KR20170057341A - 개선된 소음 억제성을 갖는 중합체 조성물 - Google Patents
개선된 소음 억제성을 갖는 중합체 조성물 Download PDFInfo
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- KR20170057341A KR20170057341A KR1020177010052A KR20177010052A KR20170057341A KR 20170057341 A KR20170057341 A KR 20170057341A KR 1020177010052 A KR1020177010052 A KR 1020177010052A KR 20177010052 A KR20177010052 A KR 20177010052A KR 20170057341 A KR20170057341 A KR 20170057341A
- Authority
- KR
- South Korea
- Prior art keywords
- plastisol
- plasticizer
- carbon atoms
- group
- hydrogen
- 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.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims description 17
- 230000001629 suppression Effects 0.000 title description 2
- 229920001944 Plastisol Polymers 0.000 claims abstract description 96
- 239000004999 plastisol Substances 0.000 claims abstract description 96
- 239000004014 plasticizer Substances 0.000 claims abstract description 85
- 239000000758 substrate Substances 0.000 claims abstract description 50
- 238000000034 method Methods 0.000 claims abstract description 43
- 229920000642 polymer Polymers 0.000 claims abstract description 27
- 238000013016 damping Methods 0.000 claims abstract description 24
- 125000004432 carbon atom Chemical group C* 0.000 claims description 54
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 51
- 239000001257 hydrogen Substances 0.000 claims description 51
- 229910052739 hydrogen Inorganic materials 0.000 claims description 51
- 125000000217 alkyl group Chemical group 0.000 claims description 37
- 150000002148 esters Chemical class 0.000 claims description 36
- 230000032050 esterification Effects 0.000 claims description 27
- 238000005886 esterification reaction Methods 0.000 claims description 27
- 239000004800 polyvinyl chloride Substances 0.000 claims description 25
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 22
- -1 2,4-dimethyl-2-ethyl-1,3hexanediol benzoate Chemical compound 0.000 claims description 21
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 18
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 17
- 239000003981 vehicle Substances 0.000 claims description 16
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 15
- 239000000654 additive Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 14
- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluic acid Chemical compound CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 0.000 claims description 14
- 230000000996 additive effect Effects 0.000 claims description 12
- 238000000518 rheometry Methods 0.000 claims description 12
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- 235000014113 dietary fatty acids Nutrition 0.000 claims description 11
- 239000000194 fatty acid Substances 0.000 claims description 11
- 229930195729 fatty acid Natural products 0.000 claims description 11
- 239000000945 filler Substances 0.000 claims description 11
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 10
- 150000008064 anhydrides Chemical class 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 10
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- 239000002318 adhesion promoter Substances 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
- 239000011787 zinc oxide Substances 0.000 claims description 9
- JCTXKRPTIMZBJT-UHFFFAOYSA-N 2,2,4-trimethylpentane-1,3-diol Chemical group CC(C)C(O)C(C)(C)CO JCTXKRPTIMZBJT-UHFFFAOYSA-N 0.000 claims description 8
- XVKPYHKSXUGUIY-UHFFFAOYSA-N benzoic acid;2,2,4-trimethylpentane-1,3-diol Chemical compound OC(=O)C1=CC=CC=C1.CC(C)C(O)C(C)(C)CO XVKPYHKSXUGUIY-UHFFFAOYSA-N 0.000 claims description 8
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000292 calcium oxide Substances 0.000 claims description 8
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 8
- 239000011796 hollow space material Substances 0.000 claims description 8
- 239000003381 stabilizer Substances 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
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- BBPFNSOFNCUVAQ-UHFFFAOYSA-N [2-(benzoyloxymethyl)-2-ethylhexyl] benzoate Chemical compound C=1C=CC=CC=1C(=O)OCC(CC)(CCCC)COC(=O)C1=CC=CC=C1 BBPFNSOFNCUVAQ-UHFFFAOYSA-N 0.000 claims description 7
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- 150000005690 diesters Chemical class 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 239000013536 elastomeric material Substances 0.000 claims description 6
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 6
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- MFNQWQNXFKHZAJ-UHFFFAOYSA-N 3-ethylheptane-2,4-diol Chemical compound CCCC(O)C(CC)C(C)O MFNQWQNXFKHZAJ-UHFFFAOYSA-N 0.000 claims description 4
- 229940049964 oleate Drugs 0.000 claims description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 claims description 3
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 claims description 3
- 150000008052 alkyl sulfonates Chemical class 0.000 claims description 3
- 239000004927 clay Substances 0.000 claims description 3
- 229910052570 clay Inorganic materials 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 claims description 3
- 238000007765 extrusion coating Methods 0.000 claims description 3
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- 239000010439 graphite Substances 0.000 claims description 3
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- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- QQVIHTHCMHWDBS-UHFFFAOYSA-L isophthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC(C([O-])=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-L 0.000 claims description 3
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 3
- 239000001095 magnesium carbonate Substances 0.000 claims description 3
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 3
- 239000010445 mica Substances 0.000 claims description 3
- 229910052618 mica group Inorganic materials 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- 239000002480 mineral oil Substances 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 3
- 239000003209 petroleum derivative Substances 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 125000005498 phthalate group Chemical group 0.000 claims description 3
- 239000000049 pigment Substances 0.000 claims description 3
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 235000015096 spirit Nutrition 0.000 claims description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 claims description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims description 3
- 150000003626 triacylglycerols Chemical class 0.000 claims description 3
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 claims description 3
- 125000005591 trimellitate group Chemical group 0.000 claims description 3
- 241001265801 Amynthas fusing Species 0.000 claims description 2
- 238000002076 thermal analysis method Methods 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 25
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 14
- 239000000463 material Substances 0.000 description 14
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000004604 Blowing Agent Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
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- RDOFJDLLWVCMRU-UHFFFAOYSA-N Diisobutyl adipate Chemical compound CC(C)COC(=O)CCCCC(=O)OCC(C)C RDOFJDLLWVCMRU-UHFFFAOYSA-N 0.000 description 5
- CVUYNSYCMSZDNN-UHFFFAOYSA-N [2,2,4-trimethyl-3-(2-methylbenzoyl)oxypentyl] 2-methylbenzoate Chemical group C=1(C(=CC=CC=1)C(=O)OCC(C(C(C)C)OC(=O)C=1C(=CC=CC=1)C)(C)C)C CVUYNSYCMSZDNN-UHFFFAOYSA-N 0.000 description 5
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- 150000002009 diols Chemical class 0.000 description 5
- 230000004927 fusion Effects 0.000 description 5
- WVWZECQNFWFVFW-UHFFFAOYSA-N methyl 2-methylbenzoate Chemical compound COC(=O)C1=CC=CC=C1C WVWZECQNFWFVFW-UHFFFAOYSA-N 0.000 description 5
- 229940095102 methyl benzoate Drugs 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- NXQMCAOPTPLPRL-UHFFFAOYSA-N 2-(2-benzoyloxyethoxy)ethyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCCOCCOC(=O)C1=CC=CC=C1 NXQMCAOPTPLPRL-UHFFFAOYSA-N 0.000 description 4
- BUYHVRZQBLVJOO-UHFFFAOYSA-N 2-ethyl-2,4-dimethylhexane-1,3-diol Chemical compound CCC(C)C(O)C(C)(CC)CO BUYHVRZQBLVJOO-UHFFFAOYSA-N 0.000 description 4
- ZVFDTKUVRCTHQE-UHFFFAOYSA-N Diisodecyl phthalate Chemical compound CC(C)CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC(C)C ZVFDTKUVRCTHQE-UHFFFAOYSA-N 0.000 description 4
- 229920012485 Plasticized Polyvinyl chloride Polymers 0.000 description 4
- SAOKZLXYCUGLFA-UHFFFAOYSA-N bis(2-ethylhexyl) adipate Chemical compound CCCCC(CC)COC(=O)CCCCC(=O)OCC(CC)CCCC SAOKZLXYCUGLFA-UHFFFAOYSA-N 0.000 description 4
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- FTSXVYQZLNPTCM-UHFFFAOYSA-N (3-benzoyloxy-2,2,4-trimethylpentyl) benzoate Chemical compound C=1C=CC=CC=1C(=O)OCC(C)(C)C(C(C)C)OC(=O)C1=CC=CC=C1 FTSXVYQZLNPTCM-UHFFFAOYSA-N 0.000 description 3
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Abstract
Description
Claims (17)
- 하기 화학식 I 및 하기 화학식 Ⅱ의, 또는 화학식 I 및/또는 화학식 Ⅱ의 상응하는 에스테르, 무수물, 및/또는 산 클로라이드의, 하기 화학식 Ⅲ의 화합물과의 반응에 의해 형성되는 에스테르화 생성물을 포함하는 가소제:
상기 식에서,
R1 및 R2는, 수소 및 1 내지 9 개의 탄소 원자를 함유하는 선형 또는 분지형 알킬기로 이루어진 군으로부터 독립적으로 선택되되, 단 R1 및 R2는 각각 수소는 아니며;
R3 및 R4는, 수소 및 1 내지 8 개의 탄소 원자를 갖는 선형 또는 분지형 알킬기로 이루어진 군으로부터 독립적으로 선택되고, 이 때 R3 및 R4의 탄소 원자 수의 합은 0 내지 10이고;
R5 및 R6은, 수소 및 1 내지 8 개의 탄소 원자를 갖는 선형 또는 분지형 알킬기로 이루어진 군으로부터 독립적으로 선택되고, 이 때 R5 및 R6의 탄소 원자 수의 합은 0 내지 10이다. - 제 1 항에 있어서,
상기 가소제가 2,2,4-트라이메틸-1,3-펜탄다이올 다이톨루에이트, 2,2,4-트라이메틸-1,3-펜탄다이올 벤조에이트/톨루에이트, 2,4-다이메틸-2-에틸-1,3-헥산다이올 다이톨루에이트, 2,4-다이메틸-2-에틸-1,3 헥산다이올 벤조에이트/톨루에이트, 2-메틸-2-프로필-1,3-프로판다이올 다이톨루에이트, 2-메틸-2-프로필-1,3-프로판다이올 벤조에이트/톨루에이트, 또는 2-부틸-2-에틸-1,3-프로판다이올 다이벤조에이트를 포함하는, 가소제. - 중합체 성분 및 가소제를 포함하는 플라스티솔(plastisol)로서,
상기 가소제는, 하기 화학식 I 및 하기 화학식 Ⅱ의, 또는 화학식 I 및/또는 화학식 Ⅱ의 상응하는 에스테르, 무수물, 및/또는 산 클로라이드의, 하기 화학식 Ⅲ의 화합물과의 반응에 의해 형성되는 에스테르화 생성물을 포함하는, 플라스티솔:
상기 식에서,
R1 및 R2는, 수소 및 1 내지 9 개의 탄소 원자를 함유하는 선형 또는 분지형 알킬기로 이루어진 군으로부터 독립적으로 선택되고;
R3 및 R4는, 수소 및 1 내지 8 개의 탄소 원자를 갖는 선형 또는 분지형 알킬기로 이루어진 군으로부터 독립적으로 선택되고, 이 때 R3 및 R4의 탄소 원자 수의 합은 0 내지 10이고;
R5 및 R6은, 수소 및 1 내지 8 개의 탄소 원자를 갖는 선형 또는 분지형 알킬기로 이루어진 군으로부터 독립적으로 선택되고, 이 때 R5 및 R6의 탄소 원자 수의 합은 0 내지 10이다. - 제 4 항에 있어서,
단, R1 및 R2가 각각 수소가 아닌, 플라스티솔. - 제 4 항 또는 제 5 항에 있어서,
상기 가소제가 2,2,4-트라이메틸-1,3-펜탄다이올 다이톨루에이트, 2,2,4-트라이메틸-1,3-펜탄다이올 벤조에이트/톨루에이트, 2,4-다이메틸-2-에틸-1,3-헥산다이올 다이톨루에이트, 2,4-다이메틸-2-에틸-1,3 헥산다이올 벤조에이트/톨루에이트, 2-메틸-2-프로필-1,3-프로판다이올 다이톨루에이트, 2-메틸-2-프로필-1,3-프로판다이올 벤조에이트/톨루에이트, 또는 2-부틸-2-에틸-1,3-프로판다이올 다이벤조에이트를 포함하는, 플라스티솔. - 제 4 항 내지 제 7 항 중 어느 한 항에 있어서,
상기 플라스티솔이, 각각 상기 플라스티솔의 총 중량을 기준으로, 상기 가소제 10 중량% 내지 70 중량%, 상기 중합체 성분 10 중량% 내지 70 중량%, 기타 성분 10 중량% 내지 80 중량%를 포함하고,
상기 기타 성분은 제 2 가소제, 충전제, 안료, 안정제, 발포제, 중공 물질, 엘라스토머성(elastomeric) 물질, 레올로지 제어 첨가제 또는 접착 증진제를 포함하고,
상기 중합체 성분은 폴리바이닐 클로라이드, 폴리바이닐 아세테이트, 아크릴 중합체 및/또는 바이닐 클로라이드-함유 공중합체를 포함하는, 플라스티솔. - 제 7 항에 있어서,
상기 제 2 가소제는 프탈레이트; 테레프탈레이트; 아이소프탈레이트; 트라이멜리테이트; 아디페이트; 사이클로헥산다이카복실레이트; 벤조에이트; 포스페이트; 에틸렌글리콜, 프로필렌글리콜, 이들의 올리고머 및 이들의 혼합물의 다이에스테르; 사이트레이트; 석시네이트; 알킬 설포네이트; 지방산 에스테르 및 에폭시화된 지방산 에스테르; 선택적으로 치환되는, 트라이글리세라이드 및 에폭시화된 트라이글리세라이드; 다이안하이드로헥시톨 다이에스테르; 펜타에리트리톨-계 테트라에스테르; 퓨란-계 에스테르; 기타 에스테르; 케탈; 또는 중합체성 가소제를 포함하는, 플라스티솔. - 제 8 항 또는 제 9 항에 있어서,
상기 충전제가 칼슘 카보네이트, 마그네슘 카보네이트, 실리카, 점토, 운모, 흑연, 산화 아연 또는 산화 칼슘을 포함하거나, 또는
상기 충전제가 칼슘 카보네이트를 포함하는, 플라스티솔. - 제 8 항 내지 제 10 항 중 어느 한 항에 있어서,
상기 레올로지 제어 첨가제가 석유 증류물; 미네랄 오일 및 미네랄 스피릿; 지방산 에스테르; 폴리페닐 올리고머; 또는 유기 용제를 포함하는, 플라스티솔. - 제 4 항 내지 제 11 항 중 어느 한 항에 있어서,
상기 융합된 플라스티솔이, 스트레인(strain) 0.1 %, 진동수 1 Hz, 온도 램프(ramp) 속도 3 ℃/분에서 인장 클램프(tension clamp)를 가진 동적 기계적 분석기(Dynamic Mechanical Analyzer)를 사용하여 공칭 두께 0.6 내지 0.7 mm, 폭 3.2 mm 및 길이 10 내지 12 mm의 시료를 측정할 때, 최대 탄젠트 델타(Tan δmax)가 20 ℃ 내지 50 ℃ 사이에서 발생하고, 30 ℃에서의 탄젠트 델타(Tan δ30C)가 0.5 내지 2.0 범위인, 플라스티솔. - 제 12 항에 있어서,
상기 최대 탄젠트 델타(Tan δmax)가 20 ℃ 내지 40 ℃에서 발생하는, 플라스티솔. - 제 4 항 내지 제 13 항 중 어느 한 항의 플라스티솔을 기판상에 부착시키는 것을 포함하는, 기판의 진동 댐핑(vibration damping)을 개선하는 방법.
- 제 14 항에 있어서,
상기 부착은
a. 상기 플라스티솔을 상기 기판상에 적용하고,
b. 상기 플라스티솔을 융합시켜 플라스티솔-피복된 기판을 제조하고,
c. 상기 플라스티솔-피복된 기판을 주위 온도로 냉각시키는 것
을 포함하며, 이 때
상기 플라스티솔을 상기 기판상에 적용하는 것은, 상기 기판을 상기 플라스티솔로 코팅하는 것을 포함하고, 상기 코팅은 분무 코팅 및/또는 압출 코팅을 포함하는, 방법. - 제 14 항에 있어서,
상기 부착은
a. 상기 플라스티솔을 시트로 융합시키고,
b. 상기 시트를 상기 기판에 접착시키는 것
을 포함하는, 방법. - 제 17 항에 있어서,
상기 기판이 차륜 차량(wheeled vehicle)의 일부인, 방법.
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US20160075858A1 (en) | 2016-03-17 |
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US20160075857A1 (en) | 2016-03-17 |
WO2016044238A1 (en) | 2016-03-24 |
KR102489787B1 (ko) | 2023-01-17 |
EP3194483A1 (en) | 2017-07-26 |
WO2016044230A1 (en) | 2016-03-24 |
US20160075856A1 (en) | 2016-03-17 |
CN106715558B (zh) | 2019-06-21 |
US20160075855A1 (en) | 2016-03-17 |
EP3194484A1 (en) | 2017-07-26 |
JP2017528587A (ja) | 2017-09-28 |
KR102479318B1 (ko) | 2022-12-19 |
WO2016044238A8 (en) | 2017-04-27 |
US10077352B2 (en) | 2018-09-18 |
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