CN106163797B - 包含粘合层的树脂金属复合体 - Google Patents
包含粘合层的树脂金属复合体 Download PDFInfo
- Publication number
- CN106163797B CN106163797B CN201480077393.4A CN201480077393A CN106163797B CN 106163797 B CN106163797 B CN 106163797B CN 201480077393 A CN201480077393 A CN 201480077393A CN 106163797 B CN106163797 B CN 106163797B
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- China
- Prior art keywords
- adhesive layer
- resin
- cation
- metal composite
- metal
- Prior art date
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- 229920005989 resin Polymers 0.000 title claims abstract description 71
- 239000011347 resin Substances 0.000 title claims abstract description 71
- 239000012790 adhesive layer Substances 0.000 title claims abstract description 69
- 239000010410 layer Substances 0.000 claims abstract description 74
- 229910052751 metal Inorganic materials 0.000 claims abstract description 55
- 239000002184 metal Substances 0.000 claims abstract description 55
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 239000000126 substance Substances 0.000 claims abstract description 17
- 239000000178 monomer Substances 0.000 claims abstract description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 12
- 229920001897 terpolymer Polymers 0.000 claims abstract description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 11
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims abstract description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 7
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 6
- 125000004185 ester group Chemical group 0.000 claims abstract description 6
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- 239000001257 hydrogen Substances 0.000 claims abstract description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 5
- 239000005977 Ethylene Substances 0.000 claims abstract description 4
- 239000002905 metal composite material Substances 0.000 claims description 46
- -1 oxide Chemical compound 0.000 claims description 33
- 229920001577 copolymer Polymers 0.000 claims description 27
- 150000001768 cations Chemical class 0.000 claims description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 11
- 229920000554 ionomer Polymers 0.000 claims description 11
- 229920000642 polymer Polymers 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 9
- 239000004952 Polyamide Substances 0.000 claims description 8
- 229920002647 polyamide Polymers 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 7
- 239000004711 α-olefin Substances 0.000 claims description 7
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 6
- 229920006027 ternary co-polymer Polymers 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 5
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 5
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 5
- 229920000098 polyolefin Polymers 0.000 claims description 5
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- 229920000106 Liquid crystal polymer Polymers 0.000 claims description 4
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 229920002396 Polyurea Polymers 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims description 4
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 4
- 229920000147 Styrene maleic anhydride Polymers 0.000 claims description 4
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 4
- 229920005669 high impact polystyrene Polymers 0.000 claims description 4
- 239000004797 high-impact polystyrene Substances 0.000 claims description 4
- 239000000155 melt Substances 0.000 claims description 4
- 229920000058 polyacrylate Polymers 0.000 claims description 4
- 229920001230 polyarylate Polymers 0.000 claims description 4
- 229920000728 polyester Polymers 0.000 claims description 4
- 229920001296 polysiloxane Polymers 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 229920006249 styrenic copolymer Polymers 0.000 claims description 4
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 3
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 claims description 3
- 229920002943 EPDM rubber Polymers 0.000 claims description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 3
- 150000004703 alkoxides Chemical class 0.000 claims description 3
- 229920001400 block copolymer Polymers 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- 229920001971 elastomer Polymers 0.000 claims description 3
- 239000000806 elastomer Substances 0.000 claims description 3
- 239000011256 inorganic filler Substances 0.000 claims description 3
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 3
- 229940006487 lithium cation Drugs 0.000 claims description 3
- 239000012766 organic filler Substances 0.000 claims description 3
- 239000004417 polycarbonate Substances 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 229920002635 polyurethane Polymers 0.000 claims description 3
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- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229940006486 zinc cation Drugs 0.000 claims description 3
- 239000004641 Diallyl-phthalate Substances 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 claims description 2
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 claims description 2
- 229920000638 styrene acrylonitrile Polymers 0.000 claims description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims 1
- 229940096405 magnesium cation Drugs 0.000 claims 1
- 229920006380 polyphenylene oxide Polymers 0.000 claims 1
- 230000035939 shock Effects 0.000 abstract description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 6
- 125000002843 carboxylic acid group Chemical group 0.000 abstract description 5
- 229910052799 carbon Chemical group 0.000 abstract 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract 1
- 150000001336 alkenes Chemical class 0.000 abstract 1
- 125000000217 alkyl group Chemical group 0.000 abstract 1
- 238000007334 copolymerization reaction Methods 0.000 abstract 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract 1
- 239000000463 material Substances 0.000 description 24
- 239000004743 Polypropylene Substances 0.000 description 13
- 229920001155 polypropylene Polymers 0.000 description 13
- 239000002023 wood Substances 0.000 description 13
- 239000004566 building material Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 229920001955 polyphenylene ether Polymers 0.000 description 5
- 239000011155 wood-plastic composite Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000004575 stone Substances 0.000 description 4
- 238000012441 weak partitioning chromatography Methods 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 3
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 3
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000011449 brick Substances 0.000 description 3
- 239000004567 concrete Substances 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 239000000454 talc Substances 0.000 description 3
- 229910052623 talc Inorganic materials 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- YWMAPNNZOCSAPF-UHFFFAOYSA-N Nickel(1+) Chemical compound [Ni+] YWMAPNNZOCSAPF-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 229910052622 kaolinite Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 229940006444 nickel cation Drugs 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000010456 wollastonite Substances 0.000 description 2
- 229910052882 wollastonite Inorganic materials 0.000 description 2
- MRDJTSOMGCYWFZ-UHFFFAOYSA-N C(=CC1=CC=CC=C1)C=CC#N.C(=CC1=CC=CC=C1)C=CC#N Chemical compound C(=CC1=CC=CC=C1)C=CC#N.C(=CC1=CC=CC=C1)C=CC#N MRDJTSOMGCYWFZ-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229920000034 Plastomer Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229920002522 Wood fibre Polymers 0.000 description 1
- 229920001587 Wood-plastic composite Polymers 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 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 1
- 239000007769 metal material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000002025 wood fiber Substances 0.000 description 1
Classifications
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- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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- B32B15/085—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyolefins
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- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
本发明是为了改善上述问题而提出的,其目的是提供树脂金属复合体,该树脂金属复合体在金属层和树脂层之间包含含有三元共聚物或二元共聚物的粘合层,因此耐冲击性、耐热冲击性及粘合性优异。所述目的通过本发明一实施例的包含粘合层的树脂金属复合体来实现,该包含粘合层的树脂金属复合体包含金属层、树脂层及在所述金属层和所述树脂层之间的粘合层,构成所述粘合层的粘合层组合物为由以下a)、b)、c)及d)单体中的两个单体或者三个单体共聚而成的二元共聚物或者三元共聚物,其中a)为由以下化学式1表示的α‑烯烃,[化学式1]RCH=CH2(在所述[化学式1]中,R为氢或者碳原子数为1至8的烷基自由基。);b)为丙烯酸酯或者甲基丙烯酸酯中的至少一种;c)为碳原子数为3至20的α,β‑乙烯不饱和丙烯酸、甲基丙烯酸、磺酸或者磷酸中的至少一种;d)为包含缩水甘油基、羟基、马来酸酐基、羧酸基或者酯基中的一种的单体。
Description
技术领域
本发明涉及一种包含粘合层的树脂金属复合体,更为详细地,涉及一种在金属层和树脂层之间包含粘合层且该粘合层为由以下a)、b)、c)及d)单体中的两个或者三个单体共聚而成的二元共聚物或者三元共聚物的、耐冲击性、耐热冲击性及粘合性优异的树脂金属复合体。其中,
a)为由以下化学式1来表示的α-烯烃,
[化学式1]
RCH=CH2
在所述[化学式1]中,R为氢或者碳原子数为1至8的烷基自由基;
b)为丙烯酸酯或者甲基丙烯酸酯中的至少一种;
c)为碳原子数为3至20的α,β-乙烯不饱和丙烯酸(α,β-ethylenated unsaturatedacrylic acid)、甲基丙烯酸、磺酸或者磷酸中的至少一种;
d)为包含缩水甘油基、羟基、马来酸酐基、羧酸基或者酯基中的一种的单体。
背景技术
建筑材料根据用途分为结构材料和外观材料,其中结构材料为构造建筑物骨架的材料,因此要求较高的力学强度和耐久性。即,需要避免产生在整个建筑的外壁的变形或者破坏等结构异常,因此这里尤其重要的是施工难度、对长期使用的性质、重量、加工性、对特殊场所的耐蚀性及耐火性等。
结构材料主要使用石材、砖、木材、钢材及水泥等,石材及砖等还作为饰面材料来使用。
石材的耐久性、耐磨性及强度优异,因此以往已作为结构材料来使用,但其加工需要付出很多努力,并且重量大,因此具有难以处理的问题和施工性不好的缺点。因此,最近更多作为利用石材所具有的独特性质的装饰材料或者饰面材料来使用。
此外,砖的施工性较好,并且结构强度、耐久性、耐火性及生产性优异,因此多作为结构材料及内部装饰来使用,但是当作为结构材料来使用时,虽然对垂直压力的耐力较好,但是对于横向力(橫力)来讲结构性非常脆弱,因此具有不适合在地震多发地、尤其在高层建筑上使用的问题。
另外,木材与其比重相比强度高,加工性优异,因此根据木材的方向性作为结构材料和饰面材料来使用。然而木材具有根据使用部位进行腐蚀和耐火性显著低的问题。
作为另一种结构材料最为广泛使用的物质有混凝土,混凝土为用水混合水泥、沙子和小石子并进行搅拌后硬化的材料,具有优异的耐火性及耐久性,与钢筋及钢架一起在提高结构体的刚性中使用。然而,混凝土的比重大,并且在制造结构体形状时必须使用模具,因此具有所需成本较高的问题。并且由于是必须使用水的湿式结构,因此具有在工期内受到外部条件的影响,在完成结构体为止需要较长时间的问题。
为了解决这种以往建筑材料所具有的问题,最近开发各种建筑材料,尤其是持续地要求一种具有高稳定性的同时重量轻、并且外观优异的土木等木材,因此通过对木材和塑料进行混合而制成的塑合木(Wood Plastic Composite,下面称为WPC)的型材挤压产品作为外装建筑材料备受关注。
WPC为在聚乙烯、聚丙烯等多种热塑性树脂中添加木粉的的材料,具有塑料的优异加工性和木材的秀丽外观,并且与以往的木材或者塑料的单一材料相比具有更高的强度、低廉的价格及能够应用在各种领域的优点,因此在外装用建筑材料、栅栏、汽车车身、室内装饰、招牌等多种领域中使用。此外,最近为了减轻WPC的重量,并且改善包括弯曲强度的各种机械物理性质,引进了通过在金属表面上共挤压WPC而制作金属-树脂层压材料的技术。
金属-树脂层压材料其重量轻,绝热性、防火性及机械物理性质优异,但是当作为外装用建筑材料来使用时,若施加物理冲击,则会因金属和树脂层之间的剥离而引起裂缝(Crack),并且因金属和树脂之间的导热性差距大而引起温度变化并导致热冲击,从而产生裂缝(Crack)。
因此,仍然要求一种耐冲击性及热稳定性高的建筑材料,以便能够将金属-树脂层压材料作为外装材料来使用。
发明内容
本发明是为了改善如上所述的问题而提出的,其目的在于提供一种树脂金属复合体,该树脂金属复合体在金属层和树脂层之间包含粘合层,该粘合层包含三元共聚物或者二元共聚物,因此该树脂金属复合体的耐冲击性、耐热冲击性及粘合性优异。
此外,其目的在于提供一种树脂金属复合体,该树脂金属复合体利用具有两个缝隙的双重挤压机来挤压树脂层及粘合层的同时进行粘合而成,因此均匀性及耐久性优异。
所述目的通过本发明的一实施例的包含粘合层的树脂金属复合体来实现,该包含粘合层的树脂金属复合体包含金属层、树脂层及在所述金属层和所述树脂层之间的粘合层,构成所述粘合层的粘合层组合物为由以下a)、b)、c)及d)单体中的两个或者三个单体来共聚而成的二元共聚物或者三元共聚物。
a)为由以下化学式1来表示的α-烯烃,
[化学式1]
RCH=CH2
(在所述[化学式1]中,R为氢或者碳原子数为1至8的烷基自由基。)
b)为丙烯酸酯或者甲基丙烯酸酯中的至少一种,
c)为碳原子数为3至20的α,β-乙烯不饱和丙烯酸、甲基丙烯酸、磺酸或者磷酸中的至少一种,
d)为包含缩水甘油基、羟基、马来酸酐基、羧酸基或者酯基中的一种的单体。
此时,所述c)可被包含金属阳离子的碱中和0.01%至50%,从而以金属盐形式存在。所述金属阳离子为锂阳离子(Li+)、钠阳离子(Na+)、钾阳离子(K+)、锌阳离子(Zn2+)、钙阳离子(Ca2+)、钴阳离子(Co2+)、镍阳离子(Ni2+)、铜阳离子(Cu2+)、铅阳离子(Pb2+)或者镁阳离子(Mg2+)中的至少一种。
此外,所述碱为蚁酸酯、醋酸酯、硝酸盐、碳酸盐、重碳酸盐、氧化物、氢氧化物或者醇盐中的至少一种。
尤其,所述三元共聚物由a)、b)及c)共聚而成,所述a)为15至99.98wt%,所述b)为0.01至50wt%,所述c)为0.01至35wt%。
所述粘合层组合物进一步包含添加物,所述添加物为聚氨酯、聚酯、聚酰胺弹性体、聚酰胺-离聚物、聚氨酯-离聚物、热塑性共聚醚酯嵌段共聚物、聚碳酸酯、聚烯烃、聚烯烃塑料、聚酰胺、共聚聚酰胺、聚乙烯醇、丙烯腈-丁二烯-苯乙烯共聚物、聚芳酯、聚丙烯酸酯、聚苯醚、冲击-改性的聚苯醚、高冲击聚苯乙烯、邻苯二甲酸二烯丙酯聚合物、苯乙烯-丙烯腈、苯乙烯-马来酸酐聚合物、苯乙烯类共聚物、功能性苯乙烯类共聚物、功能性苯乙烯类三元共聚物、苯乙烯类三元共聚物、纤维素聚合物、液晶聚合物、乙烯-丙烯-二烯三元共聚物、乙烯-醋酸乙烯酯共聚物、乙烯-丙烯共聚物、乙烯醋酸乙烯酯、聚脲或者聚硅氧烷中的至少一种。
此外,在本发明的一实施例中,相对于所述粘合层组合物100重量份,所述添加物为0.001至20重量份,粘合层的厚度为0.001mm至100mm,粘合层的熔融指数为1g/10min至300g/10min。
此外,与所述粘合层接合的所述金属层的表面为凹凸结构,所述树脂层及所述粘合层通过挤压的同时粘合而形成。
本发明能够提供一种树脂金属复合体,该树脂金属复合体由于使用在金属和树脂的结合中最适合的包含三元共聚物或者二元共聚物的粘合层组合物,因此耐冲击性、耐热冲击性及粘合性优异。
此外,本发明中的金属层表面具有凹凸结构,因此与粘合层结合的金属层的表面积增加,能够提供高度的粘合力。
此外,为了制作树脂金属复合体使用具有两个挤型模的双重挤压机,因此能够提供一种粘合力强并且所涂覆的粘合层厚度均匀的树脂金属复合体。
附图说明
图1为表示本发明的一实施例的树脂金属复合体的层压形状的剖视图,
图2为表示本发明的一实施例的金属层表面的凹凸结构的剖视图,
图3为表示根据本发明的实施例使用双重挤压机挤压树脂层及粘合层的剖视图,
图4的(a)为表示根据本发明的比较例1制作的树脂金属复合体的照片,图4的(b)为放大显示图4的(a)的照片,
图5的(a)为表示根据本发明的比较例2制作的树脂金属复合体的照片,图5的(b)为放大显示图5的(a)的照片,
图6的(a)为表示根据本发明的实施例制作的树脂金属复合体的照片,图6的(b)为放大显示图6的(a)的照片。
具体实施方式
下面,参照附图,并且利用本发明的一个优选实施方式,对包含粘合层的树脂金属复合体及其制作方法进行详细说明。
参照附图和详细后述的实施例,应能清楚地理解本发明的优点和特征、以及用于达到这些优点和特征的方法。但是,本发明并不局限于以下公开的实施例,可由各种不同的形式来实现。本实施例只是用于完整地公开本发明,且为了向本领域的技术人员完整地告知发明的范畴而提供的,本发明应由权利要求的范畴来定义。在通篇说明书中相同的附图标记指代相同的结构要素。
除非另有定义,在本说明书中使用的所有用语(包括技术及科学用语)可作为本发明所属技术领域中具有一般知识的人能够共同理解的意思来使用。另外,在一般使用的词典中所定义的用语,除非有明确而特别的定义,不被理想地或过度地解释。
本发明涉及一种树脂金属复合体,如图1所示,其为包含金属层10及树脂层30,且在所述金属层10和所述树脂层30之间包含粘合层20,由此通过粘合层20结合金属层10和树脂层30的形式。
[附图标记说明]
10:金属层
20:粘合层
30:树脂层
11、12:投入部
21:第一缝隙
22:第二缝隙
构成所述金属层10的金属物质不受特别的限制,只要能够与树脂结合的金属就都能使用,但优选为铝、铁、铜、铬、镍、硅、锰、钨、锌、镁或者其合金中的至少一种,此时具有提高树脂金属复合体的耐久性的效果。
对于构成所述树脂层30的树脂层组合物来说,只要是能够在金属上层压而使用的树脂就不受限制地都能使用,但优选为有机填料或者无机填料中的至少一种,所述有机填料可为选自木粉、木颗粒、木纤维或者脂粉中的一种,所述无机填料可为选自滑石、碳酸钙、硅灰石(wollastonite)或者高岭石(kaolinite)中的一种以上,当使用有机填料或者无机填料时,美观优异,能够作为建筑物的外装材料来使用。
所述粘合层20位于所述金属层10和所述树脂层30之间,用于结合所述金属层10和所述树脂层30。
所述粘合层组合物可包含由以下a)、b)、c)及d)单体中的两个或者三个单体来共聚而成的二元共聚物或者三元共聚物中的至少一种。
a)为由以下[化学式1]来表示的α-烯烃,在以下[化学式1]中,取代基R可为氢或者碳原子数为1至8的烷基自由基。通过使用包含α-烯烃的共聚物,能够制作轻质的树脂金属复合体。
[化学式1]
RCH=CH2
b)可为丙烯酸酯或者甲基丙烯酸酯,优选可为甲基丙烯酸酯。所述b)可通过使用能够形成软化的共聚物的单体,从而防止树脂金属复合体在频繁的温度变化中产生裂缝。
c)为碳原子数为3至20的α,β-乙烯不饱和丙烯酸、甲基丙烯酸、磺酸或者磷酸中的至少一种,优选可为α,β-乙烯不饱和丙烯酸或者甲基丙烯酸。
此外,d)可为包含缩水甘油基、羟基、马来酸酐基、羧酸基或者酯基中的一种的单体。
此时,构成粘合层组合物的聚合物优选为由所述a)和c)共聚而成的二元共聚物或者由a)、b)及c)共聚而成的三元共聚物。
由所述a)和c)共聚而成的二元共聚物的结构具有能够通过与金属盐进行反应来形成离聚物(ionomer)的酸基。
详细地,所述c)能够被中和成金属盐来形成离聚物,此时,所述c)被包含金属阳离子的碱中和50%以下,优选被中和0.01%至50%,更加优选被中和10%至35%而形成的。
当中和度超过50%时,因通过离子金属盐形成的离子簇(ionic cluster)以及由此产生的离子结合强度增加,从而导致难以成型的问题;当中和度小于0.01%时,在所要求的物理性质提高上所需要的金属盐不足。
在碱中包含的金属阳离子为碱金属阳离子、碱土金属阳离子或者电子价为二价以下的过渡金属阳离子,优选为锂阳离子(Li+)、钠阳离子(Na+)、钾阳离子(K+)、锌阳离子(Zn2 +)、钙阳离子(Ca2+)、钴阳离子(Co2+)、镍阳离子(Ni2+)、铜阳离子(Cu2+)、铅阳离子(Pb2+)或者镁阳离子(Mg2+)中的至少一种,更加优选可为钾阳离子(K+)或者锌阳离子(Zn2+)。
在碱中包含的金属阳离子用于交联由a)及c)聚合而成的聚合物,由此形成的离聚物具有通过金属盐的离子簇(ionic cluster)伪交联(pseudo-crosslinked)的结构,但在高温下离子结合力弱,因此能够进行熔化加工。
此外,所述碱为蚁酸酯(formate)、醋酸酯(acetate)、硝酸盐(nitrate)、碳酸盐(carbonate)、重碳酸盐(bicarbonate)、氧化物(oxide)、氢氧化物(hydroxide)或者醇盐(hydroxide)中的至少一种,优选为蚁酸酯(formate)或醋酸酯。
在由a)、b)及c)形成的三元共聚物中,所述a)为15至99.98wt%,所述b)为50wt%以下,优选可为0.01至50wt%;所述c)为35wt%以下,优选可为0.01至35wt%以下。
当形成离聚物的c)超过35wt%时,由离子金属盐形成的离子簇(ionic cluster)和由此形成的离子结合强度增加,具有难以成型的问题;当小于0.01%时,对所要求的物理性质提高上所需要的金属盐不足,难以满足建筑外装材料所要求的耐冲击性及耐热冲击性。
粘合层组合物可包含添加物,所述添加物若为所属技术领域中常用的添加物则不特别限制,但具体可为聚氨酯、聚酯、聚酰胺弹性体、聚酰胺-离聚物、聚氨酯-离聚物、热塑性共聚醚酯嵌段共聚物(thermoplastic copolyetherester block copolymer)、聚碳酸酯、聚烯烃(polyolefin)、聚烯烃塑料(polyolefin plastomer)、聚酰胺(polyamide)、共聚聚酰胺(copolymeric polyamide)、聚乙烯醇(polyvinyl alcohol)、丙烯腈-丁二烯-苯乙烯共聚物(acrylonitrile-butadiene-styrene copolymer)、聚芳酯(polyarylate)、聚丙烯酸酯(polyacrylate)、聚苯醚(polyphenylene ether)、冲击-改性的聚苯醚(impact-modified polyphenylene ether)、高冲击聚苯乙烯(high impact polystyrene)、邻苯二甲酸二烯丙酯聚合物(diallyl phthalate polymer)、苯乙烯-丙烯腈(styrene-acrylonitrile)、苯乙烯-马来酸酐聚合物(styrene-maleic anhydride polymer),苯乙烯类共聚物(styrenic copolymer)、功能性苯乙烯类共聚物(functionalized styreniccopolymer)、功能性苯乙烯类三元共聚物(functionalized styrenic terpolymer)、苯乙烯类三元共聚物(styrenic terpolymer)、纤维素聚合物(cellulose polymer)、液晶聚合物(liquid crystal polymer)、乙烯-丙烯-二烯三元共聚物(ethylene-propylene-dieneterpolymer)、乙烯-醋酸乙烯酯共聚物(ethylene-vinyl acetate copolymer)、乙烯-丙烯共聚物(ethylene-propylene copolymer)、乙烯醋酸乙烯酯(ethylene vinyl acetate)、聚脲(polyurea)或者聚硅氧烷(polyurea)中的至少一种。
此外,相对于粘合层组合物100重量份,所述添加物为20重量份以下,优选可为0.001至20重量份,更加优选可为0.1至15重量份。当超过20重量份时,共聚物的含量相对减少,会产生粘合性和稳定性等物理性质降低的问题,当小于0.001重量份时,会产生防裂缝效率降低的问题。
在包含所述金属层10、所述粘合层20及所述树脂层30的树脂金属复合体中,所述粘合层20的厚度为100mm以下,或者优选可为0.001mm至100mm,更加优选可为1mm至50mm。当超过100mm时,会产生包含粘合层20的树脂金属复合体的加工性差的问题,当小于0.001mm时,会导致制造成本增加及粘合性的急剧下降,从而导致问题。
此外,所述粘合层20的熔融指数在230℃和2.16kg的荷载中为300g/10min以下,优选为1g/10min至300g/10min,更加优选可为10g/10min至100g/10min,当熔融指数超过300g/10min时,会降低均匀性、机械物性及耐热冲击性,当小于1g/10min时,会降低加工性。
与所述粘合层20结合的所述金属层10的表面可为凹凸结构,从而增加能够与粘合层20组合物接触的金属层10的表面积,因此能够提高树脂金属复合体的稳定性及耐久性。
本发明的一实施例的树脂金属复合体的制作方法不受特别的限制,但优选为挤压法,更加优选地,所述树脂层可通过将树脂层组合物由双重挤压机的第一缝隙挤压而形成,所述粘合层可通过将所述粘合层组合物由所述双重挤压机的第二缝隙挤压而形成,所述树脂层及所述粘合层可通过挤压的同时粘合而形成。
下面,为了帮助对本发明的理解,举优选实施例进行说明。
[实施例1]
使用粘合层组合物粘合包含镀锌铁的金属层和包含木粉及滑石的树脂层而制作树脂金属复合体,其中所述粘合层组合物包含三元共聚物,所述三元共聚物由包含α-烯烃、丙烯酸酯及α,β-乙烯不饱和丙烯酸的离聚物共聚而成。对该树脂金属复合体在-30℃的温度下冷却五小时后,在60℃的温度下加热五小时,并通过肉眼观察耐热冲击性。
[比较例1]
对包含镀锌铁的金属层和包含木粉及滑石的树脂层进行接合以制作树脂金属复合体,此时未使用粘合剂。对该树脂金属复合体在-30℃的温度下冷却五小时后,在60℃的温度下加热五小时,并通过肉眼观察耐热冲击性。
[比较例2]
使用与比较例1相同的金属层及树脂层,将马来酸酯化聚乙烯(MAPE)作为粘合层组合物使用并制作树脂金属复合剂,并且在相同的条件下通过肉眼观察耐热冲击性。
图4的(a)为表示根据比较例1制作的树脂金属复合体的照片,图4的(b)为放大显示该图4的(a)的照片,在挤压加工时,由于树脂层和金属层没有粘合,因此无法进行测试。
此外,图5的(a)为表示根据比较例2制作的树脂金属复合体的照片,图5的(b)为放大显示该图5的(a)的照片,在挤压加工时,虽然树脂层和金属层粘合,但在耐热冲击性实验后在树脂层表面上观察到裂缝。
相反,图6的(a)为表示根据实施例制作的树脂金属复合体的照片,图6的(b)为放大显示该图6的(a)的照片,在挤压加工时,树脂层和金属层均匀粘合,并且在耐热冲击性实验后也没有在树脂层表面上观察到裂缝。
以上对本发明的优选实施例进行了说明,但本发明的权利范围并不限于上述实施例,在所附的权利要求书的范围内可由多种形式的实施例实现。在不脱离权利要求书所要求保护的本发明精神的范围内,本发明所属技术领域的技术人员均能变形的各种范围也属于本发明的权利要求书所记载的范围内。
工业上的可应用性
本发明涉及一种树脂金属复合体,该树脂金属复合体在金属层和树脂层之间包含粘合层,该粘合层为由以下a)、b)、c)及d)单体中的两个或者三个单体共聚而成的二元共聚物或者三元共聚物,因此该树脂金属复合体具有耐冲击性及耐热冲击性显著优异的效果,能够在工业上应用。
其中,a)为由以下化学式1来表示的α-烯烃,
[化学式1]
RCH=CH2
(在所述[化学式1]中,R为氢或者碳原子数为1至8的烷基自由基。)
b)为丙烯酸酯或者甲基丙烯酸酯中的至少一种,
c)为碳原子数为3至20的α,β-乙烯不饱和丙烯酸、甲基丙烯酸、磺酸或者磷酸中的至少一种,
d)为包含缩水甘油基、羟基、马来酸酐基、羧酸基或者酯基中的一种的单体。
Claims (11)
1.一种包含粘合层的树脂金属复合体,包含:
金属层;
树脂层;及
粘合层,设置在所述金属层和所述树脂层之间,
其中所述树脂层包含有机填料和无机填料中的至少一种,
其中构成所述粘合层的粘合层组合物包含由以下a)、b)、c)及d)单体中的两个单体或者三个单体共聚而成的二元共聚物或者三元共聚物,其中,
a)为由以下化学式1表示的α-烯烃,
[化学式1]
RCH=CH2
在所述[化学式1]中,R为氢或者碳原子数为1至8的烷基自由基,
b)为丙烯酸酯或者甲基丙烯酸酯中的至少一种,
c)为碳原子数为3至20的α,β-乙烯不饱和丙烯酸、甲基丙烯酸、磺酸或者磷酸中的至少一种,
d)为包含缩水甘油基、羟基、马来酸酐基、羧酸基或者酯基中的一种的单体,
其中所述粘合层的熔融指数在230℃的温度和2.16kg的荷载的条件下为1g/10min至300g/10min。
2.根据权利要求1所述的包含粘合层的树脂金属复合体,其中,
所述c)被包含金属阳离子的碱中和0.01%至50%,从而以金属盐形式存在。
3.根据权利要求2所述的包含粘合层的树脂金属复合体,其中,
所述金属阳离子为锂阳离子Li+、钠阳离子Na+、钾阳离子K+、锌阳离子Zn2+、钙阳离子Ca2 +、钴阳离子Co2+、镍阳离子Ni2+、铜阳离子Cu2+、铅阳离子Pb2+或者镁阳离子Mg2+中的至少一种。
4.根据权利要求2所述的包含粘合层的树脂金属复合体,其中,所述碱为蚁酸酯、醋酸酯、硝酸盐、碳酸盐、氧化物、氢氧化物或者醇盐中的至少一种。
5.根据权利要求1所述的包含粘合层的树脂金属复合体,其中,所述三元共聚物由a)、b)及c)共聚而成,所述a)为15至99.98wt%,所述b)为0.01至50wt%,所述c)为0.01至35wt%。
6.根据权利要求1所述的包含粘合层的树脂金属复合体,其中,所述粘合层组合物进一步包含添加物,
所述添加物为聚氨酯、聚酯、聚酰胺弹性体、聚酰胺-离聚物、聚氨酯-离聚物、热塑性共聚醚酯嵌段共聚物、聚碳酸酯、聚烯烃、聚酰胺、聚乙烯醇、聚丙烯酸酯、聚苯醚、高冲击聚苯乙烯、邻苯二甲酸二烯丙酯聚合物、苯乙烯类共聚物、纤维素聚合物、液晶聚合物、乙烯-醋酸乙烯酯共聚物、聚脲或者聚硅氧烷中的至少一种。
7.根据权利要求6所述的包含粘合层的树脂金属复合体,其中,聚酯包括聚芳酯,聚烯烃包括乙烯-丙烯共聚物,其中乙烯-丙烯共聚物包括乙烯-丙烯-二烯三元共聚物,苯乙烯类共聚物包括功能性苯乙烯类共聚物,其中功能性苯乙烯类共聚物包括苯乙烯类三元共聚物、苯乙烯-丙烯腈和苯乙烯-马来酸酐聚合物。
8.根据权利要求6所述的包含粘合层的树脂金属复合体,其中,相对于所述粘合层组合物100重量份,所述添加物为0.001至20重量份。
9.根据权利要求1所述的包含粘合层的树脂金属复合体,其中,所述粘合层的厚度为0.001mm至100mm。
10.根据权利要求1所述的包含粘合层的树脂金属复合体,其中,与所述粘合层接合的所述金属层的表面为凹凸结构。
11.根据权利要求1所述的包含粘合层的树脂金属复合体,其中,所述树脂层及所述粘合层通过挤压的同时粘合而形成。
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- 2014-01-22 KR KR1020140007806A patent/KR101574408B1/ko active IP Right Grant
- 2014-02-12 CN CN201480077393.4A patent/CN106163797B/zh active Active
- 2014-02-12 WO PCT/KR2014/001162 patent/WO2015111786A1/ko active Application Filing
- 2014-02-12 US US15/113,238 patent/US20170028683A1/en not_active Abandoned
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KR20150087879A (ko) | 2015-07-31 |
JP6328777B2 (ja) | 2018-05-23 |
US20170028683A1 (en) | 2017-02-02 |
CN106163797A (zh) | 2016-11-23 |
WO2015111786A1 (ko) | 2015-07-30 |
JP2017510477A (ja) | 2017-04-13 |
KR101574408B1 (ko) | 2015-12-07 |
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