JPH04178459A - Resin composition for drawn polyamide film - Google Patents
Resin composition for drawn polyamide filmInfo
- Publication number
- JPH04178459A JPH04178459A JP30384990A JP30384990A JPH04178459A JP H04178459 A JPH04178459 A JP H04178459A JP 30384990 A JP30384990 A JP 30384990A JP 30384990 A JP30384990 A JP 30384990A JP H04178459 A JPH04178459 A JP H04178459A
- Authority
- JP
- Japan
- Prior art keywords
- group
- formula
- film
- weight
- coupling agent
- 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
- 239000004952 Polyamide Substances 0.000 title claims description 39
- 229920002647 polyamide Polymers 0.000 title claims description 39
- 239000011342 resin composition Substances 0.000 title claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 22
- 229920006122 polyamide resin Polymers 0.000 claims abstract description 12
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 3
- 125000003545 alkoxy group Chemical group 0.000 claims abstract 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract 2
- -1 phenol compound Chemical class 0.000 claims description 26
- 239000000126 substance Substances 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 229910052615 phyllosilicate Inorganic materials 0.000 claims description 3
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 2
- 125000002252 acyl group Chemical group 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 claims description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- 125000003452 oxalyl group Chemical group *C(=O)C(*)=O 0.000 claims description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 abstract description 32
- 239000007822 coupling agent Substances 0.000 abstract description 25
- 239000000203 mixture Substances 0.000 abstract description 19
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052901 montmorillonite Inorganic materials 0.000 abstract description 6
- 150000002989 phenols Chemical class 0.000 abstract description 5
- 238000003475 lamination Methods 0.000 abstract description 4
- 229920006280 packaging film Polymers 0.000 abstract description 2
- 239000012785 packaging film Substances 0.000 abstract description 2
- 238000013329 compounding Methods 0.000 abstract 2
- 125000001589 carboacyl group Chemical group 0.000 abstract 1
- 229920002554 vinyl polymer Polymers 0.000 abstract 1
- 238000000034 method Methods 0.000 description 24
- 238000002474 experimental method Methods 0.000 description 14
- 230000004888 barrier function Effects 0.000 description 12
- 239000007789 gas Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 239000010410 layer Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000004898 kneading Methods 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000011229 interlayer Substances 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- 239000007983 Tris buffer Substances 0.000 description 3
- OMOVVBIIQSXZSZ-UHFFFAOYSA-N [6-(4-acetyloxy-5,9a-dimethyl-2,7-dioxo-4,5a,6,9-tetrahydro-3h-pyrano[3,4-b]oxepin-5-yl)-5-formyloxy-3-(furan-3-yl)-3a-methyl-7-methylidene-1a,2,3,4,5,6-hexahydroindeno[1,7a-b]oxiren-4-yl] 2-hydroxy-3-methylpentanoate Chemical compound CC12C(OC(=O)C(O)C(C)CC)C(OC=O)C(C3(C)C(CC(=O)OC4(C)COC(=O)CC43)OC(C)=O)C(=C)C32OC3CC1C=1C=COC=1 OMOVVBIIQSXZSZ-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910001882 dioxygen Inorganic materials 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000012805 post-processing Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- PBLZLIFKVPJDCO-UHFFFAOYSA-N 12-aminododecanoic acid Chemical compound NCCCCCCCCCCCC(O)=O PBLZLIFKVPJDCO-UHFFFAOYSA-N 0.000 description 2
- BYIMSFXYUSZVLI-UHFFFAOYSA-N 3-methoxysilylpropan-1-amine Chemical compound CO[SiH2]CCCN BYIMSFXYUSZVLI-UHFFFAOYSA-N 0.000 description 2
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 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
- 238000007792 addition Methods 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000002734 clay mineral Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 239000010954 inorganic particle Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 239000005033 polyvinylidene chloride Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 150000004760 silicates Chemical class 0.000 description 2
- 239000012756 surface treatment agent Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 235000012222 talc Nutrition 0.000 description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
- 230000002087 whitening effect Effects 0.000 description 2
- IEKHISJGRIEHRE-UHFFFAOYSA-N 16-methylheptadecanoic acid;propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)CCCCCCCCCCCCCCC(O)=O.CC(C)CCCCCCCCCCCCCCC(O)=O.CC(C)CCCCCCCCCCCCCCC(O)=O IEKHISJGRIEHRE-UHFFFAOYSA-N 0.000 description 1
- LHPPDQUVECZQSW-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4,6-ditert-butylphenol Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(N2N=C3C=CC=CC3=N2)=C1O LHPPDQUVECZQSW-UHFFFAOYSA-N 0.000 description 1
- XYPTZZQGMHILPQ-UHFFFAOYSA-N 2-methyl-6-trimethoxysilylhex-1-en-3-one Chemical compound CO[Si](OC)(OC)CCCC(=O)C(C)=C XYPTZZQGMHILPQ-UHFFFAOYSA-N 0.000 description 1
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 description 1
- LVNLBBGBASVLLI-UHFFFAOYSA-N 3-triethoxysilylpropylurea Chemical compound CCO[Si](OCC)(OCC)CCCNC(N)=O LVNLBBGBASVLLI-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 description 1
- JAWSTIJAWZBKOU-UHFFFAOYSA-N 7-methylazepan-2-one Chemical compound CC1CCCCC(=O)N1 JAWSTIJAWZBKOU-UHFFFAOYSA-N 0.000 description 1
- VWPQCOZMXULHDM-UHFFFAOYSA-N 9-aminononanoic acid Chemical compound NCCCCCCCCC(O)=O VWPQCOZMXULHDM-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- HAWRMIAGSBJNQS-UHFFFAOYSA-N C12=CC=CC=C2C2=C1C=CC=C2P(O)O Chemical compound C12=CC=CC=C2C2=C1C=CC=C2P(O)O HAWRMIAGSBJNQS-UHFFFAOYSA-N 0.000 description 1
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- CTPROFFXVLRJTM-UHFFFAOYSA-N [2,3,5,6-tetrakis(2,4-ditert-butylphenyl)-4-phenylphenyl]phosphonous acid Chemical compound CC(C)(C)C1=CC(=C(C=C1)C2=C(C(=C(C(=C2C3=C(C=C(C=C3)C(C)(C)C)C(C)(C)C)P(O)O)C4=C(C=C(C=C4)C(C)(C)C)C(C)(C)C)C5=C(C=C(C=C5)C(C)(C)C)C(C)(C)C)C6=CC=CC=C6)C(C)(C)C CTPROFFXVLRJTM-UHFFFAOYSA-N 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 1
- 229960002684 aminocaproic acid Drugs 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- VNSBYDPZHCQWNB-UHFFFAOYSA-N calcium;aluminum;dioxido(oxo)silane;sodium;hydrate Chemical compound O.[Na].[Al].[Ca+2].[O-][Si]([O-])=O VNSBYDPZHCQWNB-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 description 1
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- MASNVFNHVJIXLL-UHFFFAOYSA-N ethenyl(ethoxy)silicon Chemical compound CCO[Si]C=C MASNVFNHVJIXLL-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 1
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910052621 halloysite Inorganic materials 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 229910000271 hectorite Inorganic materials 0.000 description 1
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 description 1
- 229910000273 nontronite Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- XUWHAWMETYGRKB-UHFFFAOYSA-N piperidin-2-one Chemical compound O=C1CCCCN1 XUWHAWMETYGRKB-UHFFFAOYSA-N 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000275 saponite Inorganic materials 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910021647 smectite Inorganic materials 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 1
- KLNPWTHGTVSSEU-UHFFFAOYSA-N undecane-1,11-diamine Chemical compound NCCCCCCCCCCCN KLNPWTHGTVSSEU-UHFFFAOYSA-N 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- 239000005050 vinyl trichlorosilane Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔発明の目的〕
（産業上の利用分野）
本発明は、延伸ポリアミドフィルム用樹脂組成物に関す
る。詳しくは、ポリアミド樹脂とこれに均一に分散され
た層状珪酸塩およびヒンダードフェノール系化合物およ
びシラン系カップリング剤及び／又はチタネート系カッ
プリング剤から成る延伸ポリアミドフィルム用樹脂組成
物で、さらに詳しくは、ガスバリヤ−性、透明性及び滑
り性が優れており、かつ、ラミネート、印刷、製袋など
の後加工に必要な剛性を有する延伸ポリアミドフィルム
用樹脂組成物に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] (Field of Industrial Application) The present invention relates to a resin composition for stretched polyamide film. Specifically, it is a resin composition for a stretched polyamide film comprising a polyamide resin, a layered silicate and a hindered phenol compound uniformly dispersed therein, and a silane coupling agent and/or a titanate coupling agent. The present invention relates to a resin composition for a stretched polyamide film that has excellent gas barrier properties, transparency, and slipperiness, and has the rigidity necessary for post-processing such as lamination, printing, and bag making.
（従来の技術及び発明が解決しようとする課題）ポリア
ミドフィルムは、透明性、耐ピンホール性、ガスバリヤ
−性、耐熱性および耐油性などの緒特性が優れているた
めに主に食品包装の分野で使用されている。(Prior art and problems to be solved by the invention) Polyamide films are mainly used in the field of food packaging because of their excellent properties such as transparency, pinhole resistance, gas barrier properties, heat resistance, and oil resistance. used in
しかし、近年、食品包装ではガスバリヤ−性の一層の向
上が要求されているが、用途によってはポリアミドフィ
ルムのガスバリヤ−性は十分とは言えない。特に、高湿
度下ではポリアミドフィルムのガスバリヤ−性は著しく
低下する。このため、ガスバリヤ−性が優れたエチレン
−ビニルアルコール共重合体（ＥＶＯＨ）とポリアミド
を共押出し成形したり、ポリアミドフィルムの表面にガ
スバリヤ−性の良好なポリ塩化ビニリデン（ＰＶＤＣ）
をコートすることが行われている。しかし、このＥＶＯ
ＨおよびＰＶＤＣは高価格であるだけでなく、共押出し
フィルムの層構成の増加やコーティングラインの設置な
どによる設備面のコストアップもあり、価格面で要求を
満たさない場合が多い。However, in recent years, there has been a demand for further improvement in gas barrier properties in food packaging, but the gas barrier properties of polyamide films cannot be said to be sufficient depending on the application. In particular, the gas barrier properties of polyamide films are significantly reduced under high humidity conditions. For this reason, ethylene-vinyl alcohol copolymer (EVOH), which has excellent gas barrier properties, and polyamide are coextruded, and polyvinylidene chloride (PVDC), which has good gas barrier properties, is coated on the surface of the polyamide film.
It is being done to coat. However, this EVO
H and PVDC are not only expensive, but also increase the cost of equipment due to an increase in the layer structure of the coextruded film and the installation of a coating line, so they often do not meet the price requirements.
さらに、ポリアミドフィルム、特にナイロン６フィルム
では湿度の高い環境下では吸湿することによりフィルム
の滑り性および腰（剛性）か低下してしまう。このよう
な剛性の低下はラミネート工程、印刷工程、製袋工程な
どの後工程の際にトラブルを招くことになるため、その
改善が強く要望されている。Furthermore, polyamide films, particularly nylon 6 films, absorb moisture in a humid environment, resulting in a decrease in the slipperiness and stiffness of the film. Since such a decrease in rigidity causes trouble in subsequent processes such as lamination, printing, and bag making, there is a strong demand for improvement.
前記フィルム特性のなかで、滑り性を改善する方法とし
ては、金属石鹸類、ビスアミド類、ポリオレフィン類、
無機粒子などを添加する方法が公知であり、なかでも二
酸化ケイ素、タルク、カオリンなどの不活性無機粒子を
添加することが効果的であり、実用化されている。しか
し、吸湿によるポリアミドフィルムの剛性の低下につい
ては改良が非常に困難である。例えば、タルクやガラス
繊維などの添加は透過性や耐ピンホール性を低下させ、
また吸湿性の低い変化ポリオレフィン、アイオノマー樹
脂の添加はやはり透明性を損なうだけでなく、ガスバリ
ヤ−性や剛性の低下を招く。Among the above film properties, methods for improving slipperiness include metal soaps, bisamides, polyolefins,
Methods of adding inorganic particles are known, and among them, adding inert inorganic particles such as silicon dioxide, talc, and kaolin is effective and has been put into practical use. However, it is very difficult to improve the decrease in rigidity of polyamide films due to moisture absorption. For example, additions such as talc and glass fiber reduce permeability and pinhole resistance.
Furthermore, the addition of modified polyolefins or ionomer resins with low hygroscopicity not only impairs transparency but also causes a decrease in gas barrier properties and rigidity.
そこで、ポリアミドに層状珪酸塩を均一に分散した材料
を用いて、フィルムを作成し、優れたガスバリヤ−性、
滑り性、剛性、透明性を持たせるという発明がなされて
いる。（特願昭６３−２５７３０６号）。Therefore, we created a film using a material in which layered silicate is uniformly dispersed in polyamide, and it has excellent gas barrier properties and
Inventions have been made to provide slipperiness, rigidity, and transparency. (Patent Application No. 1983-257306).
この発明は単層、多層の多様な用途に適用でき各種用途
に用いられているが、フィルムの強度等を向上させるた
め、フィルムを延伸して用いるような用途において、そ
のフィルムの延伸時に透明性が低下するという欠点があ
った。This invention can be applied to a variety of single-layer and multi-layer applications, and is used in a variety of applications. However, in applications where the film is stretched in order to improve its strength, etc. The disadvantage was that it decreased.
そこで、本発明者は、その欠点を解消するために、ポリ
アミド樹脂に層状珪酸塩を均一に分散させた材料にさら
にシランカップリング剤及び／又はチタネートカップリ
ング剤を添加して、フィルムの延伸時の透明性低下を減
少させたポリアミド樹脂組成物（特願平２−１９０４３
２号）、及びポリアミド樹脂に層状珪酸塩を均一に分散
させた材料にさらにヒンダードフェノール系化合物を添
加して、フィルムの延伸時の透明性低下を減少させたポ
リアミド樹脂組成物（特願平２−２２８３８８号）を提
案したが、フィルムの延伸時の透明性低下の減少はまだ
充分とは言えず、一部の用途には不都合を生じる場合が
あった。Therefore, in order to eliminate this drawback, the present inventor further added a silane coupling agent and/or a titanate coupling agent to a material in which layered silicate is uniformly dispersed in polyamide resin, and added a silane coupling agent and/or a titanate coupling agent to the material in which layered silicate is uniformly dispersed in polyamide resin. Polyamide resin composition that reduces the decrease in transparency (Patent application No. 2-19043
No. 2), and a polyamide resin composition in which a hindered phenol compound is further added to a material in which layered silicate is uniformly dispersed in a polyamide resin to reduce the decrease in transparency during film stretching (Patent Application No. 2). No. 2-228388) was proposed, but the decrease in transparency during film stretching was still not sufficiently reduced, and this may cause problems in some applications.
（課題を解決するための手段）
本発明は、優れたガスバリヤ−性、透明性および滑り性
を有しており、かつラミネート、印刷、製袋などの後加
工に必要な剛性を有する延伸ポリアミドフィルム用樹脂
組成物を提供することにある。(Means for Solving the Problems) The present invention provides a stretched polyamide film that has excellent gas barrier properties, transparency, and slipperiness, and has the rigidity necessary for post-processing such as lamination, printing, and bag making. An object of the present invention is to provide a resin composition for use in the present invention.
本発明は、
（Ａ）ポリアミド樹脂 ６０〜９９．９３９重量％（Ｂ
）（Ａ）に均一に分散された層状珪酸塩０．０５〜３０
重量％ 、
（Ｃ）ヒンダードフェノール系化合物
０、００１〜５重量％ および
（Ｄ）次式〔Ｉ〕で示されるシランカップリング剤及び
／又は次式（ＩＩ）で示されるチタネートカップリング
剤０．０１〜５重量％よりなることを特徴とする。The present invention comprises: (A) polyamide resin 60 to 99.939% by weight (B
) 0.05-30 phyllosilicate uniformly dispersed in (A)
% by weight, (C) 0.001 to 5% by weight of a hindered phenol compound, and (D) a silane coupling agent represented by the following formula [I] and/or a titanate coupling agent represented by the following formula (II) 0 .01 to 5% by weight.
Ｙ （Ｒ’ ） −Ｓ ｉ Ｘｓ −−−〔Ｉ〕（式
〔Ｉ〕中、Ｘは、塩素原子、アルコキシ基又はアルフキ
ジェトキシ基を表し、Ｙは、塩素原子ビニル基、メタク
リロイル基、グリシドキシ基、メルカプト基、アミノ基
、２．３〜エポキシエチル基、３．４−エポキシシクロ
ヘキシル基、ウレイド基又は式−ＣＨ２−Ｃ＝ＣＨ２基
ＯＯＨ
を表し、Ｒ１は、アルキレン基を表し、ｎは、０又はｌ
を表す。）
（式［ｎ）中、Ｒ２はアルキル基を表し、Ｒ３−Ｒ５は
、それぞれ置換もしくは非置換のアルキル基、アルカノ
イル基、（メタ）アクリロイル基、ジアルキルピロホス
フェート基、Ｎ−アミノエチル−アミノエチル基、アル
キルベンゼンスルホニル基、ジアルキルホスフェート基
又はクミルフェニル基を表し、Ｒ２とＲ３が一緒になっ
てエチレン基、オキサリル基または、式−ＣＯ−ＣＨ，
−基でも良い。）
本発明のポリアミドフィルムを構成するポリアミドとは
分子中に酸アミド結合（−ＣＯＮＨ−）を有するもので
あり、例えば、ε−カプロラクタム、６−アミノカプロ
ン酸、ε−エナントラクタム、７−アミノへブタン酸、
ＩＩ−アミノウンデカン酸、９−アミノノナン酸、α−
ピロリドン、α−ピペリドンなどから得られる重合体ま
たは共重合体；ヘキサメチレンジアミン、ノナメチレン
ジアミン、ウンデカメチレンジアミン、ドデカメチレン
ジアミン、メタキシリレンジアミンなどのジアミンとテ
レフタル酸、イソフタル酸、アジピン酸、セバシン酸な
どのジカルボン酸とを重縮合して得られる重合体もしく
は共重合体もしくはこれらのブレンド物を挙げることが
できる。Y (R') -S i Represents a glycidoxy group, mercapto group, amino group, 2.3-epoxyethyl group, 3.4-epoxycyclohexyl group, ureido group or formula -CH2-C=CH2 group OOH, R1 represents an alkylene group, and n , 0 or l
represents. ) (In formula [n), R2 represents an alkyl group, and R3-R5 are each substituted or unsubstituted alkyl group, alkanoyl group, (meth)acryloyl group, dialkylpyrophosphate group, N-aminoethyl-aminoethyl group, an alkylbenzenesulfonyl group, a dialkyl phosphate group, or a cumylphenyl group, and R2 and R3 together represent an ethylene group, an oxalyl group, or a formula -CO-CH,
- It may be a group. ) The polyamide constituting the polyamide film of the present invention has an acid amide bond (-CONH-) in its molecule, and includes, for example, ε-caprolactam, 6-aminocaproic acid, ε-enantholactam, and 7-aminohebutane. acid,
II-aminoundecanoic acid, 9-aminononanoic acid, α-
Polymers or copolymers obtained from pyrrolidone, α-piperidone, etc.; diamines such as hexamethylene diamine, nonamethylene diamine, undecamethylene diamine, dodecamethylene diamine, metaxylylene diamine, and terephthalic acid, isophthalic acid, adipic acid, Examples include polymers or copolymers obtained by polycondensation with dicarboxylic acids such as sebacic acid, or blends thereof.
ポリアミドは、平均分子量が９，０００〜３０．０００
のものが好ましい。Polyamide has an average molecular weight of 9,000 to 30,000
Preferably.
ポリアミドフィルムを構成する層状珪酸塩としては、そ
の厚みが６〜２０人で、−辺の長さが０、００２〜１μ
ｍの平板状のものが好ましい。The layered silicate constituting the polyamide film has a thickness of 6 to 20 mm, and a side length of 0.002 to 1 μm.
A plate-like material with a diameter of m is preferable.
また、層状珪酸塩はポリアミド中に均一に分散すること
が必要であるが、分散した際にそれぞれが平均的に２０
Å以上の眉間距離を保ち、均一に分散されていることが
好ましい。ここで層間距離とは層状珪酸塩の平板の重心
間の距離を言い、均一に分散するとは層状珪酸塩の一枚
一枚が、もしくは平均的に重なりが５層以下の多層物が
、平均にまたはランダムに、もしくは平行とランダムが
混在した状態で、その５０重量％以上が、好ましくは７
０重量％以上が局所的な塊を形成することなく分散する
状態を言う。従って層状珪酸塩とは例えば−辺がＯ，Ｏ
Ｏ２〜１μｍ１厚みが６〜２０人の物質の一単位を示す
ものである。In addition, it is necessary to uniformly disperse the layered silicates in the polyamide, but when dispersed, each layer has an average of 20
It is preferable to maintain a glabellar distance of Å or more and to be uniformly dispersed. Here, the interlayer distance refers to the distance between the centers of gravity of flat plates of layered silicate, and uniform distribution means that each sheet of layered silicate, or a multilayered material with an average overlap of 5 or less layers, is distributed uniformly. or randomly, or in a mixed state of parallel and random, 50% by weight or more is preferably 7
This refers to a state in which 0% by weight or more is dispersed without forming local lumps. Therefore, layered silicates are, for example, -sides O, O
O2 ~ 1 μm 1 thickness represents one unit of substance of 6 to 20 people.
このような層状珪酸塩の原料としては、珪酸マグネシウ
ムまたは珪酸アルミニウムの層から構成される層状フィ
ロ珪酸鉱物を例示することができる。具体的には、モン
モリロナイト、サポナイト、バイデライト、ノントロナ
イト、ヘクトライト、スティブンサイトなどのスメクタ
イト系粘土鉱物やバーミキュライト、ハロイサイトなど
を例示することができ、これらは天然のものであっても
、合成されたものであってもよい。これらのなかでもモ
ンモリロナイトが好ましい。As a raw material for such a layered silicate, a layered phyllosilicate mineral composed of a layer of magnesium silicate or aluminum silicate can be exemplified. Specifically, examples include smectite clay minerals such as montmorillonite, saponite, beidellite, nontronite, hectorite, and stevensite, vermiculite, and halloysite. It may be something that has been done. Among these, montmorillonite is preferred.
層状珪酸塩の配合量は、全体に対して、０．０５〜３０
重量％であり、０．１〜１０重量％が好ましい。層状珪
酸塩の配合量が０．０５重量％未満であるとガスバリヤ
−性、滑り性、剛性などの改良効果が低いので好ましく
なく、３０重量％を越えると透明性が著しく低下するの
で好ましくない。The blending amount of layered silicate is 0.05 to 30
% by weight, preferably from 0.1 to 10% by weight. If the amount of the layered silicate is less than 0.05% by weight, the effect of improving gas barrier properties, slipperiness, rigidity, etc. will be low, which is undesirable, and if it exceeds 30% by weight, the transparency will drop significantly, which is not preferred.
ポリアミドに層状珪酸塩を均一に分散させる方法につい
ては特に制限はないが、本発明の層状珪酸塩の原料が多
層状粘土鉱物である場合には、膨潤化剤と接触させて、
予め層間を拡げて層間にモノマーを取り込みやすくした
のち、ポリアミドモノマーと混合し、重合する方法（特
開昭６２−７４９５７号公報参照）を適用することがで
きる。There are no particular restrictions on the method for uniformly dispersing the layered silicate in polyamide, but when the raw material for the layered silicate of the present invention is a multilayered clay mineral, it may be brought into contact with a swelling agent,
It is possible to apply a method (see Japanese Patent Application Laid-open No. 74957/1983) in which the interlayer gap is widened in advance to make it easier to incorporate the monomer between the layers, and then the mixture is mixed with a polyamide monomer and polymerized.
また、膨潤化剤に高分子化合物を用い、予め層間を１０
０Å以上に拡げて、これをポリアミド樹脂もしくはこれ
を含む樹脂と溶融混練して均一に分散させる方法（特願
平１−１２４４０２号参照）を適用することができる。In addition, a polymer compound is used as a swelling agent, and the gap between the layers is
It is possible to apply a method in which the resin is spread to a thickness of 0 Å or more and then uniformly dispersed by melt-kneading it with a polyamide resin or a resin containing the polyamide resin (see Japanese Patent Application No. 1-124402).
さらに、層状珪酸塩を高濃度で含むポリアミド組成物を
予め前記方法で調整し、この組成物と層状珪酸塩を含ま
ないポリアミドを混合する方法を適用することができる
。Furthermore, it is possible to apply a method in which a polyamide composition containing a high concentration of layered silicate is prepared in advance by the method described above, and this composition is mixed with a polyamide that does not contain layered silicate.
本発明のヒンダードフェノール系化合物は、−船釣には
、酸化防止剤、加工安定剤として使用され、分子中に２
．６もしくは２．４にアルキル置換フェノール構造を有
する化合物であり、そのヒドロキシ基は、亜リン酸など
の酸でエステル化されていてもよい。さらに、アルキル
置換フェノール構造は、分子中の１か所以上の箇所に存
在していてもよい。The hindered phenol compound of the present invention is used as an antioxidant and processing stabilizer for boat fishing, and has 2
．． It is a compound having an alkyl-substituted phenol structure at 6 or 2.4, and the hydroxy group thereof may be esterified with an acid such as phosphorous acid. Furthermore, the alkyl-substituted phenol structure may be present at one or more locations in the molecule.
具体的には、トリエチレングリコール−ビス［：３−（
３−ｔ−ブチル−５−メチル−４−ヒドロキシフェニル
）プロピオネート〕、
１．６−ヘキサンシオールービス（３−（３゜５−ジ−
ｔ−ブチル−４ヒドロキシ−フェニルプロピオネート〕
、
ペンタエリスリチル−テトラキス（３−（３゜５−ジ−
ｔ−ブチル−４ヒドロキシ−フェニルプロピオネート〕
、
Ｎ、Ｎ−一へキサメチレンビス（３，５−ジ−ｔ−ブチ
ル−４ヒドロキシンマミド）、３．５−ジ−ｔ−ブチル
−４ヒドロキシーペンシルフオスフオネートージエチル
エステル、トリス（２，４−ジ−ｔ−ブチルフェニル）
フォスファイト、
テトラキス（２，４−ジ−ｔ−ブチルフェニル）−４，
４−−ビフエニレンフォスフォナイト、２−−（２−ヒ
ドロキシ−３，５−ビス（α。Specifically, triethylene glycol-bis[:3-(
3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanethiol bis(3-(3゜5-di-
t-Butyl-4-hydroxy-phenylpropionate]
, pentaerythrityl-tetrakis (3-(3゜5-di-
t-Butyl-4-hydroxy-phenylpropionate]
, N,N-1hexamethylenebis(3,5-di-t-butyl-4-hydroxymamide), 3,5-di-t-butyl-4-hydroxypencil phosphonate diethyl ester, Tris 2,4-di-t-butylphenyl)
Phosphite, tetrakis(2,4-di-t-butylphenyl)-4,
4--Biphenylenephosphonite, 2--(2-hydroxy-3,5-bis(α.
α−ジメチルベンジル）フェニル〕−２Ｈ−ベンゾトリ
アゾール、
２−（３，５−ジ−ｔ−ブチル−２−ヒドロキシフェニ
ル）ベンゾトリアゾールおよび、１．３．５−トリメチ
ル−２，４，６−トリス（３，５−ジ−ｔ−ブチル−４
−ホドロキシベンジル）ベンゼンなどを挙げることがで
きる。α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole and 1.3.5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4
-Phodroxybenzyl)benzene and the like.
本発明に用いる前記式〔Ｉ〕で示されるシランカップリ
ング剤は、オルガノファンクショナルシラン（Ｏｒｇａ
ｎｏｆｕｎｃＬｉｏｎａｌ ５ｉｌａｎｅ） 、カップ
リングエージェント（Ｃｏｕｐｌｉｎｇ Ａｇｅｎｔ）
、アドヒージョンプロモーター（Ａｄｈｅｓｉｏｎ
Ｐｒｏｍｏｔｅｒ）等とも呼ばれ、無機質等の表面処理
剤として一般に用いられているものである。The silane coupling agent represented by the formula [I] used in the present invention is an organofunctional silane (Orga
nofuncLional 5ilane), Coupling Agent
, Adhesion promoter
It is also called a sulfuric acid (promoter), etc., and is generally used as a surface treatment agent for inorganic materials and the like.
本発明に用いるシランカップリング剤としてはたとえば
、γ−クロロプロピルトリメトキシシラン、ビニルトリ
クロルシラン、ビニルエトキシシラン、ビニルトリメト
キシシラン、ビニルトリス（β−メトキシエトキシ）シ
ラン、γ−メタクリロイルプロピルトリメトキシシラン
、β−（３゜４−エポキシシクロヘキシル）エチルトリ
ットキシシラン、γ−グリシドキシプロビルトリメトキ
シシラン、γ−メルカプトプロピルトリメトキシシラン
、γ−アミノプロピルメトキシシラン、Ｎ−β−（アミ
ノエチル）−γ−アミノプロピルトリメトキシシラン、
γ−ウレイドプロピルトリエトキシシラン等を挙げるこ
とができ、中でもγ−グリシドキシプロピルトリメトキ
シシラン及びγ−アミノプロピルメトキシシランが好ま
しい。Examples of the silane coupling agent used in the present invention include γ-chloropropyltrimethoxysilane, vinyltrichlorosilane, vinylethoxysilane, vinyltrimethoxysilane, vinyltris(β-methoxyethoxy)silane, γ-methacryloylpropyltrimethoxysilane, β-(3゜4-epoxycyclohexyl)ethyltritoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropylmethoxysilane, N-β-(aminoethyl)- γ-aminopropyltrimethoxysilane,
Examples include γ-ureidopropyltriethoxysilane, among which γ-glycidoxypropyltrimethoxysilane and γ-aminopropylmethoxysilane are preferred.
本発明に用いる前記式（ＩＩ）で示されるチタネートカ
ップリング剤は、前記シランカップリング剤と同様に無
機質等の表面処理剤として一般に用いられているもので
あり、式（ＩＩ）で示されるチタネートの塩及び配位化
合物を含む。The titanate coupling agent represented by the formula (II) used in the present invention is generally used as a surface treatment agent for inorganic materials, etc., like the silane coupling agent, and the titanate coupling agent represented by the formula (II) including salts and coordination compounds.
具体例としては、次式（ａ）〜（ＩＩ）で示されるチタ
ネートカップリング剤を挙げることが出来る。Specific examples include titanate coupling agents represented by the following formulas (a) to (II).
Ｃｔｌ
ＣＨｓ−Ｃｔｌ−０−ＴＩ−←０−Ｃ２Ｈ４−ＮＨ−Ｃ
Ｊ＜−ＮＨ２）３（Ｃ）（Ｃ＊ Ｈ＋ ｔ −０＋−Ｖ
−Ｔ ｉ・［Ｐ脅０−ＣｗＨｔｔ）ｔＯＨ］２（ｄ ）
本発明に用いるシランカップリング剤及び／又はチタネ
ートカップリング剤は、それぞれ単独で用いてもよいし
、２種以上のシランカップリング剤又は、チタネートカ
ップリング剤をあわせて用いてもよいが、ヒンダードフ
ェノール系化合物と併用して用いなければならない。Ctl CHs-Ctl-0-TI-←0-C2H4-NH-C
J<-NH2)3(C)(C* H+ t-0+-V
−T i・[P threat0−CwHtt)tOH]2(d)
The silane coupling agent and/or titanate coupling agent used in the present invention may be used alone, or two or more silane coupling agents or titanate coupling agents may be used in combination. Must be used in combination with dophenol compounds.
ヒンダードフェノール系化合物の配合量は、全体に対し
て、０．００１〜５重量％であり、好ましくは、０．０
５〜２重量％である。The blending amount of the hindered phenol compound is 0.001 to 5% by weight based on the whole, preferably 0.0% by weight.
It is 5 to 2% by weight.
ヒンダードフェノール系化合物の配合量が０．００１重
量％未溝０場合には、得られた延伸フィルムの透明性が
損なわれるため好ましくなく、５重量％を越える場合に
は、フィルムに成形する時に、目ヤニが発生したり、ブ
リード物が多くなったりし、またフィルムが着色しやす
くなるので好ましくない。If the blending amount of the hindered phenol compound is 0.001% by weight, it is not preferable because the transparency of the obtained stretched film will be impaired, and if it exceeds 5% by weight, it will be difficult to form the film. This is not preferable because it causes eye stains, increases the amount of bleed, and makes the film more likely to be colored.
また、シランカップリング剤及び／又はチタネートカッ
プリング剤の配合量は、全体に対して、０．０１〜５重
量％であり、好ましくは、０．０５〜２重量％である。Further, the amount of the silane coupling agent and/or titanate coupling agent blended is 0.01 to 5% by weight, preferably 0.05 to 2% by weight, based on the total weight.
カップリング剤の配合量が０．０１重量％未０の場合に
は、得られた延伸フィルムの透明性が損なわれるため好
ましくなく、５重量％を越える場合には、フィルムに成
形する時に、目ヤニが発生したり、ブリード物が多くな
ったりし、またフィルムが着色しやすくなるので好まし
くない。If the amount of the coupling agent is less than 0.01% by weight, it is undesirable because the transparency of the obtained stretched film will be impaired, and if it exceeds 5% by weight, it will be difficult to This is undesirable because it causes tar and bleed, and the film tends to be colored.
ヒンダードフェノール系化合物およびシランカップリン
グ剤及び／又はチタネートカップリング剤をポリアミド
およびこれに均一に分散した珪酸塩から成る組成物に添
加する方法については、特に制限は無く、珪酸塩を含む
ポリアミドにヒンダードフェノール系化合物およびシラ
ンカップリング剤及び／又はチタネートカップリング剤
をブレンドし、直接フィルムを成膜してもよいし、珪酸
塩を含むポリアミドとヒンダードフェノール系化合物お
よびシランカップリング剤及び／又はチタネートカップ
リング剤を２軸混練機にて溶融混合した組成物を得、こ
れを用いてフィルムを成膜してもよいし、最初に珪酸塩
を含むポリアミドとヒンダードフェノール系化合物を２
軸混練機にて溶融混合した組成物にさらにシランカップ
リング剤及び／又はチタネートカップリング剤を２軸混
練機にて溶融混合して得た組成物を用いてフィルムを成
膜してもよいし、さらには、この逆の順序によってもよ
い。There are no particular restrictions on the method of adding the hindered phenol compound and the silane coupling agent and/or the titanate coupling agent to the composition consisting of the polyamide and the silicate homogeneously dispersed therein. A film may be formed directly by blending a hindered phenol compound and a silane coupling agent and/or a titanate coupling agent, or by blending a silicate-containing polyamide, a hindered phenol compound, a silane coupling agent, and/or a titanate coupling agent, and forming a film directly. Alternatively, a composition may be obtained by melt-mixing a titanate coupling agent in a twin-screw kneader, and a film may be formed using this, or a polyamide containing a silicate and a hindered phenol compound may be first mixed into
A film may be formed using a composition obtained by further melt-mixing a silane coupling agent and/or a titanate coupling agent in a twin-screw kneader to the composition melt-mixed in a axial kneader. , or even in the reverse order.
また、前述した層状珪酸塩を、ポリアミド中に分散させ
る重合ないし、混練の際に、ヒンダードフェノール系化
合物およびシランカップリング剤°及び／又はチタネー
トカップリング剤を同時に添加する方法によってもよい
し、前述した層状珪酸塩を、ポリアミド中に分散させる
重合ないし、混練の際に、ヒンダードフェノール系化合
物またはシランカップリング剤及び／又はチタネートカ
ップリング剤を添加した組成物を得たのち、２種のうち
添加していない方の化合物を溶融混合する方法によって
もよい。Alternatively, a method may be used in which a hindered phenol compound and a silane coupling agent and/or a titanate coupling agent are simultaneously added during polymerization or kneading in which the above-mentioned layered silicate is dispersed in polyamide. After obtaining a composition in which a hindered phenol compound or a silane coupling agent and/or a titanate coupling agent was added during polymerization or kneading in which the above-mentioned layered silicate was dispersed in polyamide, two types of compositions were obtained. A method may also be used in which the compound that is not added is melt-mixed.
ヒンダードフェノール系化合物およびシランカップリン
グ剤及び／又はチタネートカップリング剤が層状珪酸塩
を含むポリアミドで作られたフィルムの延伸時の白化を
防止する理由については明らかではないが、ポリアミド
の分子とうしの滑り性を良くするか、ポリアミドと層状
珪酸塩の相互作用に影響し、フィルム延伸時のせん断力
によるずり応力による残留応力か気泡発生による白化を
防止するのではないかと考えられる。Although it is not clear why hindered phenolic compounds and silane coupling agents and/or titanate coupling agents prevent whitening during stretching of polyamide films containing layered silicate, It is thought that this may improve the slipperiness of the polyamide or affect the interaction between the polyamide and the layered silicate, and prevent whitening due to residual stress due to shear stress due to shear force during film stretching or the generation of bubbles.
また、本発明のポリアミドフィルムの構成成分としては
、その他にも必要に応じて、滑剤、酸化防止剤、耐熱安
定剤、耐候性付与剤、帯電防止剤、透明性改良剤などを
配合することができる。In addition, other constituent components of the polyamide film of the present invention may include lubricants, antioxidants, heat stabilizers, weather resistance agents, antistatic agents, transparency improvers, etc. as necessary. can.
ポリアミドおよびそれに均一に分散されている層状珪酸
塩およびヒンダードフェノール系化合物およびシランカ
ップリング剤及び／又はチタネートカップリング剤を含
有する混合物より、未延伸のフィルムを成形する方法に
ついては、特に制限されるものではなく、例えば、層状
珪酸塩、ヒンダードフェノール系化合物およびシランカ
ップリング剤及び／又はチタネートカップリング剤を配
合したポリアミドを２００〜３００℃の押し出しロール
面上でキャスチングしたフィルムを冷却するキャスチン
グ法（Ｔダイ法）、あるいはリング状ダイにより、筒状
に押し出したものを空冷または水冷するチューブラ−法
等の各方法を適用することができる。There are no particular restrictions on the method of forming an unstretched film from a mixture containing a polyamide, a layered silicate and a hindered phenol compound uniformly dispersed therein, and a silane coupling agent and/or a titanate coupling agent. For example, casting is a method in which a polyamide blended with a layered silicate, a hindered phenol compound, and a silane coupling agent and/or a titanate coupling agent is cast on an extrusion roll surface at 200 to 300°C and the film is cooled. Various methods can be applied, such as the T-die method, or the tubular method in which a product extruded into a cylinder using a ring-shaped die is air-cooled or water-cooled.
延伸フィルムを成形する方法としては、特に制限は無く
、上記のようにキャスティング法またはチューブラ−法
で成形した未延伸フィルムを、５０〜１８０℃の延伸温
度で一軸延伸または二軸延伸し、必要に応じて１２０℃
以上で融点より低い温度で熱固定する方法を適用するこ
とができる。There are no particular restrictions on the method for forming the stretched film, and the unstretched film formed by the casting method or tubular method as described above is uniaxially or biaxially stretched at a stretching temperature of 50 to 180°C, and then stretched as necessary. 120℃ depending on
In the above manner, a method of heat setting at a temperature lower than the melting point can be applied.
二軸延伸を行う場合はテンター法二軸延伸法またはチュ
ーブラ−法二軸延伸法などの公知の方法を適用すること
ができる。When performing biaxial stretching, a known method such as a tenter biaxial stretching method or a tubular biaxial stretching method can be applied.
フィルムはポリアミドおよびそれに均一に分散されてい
る層状珪酸塩およびヒンダードフェノール系化合物およ
びシランカップリング剤及び／又はチタネートカップリ
ング剤を含有した混合物の（実施例）
以下において実施例および比較例を掲げて本発明をさら
に詳しく説明する。なお、以下において物性の測定法は
以下のとおりである。The film is made of a polyamide and a mixture containing a layered silicate and a hindered phenol compound uniformly dispersed therein, and a silane coupling agent and/or a titanate coupling agent (Example) Examples and comparative examples are listed below. The present invention will be explained in more detail below. In addition, the measurement method of physical properties is as follows below.
■ポリアミドの分子量
ＪＩＳ Ｋ６８１０−１９７０に準じて９８％硫酸を
用いて相対粘度を測定し、分子量（Ｍｎ）を求めた。(2) Molecular weight of polyamide The relative viscosity was measured using 98% sulfuric acid in accordance with JIS K6810-1970 to determine the molecular weight (Mn).
■透明性
スガ試験機社製直読式ヘーズメータにより、ＡＳＴＭ
Ｄ−１００３に準じてフィルムの曇価（ヘーズ率）を
測定した。■Transparency ASTM
The haze value (haze rate) of the film was measured according to D-1003.
■酸素ガス透過度
モダンコントロール社製ＭＯＣＯＮ ＯＸ−ＴＲＡＮ
１００Ａにより、ＡＳＴＭ Ｄ−３９８５＝８１
に準じてフィルムの酸素ガス透過度を測定した。■Oxygen gas permeability MOCON OX-TRAN manufactured by Modern Control
ASTM D-3985=81 by 100A
The oxygen gas permeability of the film was measured according to .
測定条件は２３℃、０％ＲＨおよび１００％ＲＨである
。The measurement conditions are 23°C, 0% RH and 100% RH.
■引張特性
東洋ボールドウィン社製テンシロンＵＴＭ−３によりＡ
ＳＴＭ Ｄ−８８２に準じて引張特性を測定した。フ
ィルムの剛性の評価法として引張弾性率をもちいた。テ
ストピース水分率は２３℃、６５％ＲＨ大気中平衡水分
率である。■Tensile properties A by Tensilon UTM-3 manufactured by Toyo Baldwin Co., Ltd.
Tensile properties were measured according to STM D-882. Tensile modulus was used to evaluate film stiffness. The moisture content of the test piece is the equilibrium moisture content in the atmosphere at 23° C. and 65% RH.
実施例１
層状珪酸塩の一単位の厚みが平均８人で一辺の長さが約
０．１μｍの原料であるモンモリロナイト１００ｇをＩ
ＯＡの水に分散し、これに５１．２ ｇの１２−アミノ
ドデカン酸と２４ｍ１の濃塩酸を加え、５分間攪拌した
のち、濾過した。さらにこれを十分洗浄したのち、真空
乾燥した。この操作により、１２−アミノドデカン酸ア
ンモニウムイオンとモンモリロナイトの複合体を調整し
た。複合体中の層状珪酸塩分は約８０重量％となった。Example 1 100 g of montmorillonite, a raw material in which one unit of layered silicate has an average thickness of 8 people and a side length of about 0.1 μm, was
OA was dispersed in water, 51.2 g of 12-aminododecanoic acid and 24 ml of concentrated hydrochloric acid were added thereto, stirred for 5 minutes, and then filtered. Furthermore, after thoroughly washing this, it was vacuum dried. Through this operation, a complex of ammonium 12-aminododecanoate ion and montmorillonite was prepared. The layered silicate content in the composite was about 80% by weight.
Ｘ線解析の結果この複合体中の層状珪酸塩の層間距離は
１８．０人であった。As a result of X-ray analysis, the interlayer distance of the layered silicate in this composite was 18.0.
次に、攪拌機付きの反応容器に１０ｋｇのε−均一な状
態になるように攪拌した。Next, 10 kg of ε was placed in a reaction vessel equipped with a stirrer and stirred to a uniform state.
さらに温度を２６０℃に上昇させ、１５ｋｇ／ｄの加圧
下で１時間攪拌した。その後、放圧し、水分を反応容器
から揮散させながら、常圧下、２６０℃で２時間反応を
行い、さらに４００ｍｍＨｇの減圧下で２６０℃で、１
時間反応させた。反応終了後、反応容器の下部ノズルか
ら、ストランド状に取り出した反応物を水冷し、カッテ
ィングを行い、ポリアミドおよびモンモリロナイトから
なるペレットを得た。このペレットを熱水中に浸漬し、
未反応のモノマー約ｌＯ％を抽出、除去したのち、真空
中で乾燥した。The temperature was further raised to 260°C, and the mixture was stirred for 1 hour under a pressure of 15 kg/d. Thereafter, the pressure was released and the reaction was carried out at 260°C for 2 hours under normal pressure while evaporating water from the reaction vessel, and then at 260°C under reduced pressure of 400 mmHg for 1 hour.
Allowed time to react. After the reaction was completed, the reaction product taken out in the form of a strand from the lower nozzle of the reaction vessel was cooled with water and cut to obtain pellets consisting of polyamide and montmorillonite. The pellets are immersed in hot water,
After extracting and removing about 10% of unreacted monomers, the mixture was dried in vacuo.
この得られた組成物に、テトラキス（２，４−ジ−ｔ−
ブチルフェニル）−４，４’ −ビフェニルフォスフォ
ナイト〔日本チバガイギー（掬製ＩＲＧＡＦＯ３１６８
）（以下物質Ａと記す）を０．２５重量％ブレンドし、
２軸混練機にて、樹脂温度にイソプロピルトリイソステ
アロイルチタネート〔味の素■製プレンアクトＫＡＴＴ
Ｓ）（以下物質Ｃと記す）を０．１重量％ブレンドし、
２軸混練機にて、樹脂温度２６０℃にて溶融混練を行い
、さらに真空乾燥し、ペレット状の組成物を得た。Tetrakis (2,4-di-t-
butylphenyl)-4,4'-biphenylphosphonite [IRGAFO3168 manufactured by Nippon Ciba Geigy (Kiki)
) (hereinafter referred to as substance A) is blended at 0.25% by weight,
Using a two-screw kneader, add isopropyl triisostearoyl titanate [Plenact KATT manufactured by Ajinomoto Co., Ltd.] to the resin temperature.
S) (hereinafter referred to as substance C) is blended at 0.1% by weight,
The mixture was melt-kneaded using a twin-screw kneader at a resin temperature of 260° C., and further vacuum-dried to obtain a pellet-like composition.
このペレットを用い、直径４０１ｍの押し出し機でシリ
ンダー温度２６０℃の条件で混練し、３００ ＋ｎ＋ｎ
幅のＴ−ダイでフィルム状に押し出し、４０℃の冷却ロ
ール上で固化し、厚さ６０μのフィルムを調整した。Using these pellets, kneading was performed using an extruder with a diameter of 401 m at a cylinder temperature of 260°C, resulting in 300 + n + n
It was extruded into a film using a wide T-die and solidified on a cooling roll at 40°C to prepare a film with a thickness of 60 μm.
フィルムに含有されている層状珪酸塩の層間距離は１０
０Å以上であった。The interlayer distance of the layered silicate contained in the film is 10
It was 0 Å or more.
さらに、このフィルムを下記の装置にて８０°Ｃの雰囲
気温度で２×２に２軸延伸した。延伸時のフィルムの水
分率は０．５％とした。Furthermore, this film was biaxially stretched 2×2 at an ambient temperature of 80° C. using the following apparatus. The moisture content of the film during stretching was 0.5%.
（延伸装置）
若木製作所製 ２軸延伸機
このようにして得られた１５μのフィルムについて、前
述したポリアミドの分子量、透明性、酸素ガス透過度、
引っ張り特性の測定を行った。(Stretching device) Biaxial stretching machine manufactured by Wakagi Manufacturing Co., Ltd. Regarding the 15μ film thus obtained, the polyamide molecular weight, transparency, oxygen gas permeability,
The tensile properties were measured.
結果を第１表に示す。The results are shown in Table 1.
実施例２
実施例１において、物質Ｃの配合量を０．０７５重量％
とした以外は、実施例１と同様の実験を行った。結果を
第１表に示す。Example 2 In Example 1, the blending amount of substance C was 0.075% by weight.
The same experiment as in Example 1 was conducted except that. The results are shown in Table 1.
実施例３
実施例１において、物質Ｃの配合量を０．０５重量％と
した以外は実施例１と同様の実験を行った。Example 3 The same experiment as in Example 1 was conducted except that the amount of substance C blended was 0.05% by weight.
結果を第１表に示す。The results are shown in Table 1.
実施例４
実施例１において、物質Ａの配合量を０．０５重量％と
した以外は実施例１と同様の実験を行った。Example 4 An experiment similar to Example 1 was conducted except that the amount of substance A blended was 0.05% by weight.
結果を第１表に示す。The results are shown in Table 1.
実施例５
実施例１において、物質への配合量を０．１５重量％と
じた以外は実施例１と同様の実験を行った。Example 5 The same experiment as in Example 1 was conducted except that the amount added to the substance was limited to 0.15% by weight.
結果を第１表に示す。The results are shown in Table 1.
実施例６
実施例１において、物質Ａの代わりに、１．３゜５−ト
リエチル−２，４，６−トリス（３，５−ジ−ｔ−ブチ
ル−４−ヒドロキシベンジル）ベンゼン〔日本チバガイ
ギー（株制Ｉ ＲＧＡＮＯＸ ｌ ３３０〕 （以下物
質Ｂと記す）を用いた以外は実施例１と同様の実験を行
った。結果を第１表に示す。Example 6 In Example 1, instead of substance A, 1.3°5-triethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene [Nippon Ciba Geigy Co., Ltd. The same experiment as in Example 1 was conducted except that strain I RGANOX 1 330] (hereinafter referred to as substance B) was used.The results are shown in Table 1.
実施例７
実施例１において、物質Ａと物質Ｂの溶融混練の順序を
反対にした以外は実施例１と同様の実験を行った。結果
を第１表に示す。Example 7 An experiment similar to Example 1 was conducted except that the order of melting and kneading of Substance A and Substance B was reversed. The results are shown in Table 1.
実施例８
実施例１において、物質へと物質Ｂを同時に溶融混練し
た以外は実施例１と同様の実験を行った。Example 8 An experiment similar to Example 1 was carried out except that in Example 1, substance B was simultaneously melted and kneaded into the substance.
結果を第１表に示す。The results are shown in Table 1.
比較例１
実施例１において、物質Ｃを用いなかった以外は実施例
１と同様の実験を行った。結果を第２表に示す。Comparative Example 1 An experiment similar to Example 1 was conducted except that Substance C was not used. The results are shown in Table 2.
比較例２
実施例４において、物質Ｃを用いなかった以外は実施例
４と同様の実験を行った。結果を第２表に示す。Comparative Example 2 An experiment similar to Example 4 was conducted except that Substance C was not used. The results are shown in Table 2.
比較例３
実施例６において、物質Ｃを用いなかった以外は実施例
６と同様の実験を行った。結果を第２表に示す。Comparative Example 3 In Example 6, an experiment similar to Example 6 was conducted except that substance C was not used. The results are shown in Table 2.
比較例４
実施例１において、物質Ａを用いなかった以外は実施例
１と同様の実験を行った。結果を第２表に示す。Comparative Example 4 An experiment similar to Example 1 was conducted except that Substance A was not used. The results are shown in Table 2.
比較例５
実施例２において、物質Ａを用いなかった以外は実施例
２と同様の実験を行った。結果を第２表に示す。Comparative Example 5 An experiment similar to Example 2 was conducted except that substance A was not used. The results are shown in Table 2.
比較例６
実施例３において、物質Ａを用いなかった以外は実施例
３と同様の実験を行った。結果を第２表に示す。Comparative Example 6 In Example 3, an experiment similar to Example 3 was conducted except that substance A was not used. The results are shown in Table 2.
比較例７
実施例１において、物質Ａ及び物質Ｃを用いなかった以
外は実施例３と同様の実験を行った。結果を第２表に示
す。Comparative Example 7 In Example 1, an experiment similar to Example 3 was conducted except that Substance A and Substance C were not used. The results are shown in Table 2.
参考例１
参考のため、層状珪酸塩、ヒンダードフェノール系化合
物及びカップリング剤を含まないポリアミドの実験例を
参考例１として第２表に示す。Reference Example 1 For reference, an experimental example of polyamide containing no layered silicate, hindered phenol compound, and coupling agent is shown in Table 2 as Reference Example 1.
本発明の組成物より得られた延伸フィルムは、ガスバリ
ヤ−性、透明性、滑り性、耐衝撃性が優れているたけで
なく、優れた剛性を有していることから印刷、ラミネー
ト、製袋なとの後加工か良好であり、特に食品包装用フ
ィルムとして実用上極めて有用である。The stretched film obtained from the composition of the present invention not only has excellent gas barrier properties, transparency, slipperiness, and impact resistance, but also has excellent rigidity, so it can be used for printing, laminating, and bag making. The post-processing process is good, and it is extremely useful in practical use, especially as a food packaging film.
Claims (1)
５〜３０重量％、 （Ｃ）ヒンダードフェノール系化合物０．００１〜５重
量％及び （Ｄ）次式（ I ）で示されるシランカップリング剤及
び／又は次式（II）で示される チタネートカップリング剤０．０１〜５重量％よりなる
ことを特徴とする延伸ポリアミドフィルム用樹脂組成物
。 Ｙ（Ｒ＾１）＿ｎＳｉＸ＿３・・・・・・〔 I 〕 （式〔 I 〕中、Ｘは、塩素原子、アルコキシ基又はア
ルコキシエトキシ基を表し、Ｙは、塩素原子ビニル基、
メタクリロイル基、グリシドキシ基、メルカプト基、ア
ミノ基、２，３−エポキシエチル基、３，４−エポキシ
シクロヘキシル基、ウレイド基又は式▲数式、化学式、
表等があります▼基 を表し、Ｒ＾１は、アルキレン基を表し、ｎは、０又は
１を表す。） 式〔II〕 ▲数式、化学式、表等があります▼・・・・・・〔II〕 （式〔II〕中、Ｒ＾２はアルキル基を表し、Ｒ＾３〜Ｒ
＾５は、それぞれ置換もしくは非置換のアルキル基、ア
ルカノイル基、（メタ）アクリロイル基、ジアルキルピ
ロホスフェート基、Ｎ−アミノエチル−アミノエチル基
、アルキルベンゼンスルホニル基、ジアルキルホスフェ
ート基又はクミルフェニル基を表し、Ｒ＾２とＲ＾３が
一緒になってエチレン基、オキサリル基または、式−Ｃ
Ｏ−ＣＨ＿２−基でも良い。）(1) (A) 60 to 99.939% by weight of polyamide resin (B) 0.0 phyllosilicate uniformly dispersed in the above (A)
5 to 30% by weight, (C) 0.001 to 5% by weight of a hindered phenol compound, and (D) a silane coupling agent represented by the following formula (I) and/or a titanate cup represented by the following formula (II). A resin composition for a stretched polyamide film, comprising 0.01 to 5% by weight of a ring agent. Y(R^1)_nSiX_3...[I] (In the formula [I], X represents a chlorine atom, an alkoxy group, or an alkoxyethoxy group, and Y represents a chlorine atom vinyl group,
Methacryloyl group, glycidoxy group, mercapto group, amino group, 2,3-epoxyethyl group, 3,4-epoxycyclohexyl group, ureido group or formula ▲ Numerical formula, chemical formula,
There are tables, etc. ▼ represents a group, R^1 represents an alkylene group, and n represents 0 or 1. ) Formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・[II] (In formula [II], R^2 represents an alkyl group, and R^3~R
^5 represents a substituted or unsubstituted alkyl group, alkanoyl group, (meth)acryloyl group, dialkylpyrophosphate group, N-aminoethyl-aminoethyl group, alkylbenzenesulfonyl group, dialkylphosphate group or cumylphenyl group, and R ^2 and R^3 together form an ethylene group, an oxalyl group, or a formula -C
It may also be an O-CH_2- group. )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2303849A JP2884766B2 (en) | 1990-11-13 | 1990-11-13 | Resin composition for stretched polyamide film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2303849A JP2884766B2 (en) | 1990-11-13 | 1990-11-13 | Resin composition for stretched polyamide film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04178459A true JPH04178459A (en) | 1992-06-25 |
| JP2884766B2 JP2884766B2 (en) | 1999-04-19 |
Family
ID=17926046
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2303849A Expired - Fee Related JP2884766B2 (en) | 1990-11-13 | 1990-11-13 | Resin composition for stretched polyamide film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2884766B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07300491A (en) * | 1994-05-02 | 1995-11-14 | Nippon Unicar Co Ltd | Silane coupling agent composition |
| US5700560A (en) * | 1992-07-29 | 1997-12-23 | Sumitomo Chemical Company, Limited | Gas barrier resin composition and its film and process for producing the same |
| JP2002029012A (en) * | 2000-07-17 | 2002-01-29 | Ube Ind Ltd | Multilayered stretched film |
| JP2012001646A (en) * | 2010-06-18 | 2012-01-05 | Unitika Ltd | Polyamide resin composition and its manufacturing method |
| US8192811B2 (en) * | 2003-03-14 | 2012-06-05 | Graham Packaging Pet Technologies Inc. | Delamination-resistant multilayer container, preform and method of manufacture |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54139657A (en) * | 1978-04-21 | 1979-10-30 | Unitika Ltd | Production of improved polyamide resin composition |
| JPS6411157A (en) * | 1987-07-03 | 1989-01-13 | Toyota Central Res & Dev | Polyamide composite material |
| JPH02105856A (en) * | 1988-10-14 | 1990-04-18 | Ube Ind Ltd | Polyamide film |
-
1990
- 1990-11-13 JP JP2303849A patent/JP2884766B2/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54139657A (en) * | 1978-04-21 | 1979-10-30 | Unitika Ltd | Production of improved polyamide resin composition |
| JPS6411157A (en) * | 1987-07-03 | 1989-01-13 | Toyota Central Res & Dev | Polyamide composite material |
| JPH02105856A (en) * | 1988-10-14 | 1990-04-18 | Ube Ind Ltd | Polyamide film |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5700560A (en) * | 1992-07-29 | 1997-12-23 | Sumitomo Chemical Company, Limited | Gas barrier resin composition and its film and process for producing the same |
| US5969029A (en) * | 1992-07-29 | 1999-10-19 | Sumitomo Chemical Company, Limited | Process for producing a gas barrier resin composition |
| JPH07300491A (en) * | 1994-05-02 | 1995-11-14 | Nippon Unicar Co Ltd | Silane coupling agent composition |
| JP2002029012A (en) * | 2000-07-17 | 2002-01-29 | Ube Ind Ltd | Multilayered stretched film |
| US8192811B2 (en) * | 2003-03-14 | 2012-06-05 | Graham Packaging Pet Technologies Inc. | Delamination-resistant multilayer container, preform and method of manufacture |
| JP2012001646A (en) * | 2010-06-18 | 2012-01-05 | Unitika Ltd | Polyamide resin composition and its manufacturing method |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2884766B2 (en) | 1999-04-19 |
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