GB2166685A - Manufacturing method of laminate film - Google Patents
Manufacturing method of laminate film Download PDFInfo
- Publication number
- GB2166685A GB2166685A GB08524761A GB8524761A GB2166685A GB 2166685 A GB2166685 A GB 2166685A GB 08524761 A GB08524761 A GB 08524761A GB 8524761 A GB8524761 A GB 8524761A GB 2166685 A GB2166685 A GB 2166685A
- Authority
- GB
- United Kingdom
- Prior art keywords
- approx
- mol
- film
- polymer
- polymers
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 239000005001 laminate film Substances 0.000 title description 15
- 229920000642 polymer Polymers 0.000 claims abstract description 60
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 12
- 238000010030 laminating Methods 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 37
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 2
- 238000000465 moulding Methods 0.000 abstract description 2
- -1 aromatic dicarboxylic acids Chemical class 0.000 description 66
- 239000012071 phase Substances 0.000 description 31
- 229920000728 polyester Polymers 0.000 description 24
- 229920000106 Liquid crystal polymer Polymers 0.000 description 21
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 17
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 14
- 125000003118 aryl group Chemical group 0.000 description 14
- 125000004432 carbon atom Chemical group C* 0.000 description 12
- 239000004974 Thermotropic liquid crystal Substances 0.000 description 11
- 229910052736 halogen Inorganic materials 0.000 description 11
- 150000002367 halogens Chemical class 0.000 description 11
- 229920005989 resin Polymers 0.000 description 11
- 239000011347 resin Substances 0.000 description 11
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 10
- 239000000178 monomer Substances 0.000 description 9
- 229920000139 polyethylene terephthalate Polymers 0.000 description 9
- 239000005020 polyethylene terephthalate Substances 0.000 description 9
- 230000003252 repetitive effect Effects 0.000 description 9
- 125000003545 alkoxy group Chemical group 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 7
- 238000010128 melt processing Methods 0.000 description 7
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 6
- 229920005992 thermoplastic resin Polymers 0.000 description 6
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000004417 polycarbonate Substances 0.000 description 5
- 229920000515 polycarbonate Polymers 0.000 description 5
- XBNGYFFABRKICK-UHFFFAOYSA-N 2,3,4,5,6-pentafluorophenol Chemical compound OC1=C(F)C(F)=C(F)C(F)=C1F XBNGYFFABRKICK-UHFFFAOYSA-N 0.000 description 4
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- IZUPBVBPLAPZRR-UHFFFAOYSA-N pentachloro-phenol Natural products OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl IZUPBVBPLAPZRR-UHFFFAOYSA-N 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229920001187 thermosetting polymer Polymers 0.000 description 4
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 3
- KAUQJMHLAFIZDU-UHFFFAOYSA-N 6-Hydroxy-2-naphthoic acid Chemical compound C1=C(O)C=CC2=CC(C(=O)O)=CC=C21 KAUQJMHLAFIZDU-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- 239000004734 Polyphenylene sulfide Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000010924 continuous production Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 230000004927 fusion Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 229920001707 polybutylene terephthalate Polymers 0.000 description 3
- 229920006393 polyether sulfone Polymers 0.000 description 3
- 229920002530 polyetherether ketone Polymers 0.000 description 3
- 229920000069 polyphenylene sulfide Polymers 0.000 description 3
- 229920006295 polythiol Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 2
- LAQYHRQFABOIFD-UHFFFAOYSA-N 2-methoxyhydroquinone Chemical compound COC1=CC(O)=CC=C1O LAQYHRQFABOIFD-UHFFFAOYSA-N 0.000 description 2
- XCZKKZXWDBOGPA-UHFFFAOYSA-N 2-phenylbenzene-1,4-diol Chemical compound OC1=CC=C(O)C(C=2C=CC=CC=2)=C1 XCZKKZXWDBOGPA-UHFFFAOYSA-N 0.000 description 2
- XMEQDAIDOBVHEK-UHFFFAOYSA-N 3-bromo-4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C(Br)=C1 XMEQDAIDOBVHEK-UHFFFAOYSA-N 0.000 description 2
- QGNLHMKIGMZKJX-UHFFFAOYSA-N 3-chloro-4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C(Cl)=C1 QGNLHMKIGMZKJX-UHFFFAOYSA-N 0.000 description 2
- IJFXRHURBJZNAO-UHFFFAOYSA-N 3-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC(O)=C1 IJFXRHURBJZNAO-UHFFFAOYSA-N 0.000 description 2
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 2
- LTFHNKUKQYVHDX-UHFFFAOYSA-N 4-hydroxy-3-methylbenzoic acid Chemical compound CC1=CC(C(O)=O)=CC=C1O LTFHNKUKQYVHDX-UHFFFAOYSA-N 0.000 description 2
- FNYDIAAMUCQQDE-UHFFFAOYSA-N 4-methylbenzene-1,3-diol Chemical compound CC1=CC=C(O)C=C1O FNYDIAAMUCQQDE-UHFFFAOYSA-N 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 239000004696 Poly ether ether ketone Substances 0.000 description 2
- 239000004962 Polyamide-imide Substances 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 239000004695 Polyether sulfone Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 150000004984 aromatic diamines Chemical class 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 125000006267 biphenyl group Chemical group 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical compound OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 0.000 description 2
- VKONPUDBRVKQLM-UHFFFAOYSA-N cyclohexane-1,4-diol Chemical compound OC1CCC(O)CC1 VKONPUDBRVKQLM-UHFFFAOYSA-N 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000005304 joining Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920002312 polyamide-imide Polymers 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920001748 polybutylene Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001195 polyisoprene Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 229920002689 polyvinyl acetate Polymers 0.000 description 2
- 239000011118 polyvinyl acetate Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229920001289 polyvinyl ether Polymers 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- JMSVCTWVEWCHDZ-UHFFFAOYSA-N syringic acid Chemical compound COC1=CC(C(O)=O)=CC(OC)=C1O JMSVCTWVEWCHDZ-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- RLMGYIOTPQVQJR-WDSKDSINSA-N (1s,3s)-cyclohexane-1,3-diol Chemical compound O[C@H]1CCC[C@H](O)C1 RLMGYIOTPQVQJR-WDSKDSINSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- 229940035437 1,3-propanediol Drugs 0.000 description 1
- KZEVSDGEBAJOTK-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[5-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CC=1OC(=NN=1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O KZEVSDGEBAJOTK-UHFFFAOYSA-N 0.000 description 1
- PVRZMTHMPKVOBP-UHFFFAOYSA-N 1-n,4-n-dimethylbenzene-1,4-diamine Chemical compound CNC1=CC=C(NC)C=C1 PVRZMTHMPKVOBP-UHFFFAOYSA-N 0.000 description 1
- MWQVQEFJAIFHFZ-UHFFFAOYSA-N 2,3-dichloro-4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C(Cl)=C1Cl MWQVQEFJAIFHFZ-UHFFFAOYSA-N 0.000 description 1
- NAQNEMNLLODUCG-UHFFFAOYSA-N 2,3-dichloroterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(Cl)=C1Cl NAQNEMNLLODUCG-UHFFFAOYSA-N 0.000 description 1
- RYRZSXJVEILFRR-UHFFFAOYSA-N 2,3-dimethylterephthalic acid Chemical compound CC1=C(C)C(C(O)=O)=CC=C1C(O)=O RYRZSXJVEILFRR-UHFFFAOYSA-N 0.000 description 1
- 229940075142 2,5-diaminotoluene Drugs 0.000 description 1
- BXGYYDRIMBPOMN-UHFFFAOYSA-N 2-(hydroxymethoxy)ethoxymethanol Chemical compound OCOCCOCO BXGYYDRIMBPOMN-UHFFFAOYSA-N 0.000 description 1
- QPBGNSFASPVGTP-UHFFFAOYSA-N 2-bromoterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(Br)=C1 QPBGNSFASPVGTP-UHFFFAOYSA-N 0.000 description 1
- WIPYZRZPNMUSER-UHFFFAOYSA-N 2-chloro-4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1Cl WIPYZRZPNMUSER-UHFFFAOYSA-N 0.000 description 1
- ZPXGNBIFHQKREO-UHFFFAOYSA-N 2-chloroterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(Cl)=C1 ZPXGNBIFHQKREO-UHFFFAOYSA-N 0.000 description 1
- IWFVHBRPBOMFMG-UHFFFAOYSA-N 2-ethoxyterephthalic acid Chemical compound CCOC1=CC(C(O)=O)=CC=C1C(O)=O IWFVHBRPBOMFMG-UHFFFAOYSA-N 0.000 description 1
- NAUKGYJLYAEUBD-UHFFFAOYSA-N 2-ethylterephthalic acid Chemical compound CCC1=CC(C(O)=O)=CC=C1C(O)=O NAUKGYJLYAEUBD-UHFFFAOYSA-N 0.000 description 1
- VQBBXLZPRXHYBO-UHFFFAOYSA-N 2-methoxyterephthalic acid Chemical compound COC1=CC(C(O)=O)=CC=C1C(O)=O VQBBXLZPRXHYBO-UHFFFAOYSA-N 0.000 description 1
- OBCSAIDCZQSFQH-UHFFFAOYSA-N 2-methyl-1,4-phenylenediamine Chemical compound CC1=CC(N)=CC=C1N OBCSAIDCZQSFQH-UHFFFAOYSA-N 0.000 description 1
- UFMBOFGKHIXOTA-UHFFFAOYSA-N 2-methylterephthalic acid Chemical compound CC1=CC(C(O)=O)=CC=C1C(O)=O UFMBOFGKHIXOTA-UHFFFAOYSA-N 0.000 description 1
- NTKLFSYUWYPMCJ-UHFFFAOYSA-N 2-phenoxybenzene-1,4-diol Chemical compound OC1=CC=C(O)C(OC=2C=CC=CC=2)=C1 NTKLFSYUWYPMCJ-UHFFFAOYSA-N 0.000 description 1
- VMKYTRPNOVFCGZ-UHFFFAOYSA-N 2-sulfanylphenol Chemical compound OC1=CC=CC=C1S VMKYTRPNOVFCGZ-UHFFFAOYSA-N 0.000 description 1
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 description 1
- 229940018563 3-aminophenol Drugs 0.000 description 1
- RSFDFESMVAIVKO-UHFFFAOYSA-N 3-sulfanylbenzoic acid Chemical compound OC(=O)C1=CC=CC(S)=C1 RSFDFESMVAIVKO-UHFFFAOYSA-N 0.000 description 1
- DOFIAZGYBIBEGI-UHFFFAOYSA-N 3-sulfanylphenol Chemical compound OC1=CC=CC(S)=C1 DOFIAZGYBIBEGI-UHFFFAOYSA-N 0.000 description 1
- ICNFHJVPAJKPHW-UHFFFAOYSA-N 4,4'-Thiodianiline Chemical compound C1=CC(N)=CC=C1SC1=CC=C(N)C=C1 ICNFHJVPAJKPHW-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- WVDRSXGPQWNUBN-UHFFFAOYSA-N 4-(4-carboxyphenoxy)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1OC1=CC=C(C(O)=O)C=C1 WVDRSXGPQWNUBN-UHFFFAOYSA-N 0.000 description 1
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 description 1
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 description 1
- AHLDBNUMCNFUMG-UHFFFAOYSA-N 4-[1-(4-hydroxyphenoxy)ethoxy]phenol Chemical compound C=1C=C(O)C=CC=1OC(C)OC1=CC=C(O)C=C1 AHLDBNUMCNFUMG-UHFFFAOYSA-N 0.000 description 1
- UHNUHZHQLCGZDA-UHFFFAOYSA-N 4-[2-(4-aminophenyl)ethyl]aniline Chemical compound C1=CC(N)=CC=C1CCC1=CC=C(N)C=C1 UHNUHZHQLCGZDA-UHFFFAOYSA-N 0.000 description 1
- ZYZQSCWSPFLAFM-UHFFFAOYSA-N 4-amino-2-chlorophenol Chemical compound NC1=CC=C(O)C(Cl)=C1 ZYZQSCWSPFLAFM-UHFFFAOYSA-N 0.000 description 1
- ABJQKDJOYSQVFX-UHFFFAOYSA-N 4-aminonaphthalen-1-ol Chemical compound C1=CC=C2C(N)=CC=C(O)C2=C1 ABJQKDJOYSQVFX-UHFFFAOYSA-N 0.000 description 1
- BKNDOJUZMXDRDL-UHFFFAOYSA-N 4-butylcyclohexa-1,5-diene-1,4-diol Chemical compound CCCCC1(O)CC=C(O)C=C1 BKNDOJUZMXDRDL-UHFFFAOYSA-N 0.000 description 1
- JQVAPEJNIZULEK-UHFFFAOYSA-N 4-chlorobenzene-1,3-diol Chemical compound OC1=CC=C(Cl)C(O)=C1 JQVAPEJNIZULEK-UHFFFAOYSA-N 0.000 description 1
- FFUMDYCIOSWRLV-UHFFFAOYSA-N 4-hydroxy-2,6-dimethylbenzoic acid Chemical compound CC1=CC(O)=CC(C)=C1C(O)=O FFUMDYCIOSWRLV-UHFFFAOYSA-N 0.000 description 1
- OMNHTTWQSSUZHO-UHFFFAOYSA-N 4-hydroxy-3,5-dimethylbenzoic acid Chemical compound CC1=CC(C(O)=O)=CC(C)=C1O OMNHTTWQSSUZHO-UHFFFAOYSA-N 0.000 description 1
- QGNGOGOOPUYKMC-UHFFFAOYSA-N 4-hydroxy-6-methylaniline Chemical compound CC1=CC(O)=CC=C1N QGNGOGOOPUYKMC-UHFFFAOYSA-N 0.000 description 1
- ZFIQGRISGKSVAG-UHFFFAOYSA-N 4-methylaminophenol Chemical compound CNC1=CC=C(O)C=C1 ZFIQGRISGKSVAG-UHFFFAOYSA-N 0.000 description 1
- LMJXSOYPAOSIPZ-UHFFFAOYSA-N 4-sulfanylbenzoic acid Chemical compound OC(=O)C1=CC=C(S)C=C1 LMJXSOYPAOSIPZ-UHFFFAOYSA-N 0.000 description 1
- VARPGHCVZGMTLL-UHFFFAOYSA-N 5,7-dichloro-6-hydroxynaphthalene-2-carboxylic acid Chemical compound ClC1=C(O)C(Cl)=CC2=CC(C(=O)O)=CC=C21 VARPGHCVZGMTLL-UHFFFAOYSA-N 0.000 description 1
- MIBYFOLNIIUGNA-UHFFFAOYSA-N 5-chloro-6-hydroxynaphthalene-2-carboxylic acid Chemical compound ClC1=C(O)C=CC2=CC(C(=O)O)=CC=C21 MIBYFOLNIIUGNA-UHFFFAOYSA-N 0.000 description 1
- RHXQHKDRWDVLBY-UHFFFAOYSA-N 6-hydroxy-5-methoxynaphthalene-2-carboxylic acid Chemical compound OC(=O)C1=CC=C2C(OC)=C(O)C=CC2=C1 RHXQHKDRWDVLBY-UHFFFAOYSA-N 0.000 description 1
- XKFNZRZICQABOD-UHFFFAOYSA-N 6-hydroxy-5-methylnaphthalene-2-carboxylic acid Chemical compound OC(=O)C1=CC=C2C(C)=C(O)C=CC2=C1 XKFNZRZICQABOD-UHFFFAOYSA-N 0.000 description 1
- JCJUKCIXTRWAQY-UHFFFAOYSA-N 6-hydroxynaphthalene-1-carboxylic acid Chemical compound OC1=CC=C2C(C(=O)O)=CC=CC2=C1 JCJUKCIXTRWAQY-UHFFFAOYSA-N 0.000 description 1
- ODILNTRTDZEAJN-UHFFFAOYSA-N 6-sulfanylnaphthalene-2-carboxylic acid Chemical compound C1=C(S)C=CC2=CC(C(=O)O)=CC=C21 ODILNTRTDZEAJN-UHFFFAOYSA-N 0.000 description 1
- JHXIMYHYJSQGGB-UHFFFAOYSA-N 7-chloro-6-hydroxynaphthalene-2-carboxylic acid Chemical compound C1=C(O)C(Cl)=CC2=CC(C(=O)O)=CC=C21 JHXIMYHYJSQGGB-UHFFFAOYSA-N 0.000 description 1
- DMKFFMMKXWTWIS-UHFFFAOYSA-N 7-sulfanylnaphthalene-2-carboxylic acid Chemical compound C1=CC(S)=CC2=CC(C(=O)O)=CC=C21 DMKFFMMKXWTWIS-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- 101100272279 Beauveria bassiana Beas gene Proteins 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 229920004142 LEXAN™ Polymers 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Chemical class 0.000 description 1
- 239000004418 Lexan Substances 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229920002614 Polyether block amide Polymers 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229920002600 TPX™ Polymers 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- LUSFFPXRDZKBMF-YUMQZZPRSA-N [(1s,3s)-3-(hydroxymethyl)cyclohexyl]methanol Chemical compound OC[C@H]1CCC[C@H](CO)C1 LUSFFPXRDZKBMF-YUMQZZPRSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 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
- 125000002252 acyl group Chemical group 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- WYLQRHZSKIDFEP-UHFFFAOYSA-N benzene-1,4-dithiol Chemical compound SC1=CC=C(S)C=C1 WYLQRHZSKIDFEP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- AJPXTSMULZANCB-UHFFFAOYSA-N chlorohydroquinone Chemical compound OC1=CC=C(O)C(Cl)=C1 AJPXTSMULZANCB-UHFFFAOYSA-N 0.000 description 1
- PFURGBBHAOXLIO-OLQVQODUSA-N cis-cyclohexane-1,2-diol Chemical compound O[C@H]1CCCC[C@H]1O PFURGBBHAOXLIO-OLQVQODUSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- XBZSBBLNHFMTEB-UHFFFAOYSA-N cyclohexane-1,3-dicarboxylic acid Chemical compound OC(=O)C1CCCC(C(O)=O)C1 XBZSBBLNHFMTEB-UHFFFAOYSA-N 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002168 ethanoic acid esters Chemical class 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 150000002221 fluorine Chemical class 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- OLAKSHDLGIUUET-UHFFFAOYSA-N n-anilinosulfanylaniline Chemical compound C=1C=CC=CC=1NSNC1=CC=CC=C1 OLAKSHDLGIUUET-UHFFFAOYSA-N 0.000 description 1
- VAWFFNJAPKXVPH-UHFFFAOYSA-N naphthalene-1,6-dicarboxylic acid Chemical compound OC(=O)C1=CC=CC2=CC(C(=O)O)=CC=C21 VAWFFNJAPKXVPH-UHFFFAOYSA-N 0.000 description 1
- FZZQNEVOYIYFPF-UHFFFAOYSA-N naphthalene-1,6-diol Chemical compound OC1=CC=CC2=CC(O)=CC=C21 FZZQNEVOYIYFPF-UHFFFAOYSA-N 0.000 description 1
- MNZMMCVIXORAQL-UHFFFAOYSA-N naphthalene-2,6-diol Chemical compound C1=C(O)C=CC2=CC(O)=CC=C21 MNZMMCVIXORAQL-UHFFFAOYSA-N 0.000 description 1
- XMHBJPKFTZSWRJ-UHFFFAOYSA-N naphthalene-2,6-dithiol Chemical compound C1=C(S)C=CC2=CC(S)=CC=C21 XMHBJPKFTZSWRJ-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000011505 plaster Substances 0.000 description 1
- 229920001279 poly(ester amides) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000343 polyazomethine Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000003578 releasing effect Effects 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- WKOLLVMJNQIZCI-UHFFFAOYSA-N vanillic acid Chemical compound COC1=CC(C(O)=O)=CC=C1O WKOLLVMJNQIZCI-UHFFFAOYSA-N 0.000 description 1
- TUUBOHWZSQXCSW-UHFFFAOYSA-N vanillic acid Natural products COC1=CC(O)=CC(C(O)=O)=C1 TUUBOHWZSQXCSW-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0013—Extrusion moulding in several steps, i.e. components merging outside the die
- B29C48/0014—Extrusion moulding in several steps, i.e. components merging outside the die producing flat articles having components brought in contact outside the extrusion die
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
- B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
- B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2305/00—Condition, form or state of the layers or laminate
- B32B2305/08—Reinforcements
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2305/00—Condition, form or state of the layers or laminate
- B32B2305/22—Fibres of short length
- B32B2305/24—Whiskers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2305/00—Condition, form or state of the layers or laminate
- B32B2305/30—Fillers, e.g. particles, powders, beads, flakes, spheres, chips
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2305/00—Condition, form or state of the layers or laminate
- B32B2305/55—Liquid crystals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2309/00—Parameters for the laminating or treatment process; Apparatus details
- B32B2309/08—Dimensions, e.g. volume
- B32B2309/10—Dimensions, e.g. volume linear, e.g. length, distance, width
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2309/00—Parameters for the laminating or treatment process; Apparatus details
- B32B2309/08—Dimensions, e.g. volume
- B32B2309/10—Dimensions, e.g. volume linear, e.g. length, distance, width
- B32B2309/105—Thickness
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2367/00—Polyesters, e.g. PET, i.e. polyethylene terephthalate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
- B32B37/15—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
- B32B37/153—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state at least one layer is extruded and immediately laminated while in semi-molten state
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Laminated Bodies (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
Abstract
A high strength laminate sheet which comprises a film of a polymer adapted to form an anisotropic melt phase (liquid crystal) and a film of a thermoplastic polymer is produced by laminating the films, including moulding each film at the same time.
Description
SPECIFICATION
Manufacturing method of laminate film
The present invention relates to an industrially advantageous manufacturing method for continuously manufacturing a high strength multi-layer film containing, as at least one layer, a polymer adapted to form anisotropic melt-phase.
Polymers known as thermotropic liquid crystal polymers and which are adapted to give anisotropic melt phase are known to have very high strength in their oriented direction because of the anisotropy of their orientation, but their strength in the perpendicular direction to their oriented direction is notably lower, as compared with that in the oriented direction, so that either it is difficult to form it into film by usual continuous process or the film's utility is limited in many uses.
Heretofore, proposed are manufacturing methods of sheets or films formed of thermotropic liquid crystal polymers which show desirable characteristics in many fields. For example, Laid-Open Patent No.4626/1981,
Laid-Open Patent No.46727/1981 and Laid-Open Patent No. 161821/1980 propose internal plasticiation of molecular structure and plasticization by blending the polymers with plasticizers, etc., but these sheets or films are rather melt-processing with their anisotropy extremely reduced; as a consequence, their strength is sacrificed.
Laid Open Patent No.31718/1983 proposes a multiaxiallyoriented laminate formed by laminating uniaxial sheets of thermotropic liquid crystal polymers, in which high strength is achieved by laminating in multi-layers sheets oriented in different axial directions. But it is difficult to laminate 2 sheets in a continuous process in such a way that their axial lines make definite angles to each other. This method is not economical and is not satisfactory as an industrial manufacturing method.
The present invention has as its object resolving the technical theme of film-forming with such polymers, while maintaining high orientation and high strength, characteristics which the thermotropic liquid phase polymers possess.
Thus the present invention provides a method for continuously manufacturing a high strength laminate film on industrial scale and relates to a manufacturing method of laminate film characterized in that in manufacturing a multi-layer sheet and/or a multi-layer film formed of a polymer adapted to form anisotropic melt phase and a thermoplastic polymer having film forming ability, at least one of the polymers above-mentioned is laminated by way of cushion molding.
In the invention as defined in other words, a laminate sheet which comprises a fim of a polymer adapted to form the anisotropic melt phase and a film of a thermoplastic polymer having the film-forming property is produced by laminating at least one of both polymers. One of both polymers is first moulded to film and the other polymer is laminated thereon. Alternatively both polymers may be moulded to film at the same time and laminated on each other.
According to this invention, a method capable of industrial continuous production of multi-layer laminate film in which the strength in the direction of orientation is mostly dependent on the first polymer adapted to show anisotropic melt phase, while the strength in the lateral axial direction is mostly dependent on the thermoplastic polymer having film-forming ability, or the second polymer, and the film forming ability is conferred on the second thermoplastic polymer.
The polymers adapted to give anisotropic melt phase which is used for laminate film of this invention means polymer compositions which show optical anisotropy, when melted, and which are thermoplastic and melt-processing. They are generally classified as thermotropic liquid crystal polymers.
Polymers adapted to form such anisotropic melt phase have a property that in their fused state, polymer molecule chains show regular parallel arrangement. The state in which molecules are arranged in this fashion is often called liquid crystal state or nematic phase of liquid crystalline material. Such polymers are generally slender, flat and fairly high in rigidity along longer axis of molecule and are normally manufactured from monomers having a plurality of chain extended bonds being either in coaxial or parallel relation to each other.
The property of the anisotropic melt phase may be checked for sure by the commonly used method of polarization inspection based on utilization of orthogonal polarizers. More particularly, the confirmation of the anisotropic melt phase may be made by observing a sample put on a Leitz hot stage at a multiplicity of 40 in nitrogen atmosphere, using a Leitz polarization microscope. The aforementioned polymers are optically anisotropic. Thus they permit light to pass through, when checked between orthogonal polarizers. If a sample is optically anisotropic, a polarized light will pass through it, even if it is in stationary state.
Mentioned as the components of the polymers adapted to form anisotropic fused phase such as the aforementioned are: Q Those comprising one or more of aromatic dicarboxylic acids and acyclic dicarboxylic acids; O Those comprising one or more of aromatic diols, acyclic diols and aliphatic diols; Q3 Those comprising one or more of aromatic hydroxycarboxylic acids; Q4 Those comprising one or more of aromatic thiol carboxylic acids; (ffi) Those comprising one or more of aromatic dithiols and aromatic thiol phenols; and (ss) Those comprising one or more of aromatic hydroxyamines and aromatic diamines; and the polymers adapted to form anisotropicfused phase are composed of the following combinations: I) Polyesters formed of (y) and
II) Polyesters formed of (g only;
111) Polyesters formed of , (g and
IV) Polythiol esters formed of (i9 only;
V) Polythiol esters formed of ( ) and
VI) Polythiol esters formed of ( ) and
VII) Polyester amides formed of () ) and ; and
VIII) Polyester amides formed ofO ,0,0 and and ( .
Although not included in the categories of combinations of components above-mentioned, aromatic polyazomethines are included as polymers adapted to form anisotropic fused phase. Mentioned as particular examples of such polymers are: Poly (nitrilo-2-methyl-1 ,4-phenylene-nitriloethylidene-1 ,4- phenylene ethylidene), poly (nitrilo-2-methyl-1 ,4-phenylene nitriloethylidene-1 ,4-phenylene methylidene) and poly (nitrilo-2-chloro-1 4-phenylene nitrilomethylidene-1 4-phenylene methylidene).
Further, although not included in the categories of the combinations of the aforementioned components, polyester carbonates are included as the polymers adapted to form anisotropicfused phase. Some of them essentially comprise 4-oxybenzoyl units, dioxyphenyl units, dioxycarbonyl units and terephthaloyl units.
In the following, such compounds which are usable as components of l)-VIII) above-mentioned are listed hereunder:
Mentioned as aromatic dicarboxylic acids are: Aromatic dicarboxylic acids such as terephthalic acid, 4,4'-diphenyl dicarboxylic acid, 4,4'-triphenyl dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, diphenyl ether-4,4'-dicarboxylic acid, diphenoxyethane-4,4'-dicarboxylic acid, diphenoxybutane-4,4'-dicarboxylic acid, diphenylethane-4,4'-dicarboxylic acid, isophthalic acid, diphenyl ether-3,3'-dicarboxylic acid, diphenoxyethane-3,3'-dicarboxylic acid, diphenyl ethane-3,3'-dicarboxylic acid and naphthalene-1,6-dicarboxylic acid or alkyl, alkoxyl or halogen substitutes of the aforementioned aromatic dicarboxylic acids such as chloroterephthalic acid, dichloroterephthalic acid, bromoterephthalic acid, methyl terephthalic acid, dimethyl terephthalic acid, ethyl terephthalic acid, methoxyterephthalic acid and ethoxyterephthalic acid.
Mentioned as the acyclic dicarboxylic acids are: Acyclic dicarboxylic acids such as trans-1 ,4-cyclohexane dicarboxylic acid, cis-1,4-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, etc., or alkyl, alkoxyl or halogen substitutes of the aforementioned acyclic dicarboxylic acids such as tl-ans-1,4-(l -methyl)cyclohexane-dicarboxylic acid, trans-1 ,4-(1 -chloro)-cyclohexane dicarboxylic acid, etc.
Mentioned as aromatic diols are: Aromatic diols such as hydroquinone, resorcinol, 4,4'- dihydroxydiphenyl, 4,4'-dihydroxytriphenyl, 2,6-naphthalenediol, 4,4'-dihydroxydiphenyl ether, bis (4 hydroxyphenoxy)-ethane, 3,3'-dihydroxydiphenyl, 3,3'-dihydroxydiphenyl ether, 1,6-naphthalenediol, 2,2- bis(4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) methane, etc., or alkyl, alkoxyl or halogen substitutes of the aforementioned aromatic diols such as chlorohydroquinone, methyl hydroquinone, 1-butyl hydroquinone, phenyl hydroquinone, methoxyhydroquinone, phenoxyhydroquinone, 4-chlororesorcinol, 4-methyl resorcinol, etc.
Mentioned as the acyclic diols are: Acyclic diols such as trans-1 ,4-cyclohexanediol, cis-1 ,4- cyclohexanediol, trans-i ,4-cyclohexane dimethanol, cis-1,4-cyclohexane dimethanol, trans-1,3cyclohexanediol, cis-1 ,2-cyclohexanediol and trans-1 ,3-cyclohexanedimethanol or alkyl, alkoxyl or halogen substitutes of the aforementioned acyclic diols such as trans-1,4- (1-methyl) cyclohexanediol and trans-1,4 (1-chloro) cyclohexanediol.
Mentioned as the aliphatic diols are: Straight chain or branched aliphatic diols such as ethylene glycol, 1, 3-propanediol, 1,4-butanediol, neopentyl glycol, etc.
Mentioned as the aromatic hydroxycarboxylic acids are: Aromatic hydroxycarboxylic acids such as 4-hydroxybenzoic acid, 3-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 6-hydroxy-1-naphthoic acid, etc., or alkyl, alkoxyl or halogen substitutes of aromatic hydroxycarboxylic acids such as 3-methyl-4 hyd roxybenzoic acid, 3,5-di methyl-4-hydroxybenzoic acid, 2,6-dimethyl-4-hydroxybenzoic acid, 3-methoxy- 4-hydroxybenzoic acid, 3,5-dimethoxy-4-hydroxy-benzoic acid, 6-hydroxy-5-methyl-2-naphthoic acid, 6hydroxy-5-methoxy-2-naphthoic acid, 3-chloro-4-hydroxy-benzoic acid, 2-chloro-4-hydroxybenzoic acid, 2,3-dichloro-4-hydroxybenzoic acid, 3-5-dichloro-4-hydroxybenzoic acid, 2,5-dicm loro-4-hydroxybenzoic acid, 3-bromo-4-hydroxy-benzoic acid, 6-hydroxy-5-chloro-2-naphthoic acid, 6-hydroxy-7-chloro-2- naphthoic acid, 6-hydroxy-5,7-dichloro-2-naphthoic acid, etc.
Mentioned as the aromatic mercaptocarboxilic acid are: 4-Mercaptobenzoic acid, 3-mercaptobenzoic acid, 6-mercapto-2-naphthoic acid, 7-mercapto-2-naphthoic acid, etc.
Mentioned as the aromatic dithiolds are: Benzene-1, 4-dithiol, benzene-1 3-dithiol, 2,6-naphthalene dithiol and 2,7-naphthalene dithiols, etc.
Mentioned as the aromatic mercaptophenols are: cl-Mercaptophenol, 3-mercaptophenol, 6- mercaptophenol and 7-mercaptophenol, etc.
Mentioned as aromatic hydroxyamines and aromatic diamines are: 4-Aminophenol, N-methyl-4 aminophenol, 1 ,4-phenylenediamine, N-methyl-l P-phenylenediamine, N, N '-dimethyl-1 ,4- phenylenediamine, 3-aminophenol, 3-methyl-4-aminophenol, 2-chloro-4-aminophenol, 4-amino-i -naphthol, 4-amino-4'-hydroxydiphenyl, 4-amino-4'-hydroxydiphenyl ether, 4-amino-4'-hydroxydiphenyl methane, 4-amino-4'-hydroxydiphenyl sulfide, 4,4'-diaminophenyl sulfide (thiodianiline), 4,4'-diaminophenyl-sulfone, 2,5-diaminotoluene, 4,4'-ethylene dianiline, 4.4'-diaminodiphenoxyethane, 4,4'-diaminodiphenyl methane (methylene dianiline), 4,4'-diaminodiphenyl ether (oxydianiline), etc.
Of the aforementioned polymers l)-VIII) composed of the aforementioned components, there exist those which are adapted to form anisotropic melt phase and those which are not, depending on their components, their composition ratios and sequence distributions in these polymers. The polymers used in accordance with this invention are restricted to those of the aforementioned polymers adapted to form anisotropic melt phase.
The polyesters of the aforementioned I), II) and Ill) and polyester amides of VIII), being polymers adapted to form anisotropic fused phase which are desirable for use in exercising this invention, may be produced by various ester forming methods which enable mutual reactions of organic monomer compounds having functional groups which play the role of forming the required repetitive units by condensation. For example, such functional groups of these organic monomer compounds may include carboxyl, hydroxyl, ester and acyloxy groups, acid halides and amine group. The aforementioned organic monomer compounds may be reacted with each other by fusion acidolytic process, while keeping any heat exchange fluid out of existence.
According to this method, first, fused solution of the reaction materials is formed by heating the monomers together. As the reactions are continued, solid polymer particles become being suspended in the liquid. For the purpose of facilitating removal of volatile matters (e.g., acetic acid or water) which are produced as byproducts at the final stage of condenstion, the system may be put under vacuum.
The slurry polymerization process may be employed for forming perfect aromatic polyesters which are preferred for use in exercising this invention. By this method, the solid product is obtained in the state of being suspended in a heat exchanging medium.
Whichever process, the aforementioned fusion acidolytic process or the slurry polymerization process, is employed, the organic monomer reaction materials which are to derive the perfect aromatic polyesters may be put to use for the reactions in their denatured form (thus, as lower acyl esters) in which the hydroxyl groups of such monomers at normal temperature are esterified. As lower acyl groups, those with carbon atoms approx. 2-4 in number are preferable. Preferably, acetic acid esters of such organic monomer reaction materials are put to use for the reactions.
Further mentioned as typical examples of catalyzers which are arbitrarily usable either in the fusion acidolytic process or slurry process are: Gaseous acid catalyzers, etc., such as dialkyl tin oxide (e.g., dibutyl tin oxide), diallyl tin oxide, titanium dioxide, antimony trioxide, alkoxytitanium silicate, titanium alkoxide, alkali and alkaline earth metal salts of carboxylic acids (e.g., zinc acetate), Lewis acids (e.g., BF3), hydrogen halides (e.g., HCI), etc. The amounts of catalyzers used generally should be approx.0.001 by % by weight, particularly, approx. 0.01-0.2% by weight, based on the total weight of monomers.
The perfect aromatic polymers suitable for use in exercising this invention show a tendency of being substantially insoluble in common solvents and therefore, they are not suitable for forming from solution.
However, as already described, these polymers permit easy forming by the ordinary fushion forming process. Particularly desirable perfect aromatic polymers are soluble in some degree in pentafluorophenol.
The perfect aromatic polyesters preferable for use in exercising this invention generally should have weight average molecular weights of approx. 2,000-200,000, preferably, approx. 10,000- 50,000 and more preferably, approx. 20,000-25,000. On the other hand the preferable perfect aromatic poly (ester-amides) generally should have molecular weights of approx. 5,000-50,000, preferably, approx. 10,000-30,000, e.g., 15,000-17,000. Measurement of such molecular weights may be made by gel permeation chromatography and other standard measuring methods which do not accompany solution forming of polymer, for example, by determining terminal groups by infrared spectroscopy on compression molded films.Or the measurement of molecular weight may be made by light scattering methods on the solution of polymer in pentafluorophenol.
The aforementioned perfect aromatic polyesters and polyester amides, when dissolved in pentafluorophenol at 60"C at a concentration of 0.1 weight %, generally give logarithmic viscosity (I.V.) of at least approx. 2.0 dl/g, for example, approx. 2.0-10.0 dl/g.
The polyesters adapted to form anisotropic fused phase which are particularly desirable for use in exercising this invention should contain more than approx. 10 mol % of naphthalene part containing repetitive units such as 6-hydroxy-2-naphtoyl, 2,6-dioxynaphthalene and 2,6-dicarboxynaphthalene, etc.
Desirable polyester amides should contain repetitive units of the aforementioned naphthalene part and another part comprising 4-aminophenol or 1,4-phenylene diamine.
Particular examples are given hereunder:
(1) Polyesters essentially composed of the following repetitive units I and II.
The polyesters contain approx. 10-90 mol % of unit I and approx. 10-90 mol % of unit II. In one mode, the units I exist up to approx. 65-85 mol %, preferably, approx. 70-80 mol % (e.g., about 75 mol %). In another mode, the units II exist at as far lower concentrations as approx. 15-35 mol %, preferably, approx. 20-30 mol %, and at least part of hydrogenatoms bonded to the ring(s) are allowed to be substituted, as the case may be, by any substituent radicals selected from among a group consisting of alkyl groups with number of carbon atoms 1 -4, alkoxyl groups with number of carbon atoms 1 -4, halogens, phenyls, substituted phenyls and their combinations.
(2) Polyesters essentially composed ofthefollowing repetitive units l, ll and Ill:
These polyesters contain approx. 30 -70 mol % of unit I. They should preferably, contain approx. 40-60 mol % of unit I, approx. 20-30 mol % of units II and approx. 20-30 mol % of unit Ill and at least part of hydrogen atoms bonded to the ring(s) are allowed to be substituted, as the case may be, by any substituent radicals selected from among a goup consisting of alkyl groups with the number of carbons 1-4, alkoxyl groups with the number of carbons 1-4, halogens, phenyls, substituted phenyls and their combinations.
(3) Polyesters essentially composed of the following repetitive units 1,11, III and IV:
(where R means methyl, chloro, bromo or their combinations, being substituent radicals to hydrogen atoms on benzene ring(s).) They contain approx. 20-60 mol % of unit, I, approx. 5-18 mol % of unit II, approx. 5-35 mol % of unit ill and approx. 20-40 mol % of unit IV. These polyesters should preferably contain approx.
35-45 mol % of unit I, approx. 10-15 mol % of unit II, approx. 15-25 mol % of unit Ill and approx. 25-35 mol % of unit IV. Provided that sum total mol concentration of units II and Ill is substantially equal to the mol concentration of units IV. At least part of the hydrogen atoms which are bonded to the ring(s) are allowed to be substituted, as the case may be, by any substituent radical(s) selected from among a group consisting of alkyl radicals with the number of carbon atoms 1 -4, alkoxyl radicals with the number of carbon atoms 1 -4, halogens, phenyls, substituted phenyls and their combinations. These perfect aromatic polyesters, when dissolved at 60"C in pentafluorophenol at a concentration of 0.3 WN %, generally give their logarithmic viscosities at least 2.0 dl/g, e.g., 2.0-10.0 dl/g.
(4) Polyesters essentially composed of the following repetitive units I, II, Ill and IV:
III Dioxyallyl unit represented by a general formula: t O - Ar - O i (where Ar means a divalent group having at least one benzene ring.)
IV Dicarboxyallyl unit represented by a general formula:
(where Ar' means a divalent group having at least one benzene ring). They contain approx. 20-40 mol % of unit I, more than 10 mol % but less than approx. 50 mol % of unit II, more than 5 mol % but less than approx.
30 mol % of unit Ill and more than 5 mol % but less than approx. 30 mol % of unit IV. These polyesters should preferably contain approx. 20-30 mol % (e.g., approx. 25 mol %) of unit I, approx. 25-40 mol % (e.g., approx. 35 mol %) of unit II, approx. 15-25 mol % (e.g., approx. 20 mol %) of unit Ill and approx. 15-25 mol % (e.g., approx. 20 mol %) of unit IV. And at least part of hydrogen atoms bonded to the ring(s) are allowed to be substituted by any substituent radicals selected from among a group consisting of alkyl radicals with the number of carbon atoms 1-4, alkoxyl radicals with the number of carbon atoms 1 -4, halogens, phenyls, substituted phenyls and their combinations.
The units Ill and IV should preferably be symmetric in the sense that the divalent bonds which are joining each one of them to other units on both sides thereof inside the polymer main chain are symmetrically arranged on 1 or 2 or more of benzene rings (for example, when they exist on a naphthalene ring, they are arranged mutually at para positions or at diagonal ring positions). However, non-symmetrical units which may be derived from resorcinol and isophthalic acid are also usable.
Desirable dioxyallyl unit Ill is:
desirable dicarboxyallyl unit is:
(5) Polyesters essentially composed of the following repetitive units I, ll, and ill:
II Dioxyallyl unit represented by a general formula - Ar - (where Ar means a divalent radical having at least one benzene ring)
Ill Dicarboxyallyl unit represented by a general formula
(where Ar' means a divalent radical containing at least one benzene ring). They contain approx. 10-90 mol % of unit 1, 5-45 mol % of unit II and 5-45 mol % of unit Ill. These polyesters should preferably contain approx. 20-80 mol % of unit I, approx. 10-40 mol % of the unit II and approx. 10-40 mol % of the unit III.
More preferably, they should contain approx. 60-80 mol % of unit I, approx. 10-20 mol % of unit II and approx. 10-20 mol % of unit Ill. And at least part of hydrogen atoms bonded to the ring(s) are allowed to be substituted, as the case may be, by any substituent radical(s) selected from among a group consisting of alkyl radicals with the number of carbon atoms 1 -4, alkoxyl radicals with the number of carbon atoms 1 -4, halogens, phenyls, substituted phenyls and their combinations.
Desirable dioxyallyl unit II should be:
and desirable dicarboxyallyl unit Ill should be:
(6) Polyester amides essentially composed of the following repetitive units I, 11, III and IV:
II A general formula
(where A means a divalent radical having at least one benzene ring or divalenttrans-cyclohexane radical) liy A general formula tY - Ar - Zi} (where Ar means a divalent radical having at least one benzene ring; Y represents 0, NH or NR; and Z stands for NH or NR; where R means alkyl radicals or allyl radicals with the number of carbon atoms 1-6)
IV A general formula
tO - Ar' (where Ar' means a divalent radical having at least one benzene ring).They contain approx. 10-90 mol % of unit I, approx. 5-45 mol % of unit II, approx. 5-45 mol % of unit III and approx. 0-40 mol % of unit iV. And at least part of hydrogen atoms bonded to the ring(s) are allowed to be substituted, as the case may be, by any substituent radicals selected from among a group consisting of alkyl radicals with the number of carbon atoms 1 -4, alkoxyl radicals with the number of carbon atoms 1 -4, halogens, phenyls, substituted phenyls and their combinations.
Desirable dicarboxyallyl unit II should be
desirable unit Ill should be
desirable dioxyallyl unit IV should be
Further, in the polymers adapted to form anisotropic melt phase of this invention, polymers in which part of their high molecular chain is composed of a segment of a polymer adapted to form anisotropic melt phase hereabove-described and the remaining part is composed of a segment of a thermoplastic resin not adapted to form anisotropic melt phase may be included.
The polymer composition of this invention adapted to form an isotropic melt phase and which is melt-processable may contain one or more of (g other polymers adapted to form anisotropic melt phase, (2) thermoplastic resins not adapted to form anisotropic melt phase, (2) thermosetting resins, z low molecular organic compounds, (ss) inorganic substances. The polymer segment adapted to form anisotropic fused phase and the remaining segment are allowed to be either thermodynamically compatible or not.
Included as the thermoplastic resins hereabove mentioned in Q2 are: e.g., polyethylene, polypropylene, polybutylene, polybutadiene, polyisoprene, polyvinyl acetate, polyvinyl chloride, polyvinylidene chloride, polystyrene, acrylic resins, ABS resin, As resin, BS resin, polyurethane, silicone resin, fluorine series resins, polyacetals, polycarbonates, polyethylene terephthalate, aromatic polyesters, polyamides, polyacrilonitrile, polyvinyl alcohol, polyvinyl ether, polyethermide, polyamideimide, polyether etherimide, polyether ether ketones, polyether sulfones polyphenylene sulfide, polyphenylene oxide, etc.
Included as the thermosetting resins mentioned hereabove in O : e.g., phenoi resins, epoxy resins, melamine resin, urea resins, unsaturated polyester resins, alkid resins, etc.
Included as the low molecular organic compounds mentioned hereabove in X are; for example, substances which are to be added to general thermoplastic resins and thermosetting resins, which thus, include low molecular organic compounds used as plasticisers, light- and weather-proofing stabilizers like antioxidants or ultraviolet ray absorbers, etc., antistatic agents, fire retardants, coloring agents like dyes, pigments, etc., blowing agents, further, divinyl series compounds, bridging agents like peroxides or vulcanizing agents, etc., and lubricants for improving fluidity and mold releasing property, etc.
Further included as the inorganic substances mentioned hereabove in (g) are: e.g., materials to be added to general thermoplastic resins and thermosetting resins, which thus, include general inorganic fibers such as glass fibers, carbon fibers, metal fibers, ceramic fibers, boron fibers, asbestos, etc., powder materials such as calcium carbonate, highly dispersible silicic acid, alumina, aluminium hydroxide, talc powder, mica, glass flake, glass beas, quartz powder, silica sand, various metal powders, carbon block, barium sulfate, calcined plaster, etc., inorganic compounds such as silicon carbide, alumina, boron nitride, silicon nitride, etc., and whiskers and metal whiskers, etc.
In the polymer composition of this invention adapted to give anisotropic fused phase, its high molecular chains are highly oriented even in static state, when it is fused, and still higher orientation is achieved through flowing of the fused body, when being subjected to the fusion-forming. It is for this reason that still higher orientation is attained in the laminate film.
The thermoplastic polymer having film forming ability which is used for the laminate film of this invention needs to have a strength capable of bolstering its strength at least in the lateral axis direction relative to the direction of orientation of the thermotropic liquid crystal polymer as well as excellentfilm-forming ability by way of fusion-fo rming. Following polymers are illustrated:Polyethylene, polypropylene, polybutylene, polybutadiene, polyisoprene, polyvinyl acetate, polyvinyl chloride, polyvinlidene chloride, acrylic resins,
ABS resins, AS resins, polyurethane, silicone resins, fluorine base resins, polycarbonates, polyethylene terephthalate, polybutylene terephthalate, aromatic polyesters, polyamides, polyacrylonitrils, polyvinyl alcohol, polyvinyl ether, polyether amide, polyamide imide, polyether etherimide, polyether etherketon, polyether sulfone, polysulfone, polyphenylene sulfide, ionomer, TPX and their copolymers.
Of these polymers, polyamide, polycarbonates, polyethylene terephthalate, polybutylene terephthalate, aromatic polyesters, polyether sulfone, polyether imide, polyether ether ketone, polyphenylene sulfide, etc., are desirable.
Usable as the method of forming the laminate film of this invention are a variety of methods hitherto used for film formation from thermoplastic resins; i.e., conventional methods comprising inflation process, T-die film-forming, calender process, flowing and drawing process and combinations of these drawing processes.
When at least one type of layer of the multilayer laminate has been singly formed into a sheet or film beforehand, normal laminating devices and coating devices are usable.
Available as a preferable mode of exercising the method of this invention is a method in which a uniaxially oriented sheet adapted to form anisotropic melt phase is prepared and on this sheet, a thermoplastic polymer having film forming ability is laminated by way of melt-processing as in the conventional laminate film forming method above-described.
While the individual sheets of polymer adapted to form anisotropic fused phase which compose such a laminate may be manufactured by arbitrary accustomed methods, forming the sheet by extruding through a slit die with appropriate dimensions under an adequate temperature and pressure, followed by fushion-drawing, is a preferable manufacturing method. The "sheet" used in this method may include a variety of all relatively thin, substantially flat structures which are sometimes called sheet, slab, film, etc., in said technical field. The thicknesses of individual sheets composing the laminate are not particularly restricted, but generally depend on the objects of use of the laminates; for example, the higher the strength required, the thicker sheets need to be used. The sheets manufactured in this way substantially give uniaxial or unidirectional orientation.
The existence of such uniaxial or unidirectional orientation may be determined by measurements of tensile characteristic (i.e., tensile strength of the sheet in both longitudinal (MD) and laterl (TD) directions in accordance with the U. S. Standard Test method ASTM D 882. When the ratio of tensile strength in the longitudinal direction of the sheet (direction of extrusion) to that in the lateral direction exceeds approx. 2.0 (preferably, within a range of approx. 2.0-100), there exists appropriate uniaxial orientation. Especially preferably, this ratio should be within approx. 10-50.
With regard to the conditions of temperature and pressure at which the liquid crystal polymer is extrudable for forming the sheet, this invention does not specify any particular limitations, but anyone in the trade is allowed readily to determine these conditions. In general, the extrusion ofthethermotropic liquid crystal polymer may be performed at a temperature within a range (according to the fusion-temperature of polymer) of approx. 250-3500C and under a pressure within a range of approx. 7.0-350 kg/cm2.
In order to ensure that the sheet as extruded give the desired uniaxial orientation, the extruded polymer melt should desirably be subjected to a drawing process. The drawdown ratio generally exceeds approx. 5.0.
The drawn-out polymer is, then cooled or quenched by any appropriate means such as with use of cooling rolls, air blowing-in orwatercooling, etc.
According to the method of this invention, on the high strength, highly oriented sheet of thermotropic liquid crystal polymer obtained in this way, a thermoplastic polymer having film forming ability may be laminated integrally therewith by way of melt-processing, using a liminating device such as that of T-die extrusion system or a coating device. This method is readily continuously exercised on industrial scale.
In this instance, the sheets to be laminated may be heated to temperatures higher than the fusiion temperature of the polymer which composes the sheet without notably degrading the high degree of orientation the polymer shows. Since such a polymer maintains anisotropy even in its fused phase, use of adhesive, etc., may be spared when integrally joining sheets. However, as desired, the laminate may contain an adhesive phase as a third component.
As another preferable mode of exercising the method of this invention, the polymer adapted to form anisotropic fused phase and the thermoplastic polymer having film forming ability may be laminated by way of simultaneous melt-processing of both and the laminated sheet should desirably be subjected to a drawing process after melt-processing.
The mechanical properties of the laminate manufactured by the method of this invention sometimes may be further improved by subjecting it to a heat treatment after being formed.
[Embodiments]
This invention will become more apparent from descriptions taken in connection with embodiments thereof, but the modes of application of this invention is not restircted to these embodiments.
Examples 1 - 5 Pellets of thermotropic liquid crystal polymer obtained by polymerizing 75 mol % of p-hydroxybenzoic acid and 25 mol % of 6-hydroxy-2-naphthoic acid were dried at 140"C for 7 hours beforehand. Then a film 8.15 cm wide and 0.10 mm thick was obtained by extruding this polymer at a speed of 2.72 m/min, using a
T-die type extruder. The fushion-drawdown ratio at this time was set at 14.3.
On the thermotropic liquid crystal polymer film thus obtained, polycarbonate (Lexan 8030 manufactured by Asahi Glass), nylon 12 (Diamide 4418 manufactured by Daicell Chemical Industry), polyethylene terephthalate (manufactured byToray), polybutyleneterephthalate (Duranex manufactured by Polyplastics) and polyacrylate (Durel manufactured by Occidental) were respectively laminated on a T-die extrusion type laminating device, yielding a laminate film 8.15 cm wide and 0.15 + 0.05 mm thick.
With the laminate film thus obtained, its tensile strengths were measured in two directions - its main axial direction (MD) and in the direction (TD) at a right angle to the main axial direction. Results are shown in Table 1.
Example 6
A laminate film of thermotropic liquid crystal polymer obtained by polymerizing 75 mol % of p-hydroxybenzoic acid and 25 mol % of 6-hydroxy-2-naphthoic acid and polyethylene terephthalate was prepared by way of fushion-forming of both of them, using a multi-layer inflation film device and its tensile characteristics were measured. The results are shown in Table 2.
Example 7
A biaxially drawn laminate film was obtained by way of melt-processing of a thermotropic liquid crystal polymer obtained similarly as in Example 6 and polyethylene terephthalate, using a T-die type multi-layer extruding device and a biaxial drawing device.
TABLE 1
Tensile characteristics of laminate film
Tensile
No. Composition strengths
Comparison Thermotropic liquid crystal polymer MD 477
Example 1 (T.LCP) TD 26.6
Example 1 T.LCP/ Polycarbonate MD 335
TD 64.7
Example 2 T.LCP/12 Nylon MD 391
TD 78.4
Example 3 T.LCP / Polyethylene terephthalate MD 417
TD 96.0
Example 4 T. LCP / Po lybutylene terephtha late MD 402
TD 55.9
ExampleS T.LCP / Polyacrylate MD 421
TD 63.7
TABLE 2
Film forming method and tensile strength
Tensile
No. Composition strengths
Example 6 2 Layer inflation film MD 176
T.LCP / Polyethylene terephthalate TD 118
Example 7 2 Layer extrusion biaxial drawing MD 368 T.LCP / Polyethylene terephthalate TD 174
Claims (4)
1. A process for manufacturing a laminate sheet which comprises a film of a polymer adapted to form the anisotropic melt phase and a film of a thermoplastic polymer having the film-forming property by laminating at least one of both polymers.
2. A process as claimed in claim 1, in which the thermoplastic polymer is laminated on a uniaxially oriented film of the polymer adapted to form the anisotropic melt phase.
3. A process as claimed in claim 1, in which both polymers are moulded to film at the same time to laminate on each other.
4. A process as claimed in claim 3, which comprises a further step of stretching the obtained laminate sheet biaxially.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP59210587A JPS6189816A (en) | 1984-10-09 | 1984-10-09 | Manufacture of laminated film |
Publications (3)
Publication Number | Publication Date |
---|---|
GB8524761D0 GB8524761D0 (en) | 1985-11-13 |
GB2166685A true GB2166685A (en) | 1986-05-14 |
GB2166685B GB2166685B (en) | 1988-12-07 |
Family
ID=16591785
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB08524761A Expired GB2166685B (en) | 1984-10-09 | 1985-10-08 | Manufacturing method of laminate film |
Country Status (4)
Country | Link |
---|---|
JP (1) | JPS6189816A (en) |
KR (1) | KR900001959B1 (en) |
GB (1) | GB2166685B (en) |
SG (1) | SG67589G (en) |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0293911A2 (en) * | 1987-06-04 | 1988-12-07 | Canon Kabushiki Kaisha | Polymer liquid crystal device |
EP0503063A1 (en) * | 1990-09-28 | 1992-09-16 | Daicel Chemical Industries, Ltd. | Composite film |
US5330697A (en) * | 1987-08-21 | 1994-07-19 | Minnesota Mining And Manufacturing Company | Method of preparing films containing liquid crystalline polymers |
US5340911A (en) * | 1990-04-06 | 1994-08-23 | Mitsubishi Kasei Corporation | Liquid crystalline polyesters and methods for their production |
EP0612610A1 (en) * | 1993-02-25 | 1994-08-31 | Japan Gore-Tex, Inc. | A liquid crystal polymer film and a manufacturing process therefor |
US5360672A (en) * | 1991-04-08 | 1994-11-01 | Kuraray Co., Ltd. | Process for treating film comprising liquid crystal polymer |
EP0669207A1 (en) * | 1994-02-23 | 1995-08-30 | Japan Gore-Tex, Inc. | A liquid crystal polymer film and a process for manufacture thereof |
EP0677368A2 (en) * | 1994-03-15 | 1995-10-18 | Japan Gore-Tex, Inc. | A method for manufacturing a liquid crystal polymer film and a liquid crystal polymer film made thereby |
EP0763423A1 (en) * | 1995-09-11 | 1997-03-19 | Sumitomo Chemical Company Limited | Laminated material and paper pack container formed from said material |
US5681624A (en) * | 1993-02-25 | 1997-10-28 | Japan Gore-Tex, Inc. | Liquid crystal polymer film and a method for manufacturing the same |
EP0911150A2 (en) * | 1997-10-20 | 1999-04-28 | Hoechst Celanese Corporation | Laminates formed from wholly aromatic, amorphous stretchable liquid crystalline polymers and non-polyester thermoplastics and methods of forming same |
EP0909781A3 (en) * | 1997-10-20 | 1999-05-19 | Hoechst Celanese Corporation | Laminates formed from wholly aromatic, amorphous stretchable liquid crystalline polymers and non-liquid crystalline polyesters and methods of forming same |
US6027771A (en) * | 1993-02-25 | 2000-02-22 | Moriya; Akira | Liquid crystal polymer film and a method for manufacturing the same |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0072210A1 (en) * | 1981-08-06 | 1983-02-16 | Celanese Corporation | Multiaxially oriented high performance laminates comprising uniaxially oriented sheets of thermotropic liquid crystal polymers |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5167376A (en) * | 1974-12-09 | 1976-06-10 | Sumitomo Chemical Co | Ramineetono netsukuinboshihoho |
JPS5926471B2 (en) * | 1976-03-12 | 1984-06-27 | 帝人株式会社 | laminate |
JPS56150544A (en) * | 1980-04-24 | 1981-11-21 | Japan Styrene Paper Corp | Composite plastic sheet and its manufacture |
-
1984
- 1984-10-09 JP JP59210587A patent/JPS6189816A/en active Granted
-
1985
- 1985-10-08 GB GB08524761A patent/GB2166685B/en not_active Expired
- 1985-10-08 KR KR1019850007409A patent/KR900001959B1/en not_active IP Right Cessation
-
1989
- 1989-09-30 SG SG675/89A patent/SG67589G/en unknown
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0072210A1 (en) * | 1981-08-06 | 1983-02-16 | Celanese Corporation | Multiaxially oriented high performance laminates comprising uniaxially oriented sheets of thermotropic liquid crystal polymers |
Cited By (25)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0293911A3 (en) * | 1987-06-04 | 1989-01-18 | Canon Kabushiki Kaisha | Polymer liquid crystal device |
US5039208A (en) * | 1987-06-04 | 1991-08-13 | Canon Kabushiki Kaisha | Polymer liquid crystal device |
EP0293911A2 (en) * | 1987-06-04 | 1988-12-07 | Canon Kabushiki Kaisha | Polymer liquid crystal device |
US5330697A (en) * | 1987-08-21 | 1994-07-19 | Minnesota Mining And Manufacturing Company | Method of preparing films containing liquid crystalline polymers |
US5340911A (en) * | 1990-04-06 | 1994-08-23 | Mitsubishi Kasei Corporation | Liquid crystalline polyesters and methods for their production |
US5364669A (en) * | 1990-09-28 | 1994-11-15 | Daicel Chemical Industries, Ltd. | Composite films |
EP0503063A1 (en) * | 1990-09-28 | 1992-09-16 | Daicel Chemical Industries, Ltd. | Composite film |
EP0503063A4 (en) * | 1990-09-28 | 1993-07-21 | Daicel Chemical Industries, Ltd. | Composite film |
US5360672A (en) * | 1991-04-08 | 1994-11-01 | Kuraray Co., Ltd. | Process for treating film comprising liquid crystal polymer |
US5900292A (en) * | 1993-02-25 | 1999-05-04 | Japan Gore-Tex, Inc. | Liquid crystal polymer film and a method for manufacturing the same |
EP0612610A1 (en) * | 1993-02-25 | 1994-08-31 | Japan Gore-Tex, Inc. | A liquid crystal polymer film and a manufacturing process therefor |
US6027771A (en) * | 1993-02-25 | 2000-02-22 | Moriya; Akira | Liquid crystal polymer film and a method for manufacturing the same |
US5681624A (en) * | 1993-02-25 | 1997-10-28 | Japan Gore-Tex, Inc. | Liquid crystal polymer film and a method for manufacturing the same |
EP0669207A1 (en) * | 1994-02-23 | 1995-08-30 | Japan Gore-Tex, Inc. | A liquid crystal polymer film and a process for manufacture thereof |
EP0677368A2 (en) * | 1994-03-15 | 1995-10-18 | Japan Gore-Tex, Inc. | A method for manufacturing a liquid crystal polymer film and a liquid crystal polymer film made thereby |
EP0677368A3 (en) * | 1994-03-15 | 1995-11-29 | Japan Gore Tex Inc | |
US5534209A (en) * | 1994-03-15 | 1996-07-09 | Japan Gore-Tex, Inc. | Method for manufacturing a liquid crystal polymer film and a liquid crystal polymer film made thereby |
US5817384A (en) * | 1995-09-11 | 1998-10-06 | Sumitomo Chemical Company, Limited | Laminated material and paper pack container formed from said material |
EP0763423A1 (en) * | 1995-09-11 | 1997-03-19 | Sumitomo Chemical Company Limited | Laminated material and paper pack container formed from said material |
CN1064595C (en) * | 1995-09-11 | 2001-04-18 | 住友化学工业株式会社 | Laminated material and paper pack container formed from said material |
EP0911150A2 (en) * | 1997-10-20 | 1999-04-28 | Hoechst Celanese Corporation | Laminates formed from wholly aromatic, amorphous stretchable liquid crystalline polymers and non-polyester thermoplastics and methods of forming same |
EP0909781A3 (en) * | 1997-10-20 | 1999-05-19 | Hoechst Celanese Corporation | Laminates formed from wholly aromatic, amorphous stretchable liquid crystalline polymers and non-liquid crystalline polyesters and methods of forming same |
EP0911150A3 (en) * | 1997-10-20 | 1999-05-19 | Hoechst Celanese Corporation | Laminates formed from wholly aromatic, amorphous stretchable liquid crystalline polymers and non-polyester thermoplastics and methods of forming same |
US6268026B1 (en) | 1997-10-20 | 2001-07-31 | Hoechst Celanese Corporation | Multilayer laminate formed from a substantially stretched non-molten wholly aromatic liquid crystalline polymer and non-liquid crystalline polyester and method for forming same |
US6312772B1 (en) | 1997-10-20 | 2001-11-06 | Hoechst Celanese Corporation | Multilayer laminate formed from a substantially stretched non-molten wholly aromatic liquid crystalline polymer and non-polyester thermoplastic polymer |
Also Published As
Publication number | Publication date |
---|---|
JPS6189816A (en) | 1986-05-08 |
GB2166685B (en) | 1988-12-07 |
JPH0466696B2 (en) | 1992-10-26 |
KR900001959B1 (en) | 1990-03-27 |
KR860003289A (en) | 1986-05-23 |
GB8524761D0 (en) | 1985-11-13 |
SG67589G (en) | 1990-04-20 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US4717624A (en) | Method of manufacturing a molded article having good dimensional stability | |
US4737398A (en) | Metallic film with laminated layer of an anisotropic melt phase forming polymer | |
US5614141A (en) | Method of manufacturing laminated films | |
EP0502190B1 (en) | Composite metal plate | |
GB2166685A (en) | Manufacturing method of laminate film | |
JPH0673179B2 (en) | Magnetic disk | |
EP0398075B1 (en) | Polyester film | |
JP2982133B2 (en) | Composite film | |
JP2942840B2 (en) | Laminated film | |
JP2810097B2 (en) | Multilayer film | |
JP2784030B2 (en) | Manufacturing method of laminated film | |
JP2790961B2 (en) | Liquid crystalline polyester resin composition for blow molding or extrusion molding and molded article thereof | |
JPH04136038A (en) | Film for bonding metallic sheets and composite metallic sheet | |
JP2810096B2 (en) | Multilayer film | |
JP2784031B2 (en) | Method for producing multilayer film | |
JP2852553B2 (en) | Liquid crystalline polymer film and method for producing the same | |
JP2810095B2 (en) | Composite film | |
GB2166666A (en) | Magnetic tape | |
JPH02253952A (en) | Moistureproof film for el element | |
JPH0289617A (en) | Film and method and apparatus for manufacturing thereof | |
JPH02252738A (en) | Film for bonding to metallic sheet | |
JP2810094B2 (en) | Composite film | |
JP2848665B2 (en) | Liquid crystalline polymer film and method for producing the same | |
JPH04189538A (en) | Decorative sheet and its manufacture | |
JP2790840B2 (en) | Packaging materials for medical articles |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 20031008 |