配合した樹脂組成物を得る方法も提案されている（特許文献２参照）。この提案においては、金属化合物として具体的には、鉄、クロム、マンガン、コバルト、ニッケル、モリブデン、バナジウム、タングステン、ルテニウムが例示されており、また熱可塑性樹脂としてオレフィン系樹脂を含む各種熱可塑性樹脂が例示されているが、オレフィン系樹脂としては、ポリエチレン樹脂、ポリプロピレン樹脂が好適であると記載されている。 Furthermore, in the above proposed technique, there is a harmful effect due to the use of a surfactant. Therefore, by adding an organometallic compound or metal carbonyl to a thermoplastic resin and decomposing these metal compounds during melt-kneading, an ultrafine metal oxide is obtained. There has also been proposed a method for obtaining a resin composition blended with (see Patent Document 2). In this proposal, specific examples of the metal compound include iron, chromium, manganese, cobalt, nickel, molybdenum, vanadium, tungsten, and ruthenium, and various thermoplastic resins including an olefin resin as the thermoplastic resin. However, it is described that polyethylene resin and polypropylene resin are preferable as the olefin resin.
一方、酸基含有ポリマーの酸基の少なくとも一部が金属イオンで中和された酸基含有ポリマー金属塩は広く知られており、その代表的なものはエチレン・（メタ）アクリル酸共重合体のアルカリ金属、アルカリ土類金属、亜鉛などの金属塩として知られているアイオノマーである。このような金属塩は、エチレン・（メタ）アクリル酸共重合体と相当する金属の化合物を溶融条件下で反応させることによって得ることができるが、反応を円滑に行なうためには、高温での反応、金属化合物のマスターバッチ化、反応助剤の添加、生成水の除去など、厳密な反応条件の採用が必要である。 On the other hand, acid group-containing polymer metal salts in which at least some of the acid groups of the acid group-containing polymer are neutralized with metal ions are widely known, and a typical one is an ethylene / (meth) acrylic acid copolymer. It is an ionomer known as a metal salt of alkali metal, alkaline earth metal, zinc or the like. Such a metal salt can be obtained by reacting an ethylene / (meth) acrylic acid copolymer and a corresponding metal compound under melting conditions. It is necessary to adopt strict reaction conditions such as reaction, masterbatch of metal compounds, addition of reaction aids, removal of generated water.
そこで本発明の目的は、金属化合物が樹脂中において超微粒子状で分散している樹脂組成物を、単なる溶融ブレンドにより製造することが可能な樹脂組成物を提供することにある。本発明の別の目的は、透明性、紫外線吸収性、機械的特性等に優れた樹脂組成物を提供することにある。本発明のさらに別の目的は、酸基含有ポリマーと超微粒子状金属化合物から、超微粒子状金属化合物が分散している中和された酸基含有ポリマーの組成物を製造する方法を提供することにある。本発明のさらに別の目的は、酸基含有ポリマーと超微粒子状金属化合物から酸基含有ポリマーの金属塩を経済的に製造する方法を提供することにある。 Accordingly, an object of the present invention is to provide a resin composition capable of producing a resin composition in which a metal compound is dispersed in ultrafine particles in a resin by simple melt blending. Another object of the present invention is to provide a resin composition excellent in transparency, ultraviolet absorption, mechanical properties and the like. Still another object of the present invention is to provide a method for producing a neutralized acid group-containing polymer composition in which an ultrafine metal compound is dispersed from an acid group-containing polymer and an ultrafine metal compound. It is in. Still another object of the present invention is to provide a method for economically producing a metal salt of an acid group-containing polymer from an acid group-containing polymer and an ultrafine metal compound.
本発明により、エチレン（メタ）アクリル酸共重合体である酸基含有ポリマーと、平均粒径が３０ｎｍ以下の金属含酸素化合物の超微粒子を溶融混練して、金属含酸素化合物の一部または全部によって酸基を中和して得られるエチレン（メタ）アクリル酸共重合体ポリマーの金属塩が提供される。 According to the present invention , an acid group-containing polymer, which is an ethylene (meth) acrylic acid copolymer, and ultrafine particles of a metal oxygen-containing compound having an average particle size of 30 nm or less are melt-kneaded, and part or all of the metal oxygen-containing compound Provides a metal salt of an ethylene (meth) acrylic acid copolymer obtained by neutralizing an acid group .
前記エチレン（メタ）アクリル酸共重合体は、不飽和カルボン酸含量が５〜２５重量％のエチレン（メタ）アクリル酸共重合体である。 The ethylene (meth) acrylic acid copolymer is an ethylene (meth) acrylic acid copolymer having an unsaturated carboxylic acid content of 5 to 25% by weight.
前記金属含酸素化合物は、アルカリ金属、アルカリ土類金属、アルミニウム族金属、希土類、銅、亜鉛、マンガン及びコバルトから選ばれる金属の酸化物、炭酸塩、重炭酸塩、カルボン酸塩、硫酸塩、リン酸塩、アルミン酸塩及び金属アルコキシドから選ばれる金属含酸素化合物である。 The metal oxygenate is an oxide, carbonate, bicarbonate, carboxylate, sulfate, or metal oxide selected from alkali metals, alkaline earth metals, aluminum group metals, rare earths, copper, zinc, manganese and cobalt. It is a metal oxygen-containing compound selected from phosphates, aluminates and metal alkoxides .
また本発明により、前記エチレン（メタ）アクリル酸共重合体と、前記金属の含酸素化合物の超微粒子を混合し、１００〜２５０℃の温度で溶融混練するエチレン（メタ）アクリル酸共重合体ポリマーの金属塩の製造方法が提供される。Further, according to the present invention, the ethylene (meth) acrylic acid copolymer and the ultrafine particles of the metal oxygen-containing compound are mixed and melt-kneaded at a temperature of 100 to 250 ° C. A method for producing the metal salt is provided.
本発明によれば、透明性、機械的特性等に優れた超微粒子分散酸基含有ポリマー組成物を容易に得ることができる。本発明によればまた、透明性、紫外線吸収性、機械的特性等に優れた、超微粒子分散の酸基含有ポリマー金属塩組成物を容易に得ることができる。さらに本発明によれば、酸基含有ポリマーの金属塩を、非常に温和な条件で製造することができる。 According to the present invention, it is possible to easily obtain an ultrafine particle dispersed acid group-containing polymer composition having excellent transparency and mechanical properties. According to the present invention, it is also possible to easily obtain an acid group-containing polymer metal salt composition dispersed in ultrafine particles, which is excellent in transparency, ultraviolet absorption, mechanical properties and the like. Furthermore, according to the present invention, the metal salt of an acid group-containing polymer can be produced under very mild conditions.
本発明で使用される酸基含有ポリマーは、カルボン酸基、スルホン酸基、スルフィン酸基、リン酸基などの酸性官能基を有する樹脂状重合体であって、酸性官能基を有する単量体と他の単量体を共重合する方法、ベースとなる幹ポリマーに酸性官能基を有する単量体をグラフト共重合する方法、酸性官能基の誘導基を有するポリマーの該誘導基を酸性官能基に変換する方法などによって得ることができる。酸基含有ポリマーにおける酸性官能基としては、とくにカルボン酸基が好適である。 The acid group-containing polymer used in the present invention is a resinous polymer having an acidic functional group such as a carboxylic acid group, a sulfonic acid group, a sulfinic acid group, or a phosphoric acid group, and a monomer having an acidic functional group A method of copolymerizing a monomer having an acidic functional group to a base trunk polymer, a method of graft-copolymerizing a monomer having an acidic functional group to a polymer having an acidic functional group-derived group It can obtain by the method of converting into. As the acidic functional group in the acid group-containing polymer, a carboxylic acid group is particularly suitable.
上記酸性官能基を有する単量体として、具体的にはアクリル酸、メタクリル酸、エタクリル酸、フマル酸、マレイン酸、マレイン酸モノメチル、マレイン酸モノエチル、無水マレイン酸、無水イタコン酸、ノルボルネン−２，３−ジカルボン酸及びその無水物などを好適例として例示することができる。 Specific examples of the monomer having an acidic functional group include acrylic acid, methacrylic acid, ethacrylic acid, fumaric acid, maleic acid, monomethyl maleate, monoethyl maleate, maleic anhydride, itaconic anhydride, norbornene-2, 3-dicarboxylic acid and its anhydride can be exemplified as preferred examples.
上記酸基含有ポリマーを形成する他の単量体単位としては、エチレン、プロピレン、１−ブテン、１−ペンテン、１−ヘキセン、１−オクテン、１−デセン、４−メチル−１−ペンテンなどの炭素数２〜２０のα−オレフィン、ブタジエン、イソプレンなどのジオレフィン、スチレン、α−メチルスチレン、ビニルトルエン、イソプロペニルトルエンなどのスチレン系単量体、酢酸ビニル、プロピオン酸ビニルなどのビニルエステル、アクリル酸メチル、アクリル酸エチル、アクリル酸イソプロピル、アクリル酸ｎ−プロピル、アクリル酸イソブチル、アクリル酸ｎ−ブチル、アクリル酸ｔ−ブチル、アクリル酸−２−エチルヘキシル、アクリル酸イソオクチル、アクリル酸グリシジル、メタクリル酸メチル、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−プロピル、メタクリル酸イソブチル、メタクリル酸ｎ−ブチル、メタクリル酸グリシジル、マレイン酸ジメチル、マレイン酸ジエチルなどの不飽和カルボン酸エステル、アクリロニトリル、メタクリロニトリルなどの不飽和ニトリル、塩化ビニル、塩化ビニリデン、弗化ビニルなどの含ハロゲン不飽和単量体、その他ビニルエーテル、マレイミド、ビニルシラン化合物などを例示することができる。 Examples of other monomer units forming the acid group-containing polymer include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 4-methyl-1-pentene, and the like. C2-C20 α-olefin, diolefins such as butadiene and isoprene, styrene monomers such as styrene, α-methylstyrene, vinyltoluene and isopropenyltoluene, vinyl esters such as vinyl acetate and vinyl propionate, Methyl acrylate, ethyl acrylate, isopropyl acrylate, n-propyl acrylate, isobutyl acrylate, n-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate, glycidyl acrylate, methacryl Methyl acid, ethyl methacrylate, methacryl Isopropyl acrylate, n-propyl methacrylate, isobutyl methacrylate, n-butyl methacrylate, glycidyl methacrylate, dimethyl maleate, unsaturated carboxylic acid esters such as diethyl maleate, unsaturated nitriles such as acrylonitrile and methacrylonitrile, chloride Examples thereof include halogen-containing unsaturated monomers such as vinyl, vinylidene chloride, and vinyl fluoride, and other vinyl ethers, maleimides, vinyl silane compounds, and the like.
酸基含有ポリマーとしてより具体的には、エチレンと不飽和カルボン酸の共重合体あるいはスチレンと不飽和カルボン酸の共重合体などを好適例としてあげることができる。これらは、ランダム共重合体、グラフト共重合体、交互共重合体などであり、とくにランダム共重合体が好ましい。これらの中では、オレフィンと不飽和カルボン酸の共重合体、とりわけエチレン・不飽和カルボン酸共重合体の使用が最も好ましい。 Specific examples of the acid group-containing polymer include a copolymer of ethylene and an unsaturated carboxylic acid or a copolymer of styrene and an unsaturated carboxylic acid. These are a random copolymer, a graft copolymer, an alternating copolymer, etc., and a random copolymer is particularly preferable. Among these, it is most preferable to use a copolymer of an olefin and an unsaturated carboxylic acid, particularly an ethylene / unsaturated carboxylic acid copolymer.
好適なエチレン・不飽和カルボン酸共重合体は、エチレンと不飽和カルボン酸のみの２元共重合体であってもよく、また任意に他の単量体が共重合された多元共重合体であってもよい。このエチレン・不飽和カルボン酸共重合体における不飽和カルボン酸含有量は、１〜３０重量％、とくに５〜２５重量％の範囲にあることが好ましく、また上記多元共重合体の場合においては、他の単量体は、例えば４０重量％以下、好ましくは３０重量％以下の割合で共重合されていてもよい。 A suitable ethylene / unsaturated carboxylic acid copolymer may be a binary copolymer of only ethylene and an unsaturated carboxylic acid, or a multi-component copolymer in which other monomers are optionally copolymerized. There may be. The unsaturated carboxylic acid content in the ethylene / unsaturated carboxylic acid copolymer is preferably in the range of 1 to 30% by weight, particularly 5 to 25% by weight. In the case of the multi-component copolymer, The other monomer may be copolymerized, for example, in a proportion of 40% by weight or less, preferably 30% by weight or less.
上記エチレン共重合体を構成する不飽和カルボン酸としては、上記したものを挙げることができるが、とくにアクリル酸又はメタクリル酸であることが好ましい。また上記エチレン多元共重合体における他の単量体としては、上記したようなビニルエステルや不飽和カルボン酸エステル、一酸化炭素などを例示することができる。 Examples of the unsaturated carboxylic acid constituting the ethylene copolymer include those described above, and acrylic acid or methacrylic acid is particularly preferable. Examples of the other monomer in the ethylene multi-component copolymer include vinyl esters, unsaturated carboxylic acid esters, and carbon monoxide as described above.
エチレン・不飽和カルボン酸共重合体としては、加工性、機械強度などを考慮すると、１９０℃、２１６０ｇ荷重におけるメルトフローレートが、０．０１〜３０００ｇ／１０分、とくに０．１〜１０００ｇ／１０分のものが好ましい。とくに金属の含酸素化合物によるエチレン・不飽和カルボン酸共重合体の中和を伴わない場合においては、金属含酸素化合物の超微粒子の二次凝集を防止しつつ良好な分散状態を達成し、かつ機械的強度に優れた樹脂組成物を得るためには、上記メルトフローレートが１〜８００ｇ／１０分、とくに１０〜６００ｇ／１０分のものを使用するのが好ましい。このようなエチレン・不飽和カルボン酸共重合体を使用した場合には、金属含酸素化合物の種類によっては、若干粒径の大きいミクロンオーダーの微粒子を配合した場合においても、溶融混練により該微粒子が酸処理により超微粒子状で分散するので好ましい。また金属の含酸素化合物によるエチレン・不飽和カルボン酸共重合体の中和を伴う場合には、中和に伴いメルトフローレートの低下が起こるため、反応の制御や得られる金属塩の物性、さらには部分的に超微粒子状金属含酸素化合物を残存させる場合にはその分散性などを考慮すると、上記メルトフローレートが１０〜１０００ｇ／１０分、とくに３０〜８００ｇ／１０分のものを使用するのが好ましい。 The ethylene / unsaturated carboxylic acid copolymer has a melt flow rate of 0.01 to 3000 g / 10 min, particularly 0.1 to 1000 g / 10 at 190 ° C. and a load of 2160 g in consideration of processability and mechanical strength. Minutes are preferred. In particular, in the case where the ethylene / unsaturated carboxylic acid copolymer is not neutralized by a metal oxygen-containing compound, a good dispersion state is achieved while preventing secondary aggregation of ultrafine particles of the metal oxygen-containing compound, and In order to obtain a resin composition excellent in mechanical strength, it is preferable to use a resin having a melt flow rate of 1 to 800 g / 10 minutes, particularly 10 to 600 g / 10 minutes. When such an ethylene / unsaturated carboxylic acid copolymer is used, depending on the type of the metal oxygen-containing compound, even if microparticles having a slightly larger particle size are blended, the fine particles may be melt-kneaded. It is preferable because it is dispersed in the form of ultrafine particles by acid treatment. In addition, when the ethylene / unsaturated carboxylic acid copolymer is neutralized with a metal oxygen-containing compound, the melt flow rate decreases with the neutralization, so the reaction is controlled and the physical properties of the resulting metal salt, In the case where the ultrafine metal oxygen-containing compound is partially left, considering the dispersibility and the like, the melt flow rate is 10 to 1000 g / 10 min, particularly 30 to 800 g / 10 min. Is preferred.
本発明の樹脂組成物においては、上記酸基含有ポリマーに金属の含酸素化合物の超微粒子を分散させるものである。上記含酸素化合物の金属種として具体的には、周期律表I〜IV族金属及び周期律表VI〜VIII族金属から選ばれる金属が好ましい。より具体的には、リチウム、ナトリウム、カリウム、ルビジウム、セシウムなどのアルカリ金属、銅、銀、金などの銅族金属、ベリリウム、マグネシウム、カルシウム、ストロンチウム、バリウム、ラジウムなどのアルカリ土類金属、亜鉛、カドミウム、水銀などの亜鉛族金属、アルミニウム、ガリウム、インジウム、タリウムなどのアルミニウム族金属、チタン、珪素などのIV族金属、スカンジウム、イットリウム、ランタン、セリウム、プラセオジム、ネオジム、プロメチウム、サマリウム、ユーロピウム、ガドリニウム、テルビウム、ジスプロシウム、ホルミウム、エルビウム、ツリウム、イッテルビウム、ルテチウムなどの希土類金属、クロム、モリブデン、タングステンなどのクロム族金属、マンガン、テクネチウム、レニウムなどのマンガン族金属、鉄、コバルト、ニッケルなどの鉄族金属などを挙げることができる。金属の含酸素化合物としては、単一の金属化合物である必要性はなく、２以上の金属からなる複合化合物であってもよく、また異なる金属の化合物の混合物を使用してもよい。これら金属化合物の中では、アルカリ金属、アルカリ土類金属、アルミニウム族金属、希土類、銅、亜鉛、マンガン及びコバルトから選ばれる金属を少なくとも１種含むものが好ましく、とりわけアルカリ土類金属、アルミニウム族金属、希土類及び亜鉛から選ばれる金属を含むものが好ましい。 In the resin composition of the present invention, ultrafine particles of a metal oxygen-containing compound are dispersed in the acid group-containing polymer. Specifically, the metal species of the oxygen-containing compound is preferably a metal selected from Periodic Table Group I to IV metal and Periodic Table Group VI to VIII metal. More specifically, alkali metals such as lithium, sodium, potassium, rubidium and cesium, copper group metals such as copper, silver and gold, alkaline earth metals such as beryllium, magnesium, calcium, strontium, barium and radium, zinc , Zinc group metals such as cadmium and mercury, aluminum group metals such as aluminum, gallium, indium and thallium, group IV metals such as titanium and silicon, scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, Rare earth metals such as gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium, chromium group metals such as chromium, molybdenum and tungsten, manganese, technetium and rhenium Mention may be made of manganese metals, iron, cobalt, and iron group metals such as nickel. The metal oxygen-containing compound need not be a single metal compound, may be a composite compound composed of two or more metals, or may be a mixture of compounds of different metals. Among these metal compounds, those containing at least one metal selected from alkali metals, alkaline earth metals, aluminum group metals, rare earths, copper, zinc, manganese, and cobalt are preferable, especially alkaline earth metals and aluminum group metals. Those containing a metal selected from rare earth and zinc are preferred.
また含酸素化合物としては、酸化物、水酸化物、炭酸塩、重炭酸塩、カルボン酸塩、硫酸塩、リン酸塩、アルミン酸塩、金属アルコキサイド、含酸素ランタノイド系複塩などを例示することができ、とくに酸化物、炭酸塩、カルボン酸塩、アルミン酸塩などの使用が好ましい。尚、上記カルボン酸塩及び金属アルコキサイドにおいては、炭素数２〜２０程度のカルボン酸塩及び炭素数２〜２０のアルコキサイドの使用が好ましい。 Examples of oxygen-containing compounds include oxides, hydroxides, carbonates, bicarbonates, carboxylates, sulfates, phosphates, aluminates, metal alkoxides, oxygen-containing lanthanoid double salts, etc. In particular, the use of oxides, carbonates, carboxylates, aluminates and the like is preferable. In the carboxylate and metal alkoxide, it is preferable to use a carboxylate having about 2 to 20 carbon atoms and an alkoxide having 2 to 20 carbon atoms.
金属の含酸素化合物の具体例としては、酸化ベリリウム、酸化マグネシウム、酸化カルシウム、酸化ストロンチウム、酸化バリウム、酸化銅、酸化亜鉛、酸化カドミウム、酸化ユーロピウム、酸化ツリウム、酸化ネオジム、酸化ジスプロシウム、酸化マンガン、酸化コバルトなどの酸化物、炭酸ナトリウム、炭酸カリウム、炭酸マグネシウム、炭酸カルシウム、炭酸ストロンチウム、炭酸バリウム、炭酸亜鉛などの炭酸塩、重炭酸ナトリウム、重炭酸カリウムなどの重炭酸塩、ギ酸ナトリウム、酢酸ナトリウム、酢酸カリウム、酢酸銀、酢酸銅、酢酸マグネシウム、酢酸カルシウム、酢酸亜鉛、酢酸ネオジム、酢酸ユーロピウム、酢酸ジスプロシウムなどのカルボン酸塩、硫酸ナトリウム、硫酸カリウム、硫酸マグネシウム、硫酸カルシウム、硫酸亜鉛などの硫酸塩、アルミン酸カルシウム、アルミン酸ストロンチウムなどのアルミン酸塩、珪素、タリウム、チタン、亜鉛又はアルミニウムのアルキルアルコキサイドなどを例示することができる。 Specific examples of metal oxygenates include beryllium oxide, magnesium oxide, calcium oxide, strontium oxide, barium oxide, copper oxide, zinc oxide, cadmium oxide, europium oxide, thulium oxide, neodymium oxide, dysprosium oxide, manganese oxide, Oxides such as cobalt oxide, sodium carbonate, potassium carbonate, magnesium carbonate, calcium carbonate, carbonate such as strontium carbonate, barium carbonate, zinc carbonate, bicarbonate such as sodium bicarbonate, potassium bicarbonate, sodium formate, sodium acetate , Potassium acetate, silver acetate, copper acetate, magnesium acetate, calcium acetate, zinc acetate, neodymium acetate, europium acetate, dysprosium acetate, sodium sulfate, potassium sulfate, magnesium sulfate, calcium sulfate It can be exemplified sulfates such as zinc sulfate, calcium aluminate, aluminates, such as strontium aluminate, silicon, thallium, titanium, and alkyl alkoxide of zinc or aluminum.
本発明におけるこれら金属の含酸素化合物の超微粒子は、一般にその平均粒径が１００ｎｍ以下、好ましくは５０ｎｍ以下、一層好ましくは３０ｎｍ以下の範囲の微粒子をいう。このような粒径を有する超微粒子状の含酸素化合物は、ミクロ微粒子を粉砕又は酸処理することにより製造する方法、含酸素化合物の調製時に超微粒子として生成、析出させる方法などによって得ることができる。例えば、金属酸化物のミクロンオーダーの微粒子を炭化水素溶媒中、粒径０．５ｍｍ程度のジルコニアと混合し、攪拌棒を用いて長時間高速回転することにより超微粒子まで粉砕するビーズミル粉砕法によって得ることができる。あるいは金属酸化物の微粒子を数十重量％程度の濃度の酢酸水溶液中に懸濁させて攪拌する、あるいは金属化合物の微粒子を酸基含有ポリマーと予備的に溶融混合するというような酸処理法によっても超微粒子状のものを得ることができる。 The ultrafine particles of these metal oxygen-containing compounds in the present invention generally refer to fine particles having an average particle diameter of 100 nm or less, preferably 50 nm or less, and more preferably 30 nm or less. The ultrafine oxygen-containing compound having such a particle size can be obtained by a method of producing microparticles by pulverization or acid treatment, a method of producing and precipitating as ultrafine particles when preparing the oxygen-containing compound, and the like. . For example, micron order fine particles of a metal oxide are mixed with zirconia having a particle size of about 0.5 mm in a hydrocarbon solvent, and obtained by a bead mill pulverization method that pulverizes to ultrafine particles by rotating at high speed for a long time using a stirring rod. be able to. Alternatively, the metal oxide fine particles may be suspended in an acetic acid aqueous solution having a concentration of several tens of weight percent and stirred, or the metal compound fine particles may be preliminarily melt mixed with the acid group-containing polymer. In addition, ultrafine particles can be obtained.
本発明の超微粒子分散樹脂組成物は、酸基含有ポリマーと超微粒子状の金属含酸素化合物をドライブレンドし、これを通常の溶融混練装置、例えば一軸又は二軸の押出機、バンバリーミキサー、ニーダー、ロールなどを用いて、溶融混練するという簡単な方法によって得ることができる。溶融混練の温度は、酸基含有ポリマーや金属含酸素化合物の種類によっても異なるが、一般には酸基含有ポリマーの融点以上であって、１００〜２５０℃、好ましくは１００〜２００℃の範囲である。酸基含有ポリマーがエチレン・（メタ）アクリル酸共重合体の場合についてより詳細に述べると、配合する金属含酸素化合物が、金属種が銅族金属又は周期律表III〜VIII族金属である化合物、あるいはアルカリ金属、アルカリ土類金属又は亜鉛族金属の硫酸塩、アルミン酸塩のような該共重合体との反応性に乏しい化合物である場合には、上記のような広範囲の温度領域で好適に混合することが可能である。 The ultrafine particle-dispersed resin composition of the present invention is obtained by dry blending an acid group-containing polymer and an ultrafine metal oxygen-containing compound, and then using an ordinary melt-kneading apparatus such as a uniaxial or biaxial extruder, a Banbury mixer, a kneader. It can be obtained by a simple method of melt kneading using a roll or the like. The temperature of the melt-kneading varies depending on the kind of the acid group-containing polymer and the metal oxygen-containing compound, but is generally not lower than the melting point of the acid group-containing polymer and is in the range of 100 to 250 ° C., preferably 100 to 200 ° C. . The case where the acid group-containing polymer is an ethylene / (meth) acrylic acid copolymer will be described in more detail. The compound containing a metal oxygen compound is a copper group metal or a group III-VIII metal in the periodic table. Or a compound having poor reactivity with the copolymer such as sulfate, aluminate of alkali metal, alkaline earth metal or zinc group metal, and suitable for a wide temperature range as described above. Can be mixed.
一方、配合する金属含酸素化合物が、アルカリ金属、アルカリ土類金属又は亜鉛族金属などの酸化物、炭酸塩、カルボン酸塩などを使用する場合には反応性に富むため、エチレン・（メタ）アクリル酸共重合体の融点以上であって、１００〜２００℃、好ましくは１００〜１８０℃の範囲で、１〜６０分間程度、溶融混練することが好ましい。本発明においては、酸基含有ポリマーと超微粒子状金属含酸素化合物を溶融混練する際、溶融混練の温度及び時間を制御することにより、（１）酸基含有ポリマー、例えばエチレン・（メタ）アクリル酸共重合体と金属含酸素化合物の樹脂組成物、（２）金属含酸素化合物の一部により金属塩化された酸基含有ポリマー（例えばエチレン・（メタ）アクリル酸共重合体）と金属含酸素化合物の樹脂組成物又は（３）金属含酸素化合物が完全に反応に使用されて、金属塩化された酸基含有ポリマー（例えばエチレン・（メタ）アクリル酸共重合体）のいずれかを得ることができる。とくに本発明の上記（２）及び（３）の態様である金属塩化された酸基含有ポリマーを製造する場合には、従来ミクロ単位あるいはそれ以上の粒径の金属含酸素化合物を用いて、溶融混練により酸基含有ポリマーの金属塩（アイオノマー）を製造する場合に比べ、低い温度、短い反応時間で金属塩化が可能となり、経済的な金属塩の製法となる。また（２）及び（３）の態様の場合、押出機等で溶融混練して押出成形することにより、酸基含有ポリマーを金属塩化すると同時に、その成形物（例えばゴルフボールなど）を直接成形できるという利点がある。例えばエチレン・（メタ）アクリル酸共重合体と超微粒子状のアルカリ土類金属酸化物から、両者の組成物、該共重合体のアルカリ土類金属塩と超微粒子状のアルカリ土類金属酸化物の組成物、又は該共重合体のアルカリ土類金属塩が得られ、これらは透明性、機械的特性に優れている。また同様にエチレン・（メタ）アクリル酸共重合体と超微粒子状の酸化亜鉛から、両者の組成物、該共重合体の亜鉛塩と超微粒子状の酸化亜鉛の組成物、又は該共重合体の亜鉛塩が得られ、これらは透明性、紫外線吸収性等に優れている。 On the other hand, since the metal oxygen-containing compound to be used is highly reactive when oxides such as alkali metals, alkaline earth metals or zinc group metals, carbonates, carboxylates, etc. are used, ethylene (meta) It is preferably melt-kneaded for about 1 to 60 minutes in the range of 100 to 200 ° C, preferably 100 to 180 ° C, which is not lower than the melting point of the acrylic acid copolymer. In the present invention, when melt-kneading an acid group-containing polymer and an ultrafine metal oxygen-containing compound, by controlling the temperature and time of the melt-kneading, (1) an acid group-containing polymer such as ethylene (meth) acrylic Resin composition of acid copolymer and metal oxygen-containing compound, (2) acid group-containing polymer (for example, ethylene / (meth) acrylic acid copolymer) metal-oxygenated by a part of metal oxygen-containing compound and metal oxygen-containing A compound resin composition or (3) a metal oxygenated compound is completely used in the reaction to obtain a metallized acid group-containing polymer (for example, ethylene / (meth) acrylic acid copolymer). it can. In particular, in the case of producing the metal chloride acid group-containing polymer according to the above aspects (2) and (3) of the present invention, a metal oxygen-containing compound having a particle size of micro units or larger is used to melt Compared with the case of producing a metal salt (ionomer) of an acid group-containing polymer by kneading, metal chloride can be carried out at a low temperature and a short reaction time, which is an economical method for producing a metal salt. In the case of the embodiments (2) and (3), the acid group-containing polymer can be converted into a metal salt and simultaneously molded into a molded product (for example, a golf ball) by melting and kneading with an extruder or the like. There is an advantage. For example, from ethylene / (meth) acrylic acid copolymer and ultrafine alkaline earth metal oxide, composition of both, alkaline earth metal salt of the copolymer and ultrafine alkaline earth metal oxide Or an alkaline earth metal salt of the copolymer, which is excellent in transparency and mechanical properties. Similarly, from an ethylene / (meth) acrylic acid copolymer and ultrafine zinc oxide, a composition of both, a composition of the zinc salt of the copolymer and ultrafine zinc oxide, or the copolymer These zinc salts are obtained, and these are excellent in transparency, ultraviolet absorption and the like.
従来、樹脂中への超微粒子状無機化合物の配合においては、二次凝集による微粒子粒径の増大が懸念されていたが、本発明においてはこのような恐れは無いほか、金属含酸素化合物の種類によっては、例えば、酸化銅のような銅族化合物、酸化マグネシウムのようなアルカリ土類金属化合物、酸化亜鉛のような亜鉛化合物においては、ミクロン単位の粒径を有する微粒子を配合した場合においても、溶融混練時の温度、時間を適当に選択することにより溶融混練時に酸処理され、超微粒子が分散した状態の本発明の樹脂組成物が得られる。 Conventionally, in blending ultrafine inorganic compounds into resins, there has been a concern about the increase in particle size due to secondary aggregation, but in the present invention, there is no such fear, and the types of metal oxygen-containing compounds Depending on, for example, in a copper group compound such as copper oxide, an alkaline earth metal compound such as magnesium oxide, and a zinc compound such as zinc oxide, even when fine particles having a particle size of micron unit are blended, By appropriately selecting the temperature and time at the time of melt kneading, the resin composition of the present invention in which the acid treatment is performed at the time of melt kneading and the ultrafine particles are dispersed can be obtained.
酸基含有ポリマーと金属含酸素化合物の配合割合は、目的に応じて任意に選択することができるが、通常、酸基含有ポリマー１００重量部に対し、金属含酸素化合物を０．０１〜３０重量部、好ましくは０．１〜２０重量部程度の割合とされる。 The blending ratio of the acid group-containing polymer and the metal oxygen-containing compound can be arbitrarily selected according to the purpose, but usually the metal oxygen-containing compound is 0.01 to 30 wt. Per 100 parts by weight of the acid group-containing polymer. Parts, preferably about 0.1 to 20 parts by weight.
本発明の樹脂組成物においては、必要に応じ、その他の各種添加剤を配合することができる。このような添加剤の例として、酸化防止剤、光安定剤、帯電防止剤、紫外線吸収剤、滑剤、架橋剤、発泡剤などを例示することができる。 In the resin composition of this invention, other various additives can be mix | blended as needed. Examples of such additives include antioxidants, light stabilizers, antistatic agents, ultraviolet absorbers, lubricants, crosslinking agents, and foaming agents.
本発明の樹脂組成物、あるいは本発明の方法によって得られる酸基含有ポリマーの金属塩は、押出成形、射出成形、中空成形、圧縮成形、真空成形、発泡成形など各種成形方法により、種々の形状の成形品にして利用することができる。本発明の樹脂組成物、あるいは本発明の方法によって得られる酸基含有ポリマーの金属塩は、使用する含酸素金属化合物の種類によるが、例えば紫外線吸収材料、発光（蓄光）材料、光学部品材料、半導体材料、電磁波吸収材料、酸素吸収材料、ガスバリアー材料、帯電材料、透明フイルム材料、水性ディスパージョン材料、バインダー材料、封止材料、床（タイル）材料、塗料・インキ材料、電化製品（掃除機部品、冷蔵庫部品など）用材料、各種サニタリー用材料、玩具・雑貨材料、トナー材料、ゴルフボールのコア、マントル及び表皮材料、化粧品容器等の容器、セラミックスなどとの複合材料などとして使用することができる。また本発明において酸化物として銅酸化物を使用して得られる樹脂組成物は、抗菌材料としても有用である。 The resin composition of the present invention or the metal salt of an acid group-containing polymer obtained by the method of the present invention can be produced in various shapes by various molding methods such as extrusion molding, injection molding, hollow molding, compression molding, vacuum molding, and foam molding. It can be used as a molded product. The metal salt of the acid group-containing polymer obtained by the resin composition of the present invention or the method of the present invention depends on the type of the oxygen-containing metal compound used, but for example, an ultraviolet absorbing material, a light emitting (light storage) material, an optical component material, Semiconductor materials, electromagnetic wave absorbing materials, oxygen absorbing materials, gas barrier materials, charging materials, transparent film materials, aqueous dispersion materials, binder materials, sealing materials, floor (tile) materials, paint / ink materials, electrical appliances (vacuum cleaners) Parts, refrigerator parts, etc.), various sanitary materials, toys and miscellaneous materials, toner materials, golf ball cores, mantle and skin materials, containers for cosmetic containers, composite materials with ceramics, etc. it can. In the present invention, the resin composition obtained using copper oxide as the oxide is also useful as an antibacterial material.
また本発明で得られる超微粒子分散樹脂組成物が、酸基含有ポリマー、例えばエチレン・（メタ）アクリル酸共重合体と金属含酸素化合物の樹脂組成物や金属含酸素化合物の一部により金属塩化された酸基含有ポリマー（例えばエチレン・（メタ）アクリル酸共重合体）と金属含酸素化合物の樹脂組成物である場合には、これらの成形体（例えばフイルム）を硫化処理することにより、紫外線や熱線を遮蔽する成形体を得ることができる。 Further, the ultrafine particle-dispersed resin composition obtained in the present invention is an acid group-containing polymer, for example, a metal chloride containing a part of a resin composition of an ethylene / (meth) acrylic acid copolymer and a metal oxygen-containing compound or a metal oxygen-containing compound. In the case of a resin composition comprising an acid group-containing polymer (for example, ethylene / (meth) acrylic acid copolymer) and a metal oxygen-containing compound, these molded bodies (for example, a film) are subjected to sulfur treatment to produce ultraviolet rays. And a molded body that shields heat rays can be obtained.
以下、実施例により本発明をさらに詳細に説明する。尚、実施例において使用した原料及び物性評価方法は、以下の通りである。 Hereinafter, the present invention will be described in more detail with reference to examples. In addition, the raw material used in the Example and the physical-property evaluation method are as follows.
１．原料
（１）酸基含有ポリマー
（１−１）ＥＡＡ−１：エチレン・アクリル酸共重合体（アクリル酸含量１５重量％、メルトフローレート（ＭＦＲ）（１９０℃、２１６０ｇ荷重、以下、同じ）６０ｇ／１０分）
（１−２）ＥＡＡ−２：エチレン・アクリル酸共重合体（アクリル酸含量２０重量％、ＭＦＲ３００ｇ／１０分）
（１−３）ＥＭＡＡ−１：エチレン・メタクリル酸共重合体（メタクリル酸含量１５重量％、ＭＦＲ６０ｇ／１０分）
（１−４）ＥＭＡＡ−２：エチレン・メタクリル酸共重合体（メタクリル酸含量２０重量％、ＭＦＲ３００ｇ／１０分）
（２）金属含酸素化合物
（２−１）ｎａｎｏＺｎＯ（超微粒子状酸化亜鉛、平均粒径２０ｎｍ、堺化学（株）製）
（２−２）ｍｉｃｒｏＺｎＯ（微粒子状酸化亜鉛、粒径０．３〜０．４μｍ、堺化学（株）製）
（２−３）ｎａｎｏＭｇＯ（超微粒子状酸化マグネシウム、平均粒径１０ｎｍ、和光純薬（株）製）
（２−４）ｍｉｃｒｏＭｇＯ（微粒子状酸化マグネシウム、粒径１０〜８０μｍ、和光純薬（株）製）
（２−５）ｍｉｃｒｏＣｕ２Ｏ（微粒子状酸化銅、粒径１〜１０μｍ、Ａｌｄｒｉｃｈ（株）製）
1. Raw material (1) Acid group-containing polymer (1-1) EAA-1: Ethylene / acrylic acid copolymer (acrylic acid content 15% by weight, melt flow rate (MFR) (190 ° C., 2160 g load, hereinafter the same) 60 g / 10 minutes)
(1-2) EAA-2: ethylene / acrylic acid copolymer (acrylic acid content 20% by weight, MFR 300 g / 10 min)
(1-3) EMAA-1: Ethylene / methacrylic acid copolymer (methacrylic acid content 15% by weight, MFR 60 g / 10 min)
(1-4) EMAA-2: Ethylene / methacrylic acid copolymer (methacrylic acid content 20% by weight, MFR 300 g / 10 min)
(2) Metal Oxygen Compound (2-1) nanoZnO (Ultrafine Zinc Oxide, Average Particle Size 20 nm, manufactured by Sakai Chemical Co., Ltd.)
(2-2) microZnO (particulate zinc oxide, particle size 0.3 to 0.4 μm, manufactured by Sakai Chemical Co., Ltd.)
(2-3) nanoMgO (ultrafine magnesium oxide, average particle size 10 nm, manufactured by Wako Pure Chemical Industries, Ltd.)
(2-4) microMgO (particulate magnesium oxide, particle size 10 to 80 μm, manufactured by Wako Pure Chemical Industries, Ltd.)
(2-5) microCu 2 O (particulate copper oxide,
（３）物性測定方法
（３−１）ＭＦＲ：１９０℃、２１６０ｇ荷重
（３−２）光学特性（Ｈａｚｅ）
１ｍｍ厚みのプレスシートにつき、ＡＳＴＭ Ｄ−１００３に基づき測定した。尚、発泡サンプルについては、プレス成形と脱気を繰り返し、気泡のないサンプルを作成した。
（３−２）表面硬さ
上記プレスシートのショアＤ硬度を測定した。
（３−３）ビカット軟化点
ＪＩＳ Ｋ−７２０６に準じた
（３−４）引張特性
ＪＩＳ Ｋ６７６０に準じ、２号ダンベルを用い、引張速度２００ｍｍ／分、チャック間８０ｍｍの条件で測定した。
（３−５）広角Ｘ線回折（ＷＡＸＤ）測定
理学電機（株）製Ｘ線発生装置を用い、Ｎｉフィルターで濾光したＣｕＫα線（出力４０ｋＶ、１５０ｍＡ）を線源として行った。スキャン速度５°／分、スキャンステップ０．０２°の条件下、反射法にてデータの取り込みを行った。
（３−６）フーリエ変換赤外分光分析（ＦＴ−ＩＲ）測定
島津製作所（株）製ＩＲ Ｐｒｅｓｔｉｇｅ−２１を用い、ＡＴＲにて行った。
（３−７）紫外−可視分光（ＵＶ−ＶＩＳ）測定
日立製作所（株）製Ｕ−４０００を用い、試料厚み０．６ｍｍ、スキャン速度３００ｎｍ／分の条件下、透過法にて測定を行った。
(3) Physical property measurement method (3-1) MFR: 190 ° C., 2160 g load (3-2) Optical characteristics (Haze)
It measured based on ASTM D-1003 about the press sheet of 1 mm thickness. In addition, about the foam sample, press molding and deaeration were repeated and the sample without a bubble was created.
(3-2) Surface hardness The Shore D hardness of the press sheet was measured.
(3-3) Vicat softening point (3-4) Tensile properties according to JIS K-7206 According to JIS K6760, a No. 2 dumbbell was used and the tensile speed was 200 mm / min and the chuck spacing was 80 mm.
(3-5) Wide-angle X-ray diffraction (WAXD) measurement Using an X-ray generator manufactured by Rigaku Corporation, CuKα rays (output 40 kV, 150 mA) filtered with a Ni filter were used as a radiation source. Data was captured by the reflection method under conditions of a scan speed of 5 ° / min and a scan step of 0.02 °.
(3-6) Fourier transform infrared spectroscopic analysis (FT-IR) measurement It was performed by ATR using Shimadzu Corporation IR Prestige-21.
(3-7) Ultraviolet-Visible Spectroscopy (UV-VIS) Measurement Using U-4000 manufactured by Hitachi, Ltd., measurement was performed by a transmission method under the conditions of a sample thickness of 0.6 mm and a scanning speed of 300 nm / min. .
[実施例１]
ＥＭＡＡ−１を ７５ｇとｎａｎｏＺｎＯを３．１９ｇ（ＥＭＡＡ−１のカルボキシル基に対し、６０％当量に該当）を、東洋精機（株）製ラボプラストミルに仕込み、１１０℃の設定温度、回転数６０ｒｐｍで溶融混練した。混練開始後２〜３分の間に溶融トルクは急激に増大し、８分過ぎにはほぼ飽和に達した。また樹脂温度も開始直後から終了まで上昇が見られ、終了時点（１３分後）には１７０℃に達した。溶融混練開始後、カルボキシル基とＺｎＯとの反応より生成する水の気化によると思われる発泡が見られたが、５分後には発泡は収まった。溶融混練後のサンプルを取り出し、試験片を作成してその物性を測定した。
[Example 1]
75 g of EMAA-1 and 3.19 g of nanoZnO (corresponding to 60% equivalent with respect to the carboxyl group of EMAA-1) were charged into a laboratory plast mill manufactured by Toyo Seiki Co., Ltd. at a set temperature of 110 ° C. and a rotational speed of 60 rpm. Was melt kneaded. The melt torque increased rapidly in 2 to 3 minutes after the start of kneading, and almost reached saturation after 8 minutes. The resin temperature also increased from the start to the end, reaching 170 ° C. at the end (after 13 minutes). After the start of melt-kneading, foaming that was thought to be due to vaporization of water generated from the reaction between the carboxyl group and ZnO was observed, but foaming stopped after 5 minutes. A sample after melt-kneading was taken out, a test piece was prepared, and its physical properties were measured.
生成物のＭＦＲは１．１ｇ／分と低く、Ｈａｚｅは３．３％と透明であり、ＥＭＡＡ−１の亜鉛塩が生成している。フイルムサンプルについてＷＡＸＤの結果では、ＺｎＯ結晶に帰属される回折ピークは全く観察されず、またＦＴ−ＩＲの結果より、１７００ｃｍ−１付近の−ＣＯＯＨのＣ＝Ｏに帰属されるピークの他に、１５５０及び１６２６ｃｍ−１にＺｎ２＋と結合した−ＣＯＯのＣ＝Ｏ非対称伸縮振動に帰属されるピークが観察された。以上のことから、ｎａｎｏＺｎＯは、速やかにＥＭＡＡ−１と反応し、亜鉛塩となったことが明らかである。 The product has a low MFR of 1.1 g / min, a transparent haze of 3.3%, and a zinc salt of EMAA-1. In the WAXD result for the film sample, no diffraction peak attributed to the ZnO crystal is observed, and from the FT-IR result, in addition to the peak attributed to C═O of —COOH around 1700 cm −1 , Peaks attributed to the C═O asymmetric stretching vibration of —COO bonded to Zn 2+ at 1550 and 1626 cm −1 were observed. From the above, it is clear that nanoZnO rapidly reacted with EMAA-1 to become a zinc salt.
一方、ＵＶ−ＶＩＳの結果を、ＥＭＡＡ−１やそれをベースとする同じ中和度の亜鉛アイオノマー、及び参考例１で得られたサンプルのものと併せて図１に示す。図１においては、ＥＭＡＡ−１やそれをベースとする同じ中和度の亜鉛塩においては認められない３６５ｎｍにおける小さなピーク（３８０ｎｍの立ち上がり）が認められ、僅かなＺｎＯの残存があると考えられるが、ＷＡＸＤの結果を考慮すると、その量は微々たるものと考えられる。
また上記サンプルのその他の物性を、表２に示す。
On the other hand, the results of UV-VIS are shown in FIG. 1 together with EMAA-1, the zinc ionomer of the same neutralization degree based on EMAA, and the sample obtained in Reference Example 1. In FIG. 1, a small peak at 365 nm (rise of 380 nm) that is not observed in EMAA-1 or a zinc salt having the same neutralization degree based on EMAA-1 is observed, and it is considered that there is a slight residual ZnO. Considering the result of WAXD, the amount is considered to be insignificant.
Table 2 shows other physical properties of the sample.
[実施例２〜４]
実施例１において、ＥＭＡＡ−１の代わりにＥＡＡ−１、ＥＡＡ−２又はＥＭＡＡ−２を用い、ｎａｎｏＺｎＯを表１に示す割合で用いた以外は、実施例１と同様に溶融混練を行った。上昇パターンは異なるものの、同様なトルク上昇及び温度上昇が認められた。溶融混練３０分後のサンプルを採取し、その物性を測定した。Ｈａｚｅはいずれも３％以下であり、樹脂は透明で、ＷＡＸＤの測定結果では、いずれもＺｎＯの残存は認められず、またＦＴ−ＩＲの測定結果を合わせ考慮すると、それぞれの亜鉛塩が生成していることが明らかである。
[Examples 2 to 4]
In Example 1, melt kneading was performed in the same manner as in Example 1 except that EAA-1, EAA-2 or EMAA-2 was used instead of EMAA-1, and nanoZnO was used in the ratio shown in Table 1. Although the increase pattern was different, similar torque increase and temperature increase were observed. A sample 30 minutes after melt-kneading was collected and measured for physical properties. The haze is 3% or less, the resin is transparent, and none of the WAXD measurement results show any remaining ZnO. When the FT-IR measurement results are taken into account, the respective zinc salts are formed. It is clear that
またＵＶ−ＶＩＳの結果を、図１における対比サンプルのものと同様な対比サンプルのものと併せて図２〜４に示す。図１に見られたような３６５ｎｍにおける小さなピークは認められなかったが、図１のものと同様に、いずれも２８０ｎｍ近辺において、ＥＡＡ−１（又はＥＡＡ−２、又はＥＭＡＡ−２）やそれをベースとする同じ中和度の亜鉛塩よりも強い吸収が認められた。これは発色団である（メタ）アクリル酸基の有するカルボニル基によるものと想定しており、凝集状態の相違に基づくものと推定している。
また上記サンプルの他の物性を表２に示す。
Moreover, the result of UV-VIS is shown in FIGS. 2-4 with the thing of the contrast sample similar to the contrast sample in FIG. Although a small peak at 365 nm as seen in FIG. 1 was not observed, in the same manner as in FIG. 1, in the vicinity of 280 nm, EAA-1 (or EAA-2 or EMAA-2) and Stronger absorption was observed than the base zinc salt of the same neutralization degree. This is assumed to be due to the carbonyl group of the (meth) acrylic acid group which is a chromophore, and is presumed to be based on the difference in the aggregation state.
Other physical properties of the sample are shown in Table 2.
[参考例１〜４]
実施例１〜４において、ｎａｎｏＺｎＯの代わりに、ｍｉｃｒｏＺｎＯを使用し、設定温度１５０℃にて、同様に溶融混練を行った。溶融トルクの上昇は非常に緩やかであり、混練温度はほとんど上昇せず、設定温度に維持できた。
[Reference Examples 1 to 4]
In Examples 1 to 4, microZnO was used instead of nanoZnO, and melt kneading was similarly performed at a set temperature of 150 ° C. The increase in melting torque was very gradual, the kneading temperature hardly increased, and could be maintained at the set temperature.
１５分間混練後のサンプルにつき物性を測定した。ＷＡＸＤ及びＵＶ−ＶＩＳ（図１〜４）の結果では、いずれもＺｎＯが残存しており、またＦＴ−ＩＲの結果では若干の亜鉛塩の生成は認められているが、他の物性は表２に示すとおりでＨａｚｅも高く、亜鉛塩の生成量は少ないことが分かる。 The physical properties of the sample after kneading for 15 minutes were measured. In both the results of WAXD and UV-VIS (FIGS. 1 to 4), ZnO remains, and in the results of FT-IR, some formation of zinc salt is recognized, but other physical properties are shown in Table 2. It can be seen that the haze is high and the amount of zinc salt produced is small.
[実施例５]
ＥＡＡ−１を７５ｇとｎａｎｏＭｇＯを１．８９ｇ（ＥＡＡ−１のカルボキシル基に対し、６０％当量に該当）を、実施例１と同様にして１５０℃で溶融混練した。実施例１と同様に、混練直後から溶融トルク及び温度が上昇した。５分後にトルクが安定したところから、反応はほぼ終了したものと考えられる。
１５分混練後のサンプルにつき、物性の測定を行った。ＷＡＸＤの結果では、サンプル中にＭｇＯは残存しておらず、またＦＴ−ＩＲの結果では、マグネシウム塩の生成が確認された。他の物性についても、表２に示す通りであり、Ｈａｚｅは１．８％と低く、透明であった。
[Example 5]
75 g of EAA-1 and 1.89 g of nanoMgO (corresponding to 60% equivalent with respect to the carboxyl group of EAA-1) were melt-kneaded at 150 ° C. in the same manner as in Example 1. As in Example 1, the melting torque and temperature increased immediately after kneading. Since the torque became stable after 5 minutes, the reaction is considered to be almost completed.
The physical properties of the sample after kneading for 15 minutes were measured. As a result of WAXD, no MgO remained in the sample, and as a result of FT-IR, formation of a magnesium salt was confirmed. The other physical properties were also as shown in Table 2. The haze was as low as 1.8% and was transparent.
[参考例５]
実施例５において、ｎａｎｏＭｇＯの代わりにｍｉｃｒｏＭｇＯを使用した以外は、実施例５と同様に溶融混練を行った。ＷＡＸＤの結果ではサンプル中にＭｇＯが残存しており、またＦＴ−ＩＲの結果では、若干のマグネシウム塩の生成は認められた。他の物性につき、表２に示す通りであり、Ｈａｚｅも高く、半透明であった。
[Reference Example 5]
In Example 5, melt-kneading was performed in the same manner as in Example 5 except that microMgO was used instead of nanoMgO. In the results of WAXD, MgO remained in the sample, and in the results of FT-IR, the formation of some magnesium salts was observed. The other physical properties were as shown in Table 2. The haze was also high and translucent.
[実施例６]
ＥＡＡ−１を７５ｇとｍｉｃｒｏＣｕ２Ｏ１．５ｇを実施例１と同様にして２００℃、２２０℃及び２４０℃でそれぞれ３０分間溶融混練した。得られたサンプルをフイルム化したところ、いずれも緑色の透明フイルムが得られたところから、ミクロンオーダーのＣｕ２Ｏが溶融混練により超微粒子化されたものと考えられる。このフイルムを硫化処理して得られるフイルムは、紫外線及び近赤外線領域で強い吸収を示した。このフイルムは、太陽光線の紫外線及び熱線を同時にカットするフィルターとして有用である。
[Example 6]
In the same manner as in Example 1, 75 g of EAA-1 and 1.5 g of microCu 2 O were melt-kneaded at 200 ° C., 220 ° C., and 240 ° C. for 30 minutes. When the obtained samples were turned into films, green transparent films were obtained in all cases, and it is considered that micron-order Cu 2 O was made into ultrafine particles by melt kneading. The film obtained by sulfiding this film exhibited strong absorption in the ultraviolet and near infrared regions. This film is useful as a filter that simultaneously cuts ultraviolet rays and heat rays of sunlight.
一方、ＥＡＡ−１の代わりに、アクリル酸エチル含量２０重量％のエチレン・アクリル酸エチル共重合体を使用したときには、透明フイルムは得られず、溶融混練による微粒子化は認められなかった。またそのフイルムを硫化処理しても、近赤外線領域での吸収は認められなかった。 On the other hand, when an ethylene / ethyl acrylate copolymer having an ethyl acrylate content of 20% by weight was used instead of EAA-1, a transparent film was not obtained, and no fine particles were formed by melt-kneading. Even when the film was sulfurized, no absorption was observed in the near infrared region.
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