JPWO2019044882A1 - Polyamide resin and film made of it - Google Patents
Polyamide resin and film made of it Download PDFInfo
- Publication number
- JPWO2019044882A1 JPWO2019044882A1 JP2019539566A JP2019539566A JPWO2019044882A1 JP WO2019044882 A1 JPWO2019044882 A1 JP WO2019044882A1 JP 2019539566 A JP2019539566 A JP 2019539566A JP 2019539566 A JP2019539566 A JP 2019539566A JP WO2019044882 A1 JPWO2019044882 A1 JP WO2019044882A1
- Authority
- JP
- Japan
- Prior art keywords
- unit
- polyamide resin
- acid
- weight
- aromatic ring
- 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
- 229920006122 polyamide resin Polymers 0.000 title claims abstract description 81
- 125000003118 aryl group Chemical group 0.000 claims abstract description 76
- 150000004985 diamines Chemical class 0.000 claims abstract description 55
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical class OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 50
- 150000003839 salts Chemical class 0.000 claims abstract description 49
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims abstract description 21
- 150000003951 lactams Chemical class 0.000 claims abstract description 21
- 229920006300 shrink film Polymers 0.000 claims abstract description 14
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 34
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 24
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims description 22
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 18
- 239000001361 adipic acid Substances 0.000 claims description 17
- 235000011037 adipic acid Nutrition 0.000 claims description 17
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 16
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 6
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 claims description 3
- 229960002684 aminocaproic acid Drugs 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 description 38
- 229920002647 polyamide Polymers 0.000 description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 35
- 238000000034 method Methods 0.000 description 19
- 239000002253 acid Substances 0.000 description 13
- 238000006116 polymerization reaction Methods 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- -1 aliphatic diamine Chemical class 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 238000000465 moulding Methods 0.000 description 9
- 230000000704 physical effect Effects 0.000 description 9
- 125000004427 diamine group Chemical group 0.000 description 7
- 125000001142 dicarboxylic acid group Chemical group 0.000 description 6
- 239000008188 pellet Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 235000013305 food Nutrition 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000003607 modifier Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000005003 food packaging material Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 239000005022 packaging material Substances 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- PBLZLIFKVPJDCO-UHFFFAOYSA-N 12-aminododecanoic acid Chemical compound NCCCCCCCCCCCC(O)=O PBLZLIFKVPJDCO-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004512 die casting Methods 0.000 description 2
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- YFOOEYJGMMJJLS-UHFFFAOYSA-N 1,8-diaminonaphthalene Chemical compound C1=CC(N)=C2C(N)=CC=CC2=C1 YFOOEYJGMMJJLS-UHFFFAOYSA-N 0.000 description 1
- XAUQWYHSQICPAZ-UHFFFAOYSA-N 10-amino-decanoic acid Chemical compound NCCCCCCCCCC(O)=O XAUQWYHSQICPAZ-UHFFFAOYSA-N 0.000 description 1
- GUOSQNAUYHMCRU-UHFFFAOYSA-N 11-Aminoundecanoic acid Chemical compound NCCCCCCCCCCC(O)=O GUOSQNAUYHMCRU-UHFFFAOYSA-N 0.000 description 1
- JCUZDQXWVYNXHD-UHFFFAOYSA-N 2,2,4-trimethylhexane-1,6-diamine Chemical compound NCCC(C)CC(C)(C)CN JCUZDQXWVYNXHD-UHFFFAOYSA-N 0.000 description 1
- BTUDGPVTCYNYLK-UHFFFAOYSA-N 2,2-dimethylglutaric acid Chemical compound OC(=O)C(C)(C)CCC(O)=O BTUDGPVTCYNYLK-UHFFFAOYSA-N 0.000 description 1
- VECYFPCPMVHUEN-UHFFFAOYSA-N 2,2-dimethylheptane-1,7-diamine Chemical compound NCC(C)(C)CCCCCN VECYFPCPMVHUEN-UHFFFAOYSA-N 0.000 description 1
- QPIDRHUVWIFOBW-UHFFFAOYSA-N 2,2-dimethylhexane-1,6-diamine Chemical compound NCC(C)(C)CCCCN QPIDRHUVWIFOBW-UHFFFAOYSA-N 0.000 description 1
- GOHPTLYPQCTZSE-UHFFFAOYSA-N 2,2-dimethylsuccinic acid Chemical compound OC(=O)C(C)(C)CC(O)=O GOHPTLYPQCTZSE-UHFFFAOYSA-N 0.000 description 1
- BQNDPALRJDCXOY-UHFFFAOYSA-N 2,3-dibutylbutanedioic acid Chemical compound CCCCC(C(O)=O)C(C(O)=O)CCCC BQNDPALRJDCXOY-UHFFFAOYSA-N 0.000 description 1
- RMIUJCRSUIITNG-UHFFFAOYSA-N 2,3-dimethylbutane-1,4-diamine Chemical compound NCC(C)C(C)CN RMIUJCRSUIITNG-UHFFFAOYSA-N 0.000 description 1
- KEEWXLYVPARTPY-UHFFFAOYSA-N 2,3-dimethylheptane-1,7-diamine Chemical compound NCC(C)C(C)CCCCN KEEWXLYVPARTPY-UHFFFAOYSA-N 0.000 description 1
- DPQHRXRAZHNGRU-UHFFFAOYSA-N 2,4,4-trimethylhexane-1,6-diamine Chemical compound NCC(C)CC(C)(C)CCN DPQHRXRAZHNGRU-UHFFFAOYSA-N 0.000 description 1
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- AHBYWKWAVAMOMN-UHFFFAOYSA-N 2,4-diethylhexane-1,6-diamine Chemical compound CCC(CN)CC(CC)CCN AHBYWKWAVAMOMN-UHFFFAOYSA-N 0.000 description 1
- UVCBXTALTSTYBM-UHFFFAOYSA-N 2,4-dimethylheptane-1,7-diamine Chemical compound NCC(C)CC(C)CCCN UVCBXTALTSTYBM-UHFFFAOYSA-N 0.000 description 1
- KSQSUDDRZLCKSW-UHFFFAOYSA-N 2,4-dimethylhexane-1,6-diamine Chemical compound NCC(C)CC(C)CCN KSQSUDDRZLCKSW-UHFFFAOYSA-N 0.000 description 1
- SQAPJTNHAUBTOP-UHFFFAOYSA-N 2,4-dimethyloctane-1,8-diamine Chemical compound NCC(C)CC(C)CCCCN SQAPJTNHAUBTOP-UHFFFAOYSA-N 0.000 description 1
- YXOKJIRTNWHPFS-UHFFFAOYSA-N 2,5-dimethylhexane-1,6-diamine Chemical compound NCC(C)CCC(C)CN YXOKJIRTNWHPFS-UHFFFAOYSA-N 0.000 description 1
- RLYCRLGLCUXUPO-UHFFFAOYSA-N 2,6-diaminotoluene Chemical compound CC1=C(N)C=CC=C1N RLYCRLGLCUXUPO-UHFFFAOYSA-N 0.000 description 1
- STSHNZLPEUVYPD-UHFFFAOYSA-N 2,6-diethyl-4-propylaniline Chemical compound CCCC1=CC(CC)=C(N)C(CC)=C1 STSHNZLPEUVYPD-UHFFFAOYSA-N 0.000 description 1
- XCAXUUTZSDAIEJ-UHFFFAOYSA-N 2,6-dimethyl-4-propylaniline Chemical compound CCCC1=CC(C)=C(N)C(C)=C1 XCAXUUTZSDAIEJ-UHFFFAOYSA-N 0.000 description 1
- JZUMVFMLJGSMRF-UHFFFAOYSA-N 2-Methyladipic acid Chemical compound OC(=O)C(C)CCCC(O)=O JZUMVFMLJGSMRF-UHFFFAOYSA-N 0.000 description 1
- QUEYDGJHECZMBX-UHFFFAOYSA-N 2-ethyl-6-methyl-4-propylaniline Chemical compound CCCC1=CC(C)=C(N)C(CC)=C1 QUEYDGJHECZMBX-UHFFFAOYSA-N 0.000 description 1
- FUFUNXPZSKBIQW-UHFFFAOYSA-N 2-methyl-4-propylaniline Chemical compound CCCC1=CC=C(N)C(C)=C1 FUFUNXPZSKBIQW-UHFFFAOYSA-N 0.000 description 1
- GAGWMWLBYJPFDD-UHFFFAOYSA-N 2-methyloctane-1,8-diamine Chemical compound NCC(C)CCCCCCN GAGWMWLBYJPFDD-UHFFFAOYSA-N 0.000 description 1
- ACEKLXGWCBIDGA-UHFFFAOYSA-N 2-methylpentane-1,4-diamine Chemical compound CC(N)CC(C)CN ACEKLXGWCBIDGA-UHFFFAOYSA-N 0.000 description 1
- JZUHIOJYCPIVLQ-UHFFFAOYSA-N 2-methylpentane-1,5-diamine Chemical compound NCC(C)CCCN JZUHIOJYCPIVLQ-UHFFFAOYSA-N 0.000 description 1
- IGMCTDOFLKWLPJ-UHFFFAOYSA-N 2-octylundecanedioic acid Chemical compound CCCCCCCCC(C(O)=O)CCCCCCCCC(O)=O IGMCTDOFLKWLPJ-UHFFFAOYSA-N 0.000 description 1
- WTXAAHKEBFFHIC-UHFFFAOYSA-N 3,3-dimethyloctane-1,8-diamine Chemical compound NCCC(C)(C)CCCCCN WTXAAHKEBFFHIC-UHFFFAOYSA-N 0.000 description 1
- NEIQVECNZQYVDC-UHFFFAOYSA-N 3,4-dimethyloctane-1,8-diamine Chemical compound NCCC(C)C(C)CCCCN NEIQVECNZQYVDC-UHFFFAOYSA-N 0.000 description 1
- CKOFBUUFHALZGK-UHFFFAOYSA-N 3-[(3-aminophenyl)methyl]aniline Chemical compound NC1=CC=CC(CC=2C=C(N)C=CC=2)=C1 CKOFBUUFHALZGK-UHFFFAOYSA-N 0.000 description 1
- FGWQCROGAHMWSU-UHFFFAOYSA-N 3-[(4-aminophenyl)methyl]aniline Chemical compound C1=CC(N)=CC=C1CC1=CC=CC(N)=C1 FGWQCROGAHMWSU-UHFFFAOYSA-N 0.000 description 1
- FRWWUJNIGJTYJY-UHFFFAOYSA-N 3-methyloctane-1,8-diamine Chemical compound NCCC(C)CCCCCN FRWWUJNIGJTYJY-UHFFFAOYSA-N 0.000 description 1
- OLTBRQIRRDQOTO-UHFFFAOYSA-N 3-methylpentane-1,4-diamine Chemical compound CC(N)C(C)CCN OLTBRQIRRDQOTO-UHFFFAOYSA-N 0.000 description 1
- FJSUFIIJYXMJQO-UHFFFAOYSA-N 3-methylpentane-1,5-diamine Chemical compound NCCC(C)CCN FJSUFIIJYXMJQO-UHFFFAOYSA-N 0.000 description 1
- WECDUOXQLAIPQW-UHFFFAOYSA-N 4,4'-Methylene bis(2-methylaniline) Chemical compound C1=C(N)C(C)=CC(CC=2C=C(C)C(N)=CC=2)=C1 WECDUOXQLAIPQW-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
- ULLJDGWZKSOING-UHFFFAOYSA-N 4,4-dimethyloctane-1,8-diamine Chemical compound NCCCC(C)(C)CCCCN ULLJDGWZKSOING-UHFFFAOYSA-N 0.000 description 1
- CPWPLIIHQWYLLH-UHFFFAOYSA-N 4,5-dimethyloctane-1,8-diamine Chemical compound NCCCC(C)C(C)CCCN CPWPLIIHQWYLLH-UHFFFAOYSA-N 0.000 description 1
- NWIVYGKSHSJHEF-UHFFFAOYSA-N 4-[(4-amino-3,5-diethylphenyl)methyl]-2,6-diethylaniline Chemical compound CCC1=C(N)C(CC)=CC(CC=2C=C(CC)C(N)=C(CC)C=2)=C1 NWIVYGKSHSJHEF-UHFFFAOYSA-N 0.000 description 1
- CBEVWPCAHIAUOD-UHFFFAOYSA-N 4-[(4-amino-3-ethylphenyl)methyl]-2-ethylaniline Chemical compound C1=C(N)C(CC)=CC(CC=2C=C(CC)C(N)=CC=2)=C1 CBEVWPCAHIAUOD-UHFFFAOYSA-N 0.000 description 1
- VTDMBRAUHKUOON-UHFFFAOYSA-N 4-[(4-carboxyphenyl)methyl]benzoic acid Chemical class C1=CC(C(=O)O)=CC=C1CC1=CC=C(C(O)=O)C=C1 VTDMBRAUHKUOON-UHFFFAOYSA-N 0.000 description 1
- ZYEDGEXYGKWJPB-UHFFFAOYSA-N 4-[2-(4-aminophenyl)propan-2-yl]aniline Chemical compound C=1C=C(N)C=CC=1C(C)(C)C1=CC=C(N)C=C1 ZYEDGEXYGKWJPB-UHFFFAOYSA-N 0.000 description 1
- GUCABLZOWVOFSJ-UHFFFAOYSA-N 4-methyloctane-1,8-diamine Chemical compound NCCCC(C)CCCCN GUCABLZOWVOFSJ-UHFFFAOYSA-N 0.000 description 1
- WHLFXPIYRPOHGB-UHFFFAOYSA-N 4-methylpentane-1,4-diamine Chemical compound CC(C)(N)CCCN WHLFXPIYRPOHGB-UHFFFAOYSA-N 0.000 description 1
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- UVJGPFKXFTVLIZ-UHFFFAOYSA-N 5-methylnonane-1,8-diamine Chemical compound CC(N)CCC(C)CCCCN UVJGPFKXFTVLIZ-UHFFFAOYSA-N 0.000 description 1
- MBRGOFWKNLPACT-UHFFFAOYSA-N 5-methylnonane-1,9-diamine Chemical compound NCCCCC(C)CCCCN MBRGOFWKNLPACT-UHFFFAOYSA-N 0.000 description 1
- GAYWCADKXYCKCG-UHFFFAOYSA-N 5-pyridin-3-yl-1,2-dihydro-1,2,4-triazole-3-thione Chemical compound N1NC(=S)N=C1C1=CC=CN=C1 GAYWCADKXYCKCG-UHFFFAOYSA-N 0.000 description 1
- XDOLZJYETYVRKV-UHFFFAOYSA-N 7-Aminoheptanoic acid Chemical compound NCCCCCCC(O)=O XDOLZJYETYVRKV-UHFFFAOYSA-N 0.000 description 1
- UQXNEWQGGVUVQA-UHFFFAOYSA-N 8-aminooctanoic acid Chemical compound NCCCCCCCC(O)=O UQXNEWQGGVUVQA-UHFFFAOYSA-N 0.000 description 1
- JHRJYXZOXJXEJJ-UHFFFAOYSA-N 8-ethyloctadecanedioic acid Chemical compound OC(=O)CCCCCCC(CC)CCCCCCCCCC(O)=O JHRJYXZOXJXEJJ-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- SYEOWUNSTUDKGM-UHFFFAOYSA-N beta-methyladipic acid Natural products OC(=O)CC(C)CCC(O)=O SYEOWUNSTUDKGM-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- OREAFAJWWJHCOT-UHFFFAOYSA-N dimethylmalonic acid Chemical compound OC(=O)C(C)(C)C(O)=O OREAFAJWWJHCOT-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- HYQBVSXBLGKEDT-UHFFFAOYSA-N hexane-1,4-diamine Chemical compound CCC(N)CCCN HYQBVSXBLGKEDT-UHFFFAOYSA-N 0.000 description 1
- BBPXVYVXKAYBSS-UHFFFAOYSA-N hexane-2,5-diamine Chemical compound CC(N)CCC(C)N BBPXVYVXKAYBSS-UHFFFAOYSA-N 0.000 description 1
- TVZISJTYELEYPI-UHFFFAOYSA-N hypodiphosphoric acid Chemical compound OP(O)(=O)P(O)(O)=O TVZISJTYELEYPI-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- ABMFBCRYHDZLRD-UHFFFAOYSA-N naphthalene-1,4-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1 ABMFBCRYHDZLRD-UHFFFAOYSA-N 0.000 description 1
- HRRDCWDFRIJIQZ-UHFFFAOYSA-N naphthalene-1,8-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=C2C(C(=O)O)=CC=CC2=C1 HRRDCWDFRIJIQZ-UHFFFAOYSA-N 0.000 description 1
- XTBLDMQMUSHDEN-UHFFFAOYSA-N naphthalene-2,3-diamine Chemical compound C1=CC=C2C=C(N)C(N)=CC2=C1 XTBLDMQMUSHDEN-UHFFFAOYSA-N 0.000 description 1
- GOGZBMRXLADNEV-UHFFFAOYSA-N naphthalene-2,6-diamine Chemical compound C1=C(N)C=CC2=CC(N)=CC=C21 GOGZBMRXLADNEV-UHFFFAOYSA-N 0.000 description 1
- 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 1
- WPUMVKJOWWJPRK-UHFFFAOYSA-N naphthalene-2,7-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=CC2=CC(C(=O)O)=CC=C21 WPUMVKJOWWJPRK-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 235000020991 processed meat Nutrition 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 235000013580 sausages Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000807 solvent casting Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- SDVHRXOTTYYKRY-UHFFFAOYSA-J tetrasodium;dioxido-oxo-phosphonato-$l^{5}-phosphane Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)P([O-])([O-])=O SDVHRXOTTYYKRY-UHFFFAOYSA-J 0.000 description 1
- KLNPWTHGTVSSEU-UHFFFAOYSA-N undecane-1,11-diamine Chemical compound NCCCCCCCCCCCN KLNPWTHGTVSSEU-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/36—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino acids, polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
Abstract
３種以上の単位を含み、（Ａ）ラクタム及び／又はアミノカルボン酸に由来する単位並びに（Ｂ）ジアミン及びジカルボン酸の等モル塩に由来する単位を含み、前記（Ｂ）ジアミン及びジカルボン酸の等モル塩に由来する単位は、（Ｂ−１）芳香環構造を有さない単位及び（Ｂ−２）芳香環構造を有する単位を含む、シュリンクフィルム用ポリアミド樹脂又はそのフィルムである。Containing three or more units, including (A) units derived from lactam and / or aminocarboxylic acid and (B) units derived from isomorphic salts of diamine and dicarboxylic acid, of the above-mentioned (B) diamine and dicarboxylic acid. The unit derived from the isomorphic salt is a polyamide resin for shrink film or a film thereof, which contains (B-1) a unit having no aromatic ring structure and (B-2) a unit having an aromatic ring structure.
Description
本発明はポリアミド樹脂及びそれからなるフィルムに関する。 The present invention relates to a polyamide resin and a film made of the polyamide resin.
ポリアミド樹脂は機械的強度、熱的性質、化学的性質やガスバリヤー性に優れているため、レトルト食品などの食品包装用材料として使用されている。近年、これら食品包装用途の拡大に伴い、要求特性が多様化、高度化している。食品包装用途の一つであるハム、ソーセージなどの加工食肉製品や水物食品包装用途では、薄く、且つ実用的な機械的強度及びガスバリヤー性を維持しつつ、加熱によって包装材料を収縮させることで内容物の緊密包装が容易に可能となるような熱収縮性に優れたポリアミドフィルムが求められている。 Polyamide resins are used as food packaging materials for retort pouch foods because they have excellent mechanical strength, thermal properties, chemical properties, and gas barrier properties. In recent years, with the expansion of these food packaging applications, the required characteristics have become diversified and sophisticated. In processed meat products such as ham and sausage, which is one of the food packaging applications, and water food packaging applications, the packaging material is shrunk by heating while maintaining thin and practical mechanical strength and gas barrier properties. There is a demand for a polyamide film having excellent heat shrinkage so that the contents can be easily packed tightly.
これまで、ポリアミドフィルムの熱収縮性が改良できるポリアミド樹脂やポリアミドフィルムが開示されている。熱収縮性が改良できるポリアミド樹脂としては、ε−カプロラクタムと、ヘキサメチレンジアミンなどの脂肪族ジアミン及びテレフタル酸、イソフタル酸などの芳香族ジカルボン酸とからなるポリアミド共重合体が開示されている（例えば、特許文献１参照）。 So far, polyamide resins and polyamide films that can improve the heat shrinkage of polyamide films have been disclosed. As a polyamide resin having improved heat shrinkage, a polyamide copolymer composed of ε-caprolactam, an aliphatic diamine such as hexamethylenediamine, and an aromatic dicarboxylic acid such as terephthalic acid and isophthalic acid is disclosed (for example). , Patent Document 1).
しかしながら、内容物との緊密性をより向上させることができるポリアミドフィルムとそのフィルムが提供できるポリアミド樹脂が求められている。 However, there is a demand for a polyamide film capable of further improving the closeness to the contents and a polyamide resin capable of providing the film.
本発明の目的は、熱収縮性、耐ピンホール性等に優れるフィルム及びそれに適したポリアミド樹脂を提供することにある。 An object of the present invention is to provide a film having excellent heat shrinkage, pinhole resistance and the like, and a polyamide resin suitable therefor.
本発明者は、分子鎖中に芳香環構造を有するジアミンもしくはジカルボン酸に由来する単位を有する特定のポリアミド樹脂が熱収縮性、耐ピンホール性等に優れることを見出し、本発明に至った。 The present inventor has found that a specific polyamide resin having a unit derived from a diamine or a dicarboxylic acid having an aromatic ring structure in a molecular chain is excellent in heat shrinkage property, pinhole resistance and the like, and has reached the present invention.
即ち、本発明は、
３種以上の単位を含むポリアミド樹脂であって、
（Ａ）ラクタム及び／又はアミノカルボン酸に由来する単位並びに
（Ｂ）ジアミン及びジカルボン酸の等モル塩に由来する単位を含み、
前記（Ｂ）ジアミン及びジカルボン酸の等モル塩に由来する単位は、
（Ｂ−１）芳香環構造を有さない単位及び
（Ｂ−２）芳香環構造を有する単位
を含むシュリンクフィルム用ポリアミド樹脂である。
本発明は、好ましくは、ポリアミド樹脂の全単位中に、
前記（Ａ）ラクタム及び／又はアミノカルボン酸に由来する単位を６０〜７０重量％及び前記（Ｂ）ジアミン及びジカルボン酸の等モル塩に由来する単位を３０〜４０重量％含み、かつ、前記（Ｂ−１）芳香環構造を有さない単位を２５〜３９重量％及び前記（Ｂ−２）芳香環構造を有する単位を１〜１５重量％含む、シュリンクフィルム用ポリアミド樹脂である。That is, the present invention
A polyamide resin containing 3 or more units.
Includes (A) units derived from lactam and / or aminocarboxylic acids and (B) units derived from equimolar salts of diamines and dicarboxylic acids.
The unit derived from the equimolar salt of (B) diamine and dicarboxylic acid is
(B-1) A polyamide resin for a shrink film containing a unit having no aromatic ring structure and (B-2) a unit having an aromatic ring structure.
The present invention preferably comprises, in all units of the polyamide resin,
It contains 60 to 70% by weight of the unit derived from the (A) lactam and / or aminocarboxylic acid and 30 to 40% by weight of the unit derived from the equimolar salt of the (B) diamine and dicarboxylic acid. B-1) A polyamide resin for a shrink film containing 25 to 39% by weight of a unit having no aromatic ring structure and 1 to 15% by weight of a unit having the (B-2) aromatic ring structure.
本発明により、熱収縮性、耐ピンホール性等に優れるポリアミド樹脂とそれからなるフィルムを提供することができる。本発明のポリアミド樹脂からなるフィルムは、延伸性が良好である。本発明のポリアミド樹脂からなる延伸フィルムは、熱収縮性が良好なので、包装用材料、特に、食品包装用材料としてのシュリンクフィルムとして好適に使用できる。 INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a polyamide resin having excellent heat shrinkage, pinhole resistance and the like, and a film made of the polyamide resin. The film made of the polyamide resin of the present invention has good stretchability. Since the stretched film made of the polyamide resin of the present invention has good heat shrinkage, it can be suitably used as a packaging material, particularly as a shrink film as a food packaging material.
本明細書において「〜」を用いて示された数値範囲は、「〜」の前後に記載される数値をそれぞれ最小値及び最大値として含む範囲を示す。さらに組成物中の各成分の含有量は、組成物中に各成分に該当する物質が複数存在する場合、特に断らない限り、組成物中に存在する当該複数の物質の合計量を意味する。 The numerical range indicated by using "~" in the present specification indicates a range including the numerical values before and after "~" as the minimum value and the maximum value, respectively. Further, the content of each component in the composition means the total amount of the plurality of substances present in the composition when a plurality of substances corresponding to each component are present in the composition, unless otherwise specified.
本発明のポリアミド樹脂は、３種以上の単位を含むポリアミド樹脂であって、
（Ａ）ラクタム及び／又はアミノカルボン酸に由来する単位並びに
（Ｂ）ジアミン及びジカルボン酸の等モル塩に由来する単位を含み、
前記（Ｂ）ジアミン及びジカルボン酸の等モル塩に由来する単位は、
（Ｂ−１）芳香環構造を有さない単位及び
（Ｂ−２）芳香環構造を有する単位
を含むポリアミド樹脂である。The polyamide resin of the present invention is a polyamide resin containing three or more units.
Includes (A) units derived from lactam and / or aminocarboxylic acids and (B) units derived from equimolar salts of diamines and dicarboxylic acids.
The unit derived from the equimolar salt of (B) diamine and dicarboxylic acid is
It is a polyamide resin containing (B-1) a unit having no aromatic ring structure and (B-2) a unit having an aromatic ring structure.
［（Ａ）ラクタム及び／又はアミノカルボン酸に由来する単位］
ポリアミド樹脂に含まれる（Ａ）ラクタム及び／又はアミノカルボン酸に由来する単位は、ラクタム及び／又はアミノカルボン酸を重合に供することでポリアミド樹脂中に導入することができる。
ラクタムとしては、ε−カプロラクタム、ω−エナントラクタム、ω−ウンデカラクタム、ω−ドデカラクタム、２−ピロリドンなどが挙げられ、これらからなる群から選択される少なくとも１種が好ましい。
アミノカルボン酸としては、６−アミノカプロン酸、７−アミノヘプタン酸、８−アミノオクタン酸、１０−アミノカプリン酸、１１−アミノウンデカン酸、１２−アミノドデカン酸などが挙げられ、これらからなる群から選択される少なくとも１種が好ましい。
これらのラクタム及びアミノカルボン酸は単独で使用してもよく、２種類以上を適宜組み合わせて使用してもよい。ラクタムとアミノカルボン酸を併用する場合、任意の割合で混合して使用することができる。[(A) Unit derived from lactam and / or aminocarboxylic acid]
The unit derived from (A) lactam and / or aminocarboxylic acid contained in the polyamide resin can be introduced into the polyamide resin by subjecting lactam and / or aminocarboxylic acid to polymerization.
Examples of the lactam include ε-caprolactam, ω-enantractum, ω-undecalactam, ω-dodecalactam, 2-pyrrolidone and the like, and at least one selected from the group consisting of these is preferable.
Examples of the aminocarboxylic acid include 6-aminocaproic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, 10-aminocapric acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and the like. At least one selected is preferred.
These lactams and aminocarboxylic acids may be used alone or in combination of two or more. When lactam and aminocarboxylic acid are used in combination, they can be mixed and used in any ratio.
ポリアミド樹脂の全単位中に含まれる（Ａ）ラクタム及び／又はアミノカルボン酸に由来する単位の含有率は、例えば５０〜９８重量％であり、好ましくは５５〜９０重量％であり、より好ましくは６０〜８８重量％、特に好ましくは６０〜７０重量％である。ラクタム及び／又はアミノカルボン酸に由来する単位の含有率が上記下限以上であると機械的強度がより向上する傾向がある。上記上限以下であると延伸性や熱収縮性がより向上する傾向がある。 The content of the unit derived from (A) lactam and / or aminocarboxylic acid contained in all the units of the polyamide resin is, for example, 50 to 98% by weight, preferably 55 to 90% by weight, and more preferably. It is 60 to 88% by weight, particularly preferably 60 to 70% by weight. When the content of the unit derived from lactam and / or aminocarboxylic acid is at least the above lower limit, the mechanical strength tends to be further improved. When it is not more than the above upper limit, the stretchability and the heat shrinkage tend to be further improved.
［（Ｂ）ジアミン及びジカルボン酸の等モル塩に由来する単位］
ポリアミド樹脂は、（Ｂ）ジアミン及びジカルボン酸の等モル塩に由来する単位として、（Ｂ−１）芳香環構造を有さない単位と、（Ｂ−２）芳香環構造を有する単位とを含む。ここで、ジアミン及びジカルボン酸の等モル塩に由来する単位は、ジアミン及びジカルボン酸の等モル塩又は等モル混合物を重合して形成される単位であり、１種類のジアミン及び１種類のジカルボン酸の組合せで１種類の単位とみなす。なお、当該単位を構成するジアミン及びジカルボン酸は直接縮合していても、他の単位又は他の単位を構成するジアミン若しくはジカルボン酸を介して縮合していてもよい。[(B) Unit derived from equimolar salt of diamine and dicarboxylic acid]
The polyamide resin contains (B) a unit having no aromatic ring structure and (B-2) a unit having an aromatic ring structure as a unit derived from an equimolar salt of diamine and a dicarboxylic acid. .. Here, the unit derived from the equimolar salt of diamine and dicarboxylic acid is a unit formed by polymerizing an equimolar salt of diamine and dicarboxylic acid or an equimolar mixture, and is one kind of diamine and one kind of dicarboxylic acid. The combination of is regarded as one type of unit. The diamine and dicarboxylic acid constituting the unit may be directly condensed, or may be condensed via another unit or a diamine or dicarboxylic acid constituting another unit.
（Ｂ−１）芳香環構造を有さない単位
ポリアミド樹脂に含まれる（Ｂ−１）芳香環構造を有さない単位は、ジアミン及びジカルボン酸の等モル塩又は等モル混合物に由来する芳香環構造を有さない単位であり、芳香環構造を有するジアミン以外のジアミンと、芳香環構造を有するジカルボン酸以外のジカルボン酸とを重合することで形成される。(B-1) Unit without aromatic ring structure The unit without aromatic ring structure contained in the polyamide resin (B-1) is an aromatic ring derived from an isomorphic salt of diamine and dicarboxylic acid or an equimolar mixture. It is a unit having no structure, and is formed by polymerizing a diamine other than a diamine having an aromatic ring structure and a dicarboxylic acid other than a dicarboxylic acid having an aromatic ring structure.
芳香環構造を有するジアミン以外のジアミンとしては、エチレンジアミン、テトラメチレンジアミン、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などの直鎖状脂肪族ジアミン；１−ブチル−１，２−エタンジアミン、１，１−ジメチル−１，４−ブタンジアミン、１−エチル−１，４−ブタンジアミン、１，２−ジメチル−１，４−ブタンジアミン、１，３−ジメチル−１，４−ブタンジアミン、１，４−ジメチル−１，４−ブタンジアミン、２，３−ジメチル−１，４−ブタンジアミン、２−メチル−１，５−ペンタンジアミン、３−メチル−１，５−ペンタンジアミン、２，２−ジメチル−１，６−ヘキサンジアミン、２，５−ジメチル−１，６−ヘキサンジアミン、２，４−ジメチル−１，６−ヘキサンジアミン、３，３−ジメチル−１，６−ヘキサンジアミン、２，２，４−トリメチル−１，６−ヘキサンジアミン、２，４，４−トリメチル−１，６−ヘキサンジアミン、２，４−ジエチル−１，６−ヘキサンジアミン、２−メチル−１，７−ヘプタンジアミン、２，２−ジメチル−１，７−ヘプタンジアミン、２，３−ジメチル−１，７−ヘプタンジアミン、２，４−ジメチル−１，７−ヘプタンジアミン、２，５−ジメチル−１，７−ヘプタンジアミン、２−メチル−１，８−オクタンジアミン、３−メチル−１，８−オクタンジアミン、４−メチル−１，８−オクタンジアミン、１，４−ジメチル−１，８−オクタンジアミン、２，４−ジメチル−１，８−オクタンジアミン、３，４−ジメチル−１，８−オクタンジアミン、４，５−ジメチル−１，８−オクタンジアミン、２，２−ジメチル−１，８−オクタンジアミン、３，３−ジメチル−１，８−オクタンジアミン、４，４−ジメチル−１，８−オクタンジアミン、５−メチル−１，９−ノナンジアミンなどの分岐状脂肪族ジアミンが挙げられ、これらからなる群から選択される少なくとも１種が好ましく、直鎖状脂肪族ジアミンから選択される少なくとも１種がより好ましい。
芳香環構造を有するジアミン以外のジアミンは１種類で使用してもよいし、２種類以上を適宜組み合わせて使用してもよい。Examples of diamines other than diamines having an aromatic ring structure include linear aliphatic diamines such as ethylenediamine, tetramethylenediamine, hexamethylenediamine, nonamethylenediamine, undecamethylenediamine, and dodecamethylenediamine; 1-butyl-1,2. -Etandiamine, 1,1-dimethyl-1,4-butanediamine, 1-ethyl-1,4-butanediamine, 1,2-dimethyl-1,4-butanediamine, 1,3-dimethyl-1,4 -Butanediamine, 1,4-dimethyl-1,4-butanediamine, 2,3-dimethyl-1,4-butanediamine, 2-methyl-1,5-pentanediamine, 3-methyl-1,5-pentane Diamine, 2,2-dimethyl-1,6-hexanediamine, 2,5-dimethyl-1,6-hexanediamine, 2,4-dimethyl-1,6-hexanediamine, 3,3-dimethyl-1,6 -Hexamethylenediamine, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, 2,4-diethyl-1,6-hexanediamine, 2-methyl -1,7-Hexamethylenediamine, 2,2-dimethyl-1,7-heptanediamine, 2,3-dimethyl-1,7-heptandiamine, 2,4-dimethyl-1,7-heptandiamine, 2,5 −Diamine-1,7-heptandiamine, 2-methyl-1,8-octanediamine, 3-methyl-1,8-octanediamine, 4-methyl-1,8-octanediamine, 1,4-dimethyl-1 , 8-octanediamine, 2,4-dimethyl-1,8-octanediamine, 3,4-dimethyl-1,8-octanediamine, 4,5-dimethyl-1,8-octanediamine, 2,2-dimethyl Branched aliphatic diamines such as -1,8-octanediamine, 3,3-dimethyl-1,8-octanediamine, 4,4-dimethyl-1,8-octanediamine, 5-methyl-1,9-nonandiamine At least one selected from the group consisting of these is preferable, and at least one selected from the linear aliphatic diamine is more preferable.
One type of diamine other than the diamine having an aromatic ring structure may be used, or two or more types may be appropriately combined and used.
芳香環構造を有するジカルボン酸以外のジカルボン酸としては、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、ウンデカンジオン酸、ドデカンジオン酸、トリデカンジオン酸、テトラデカンジオン酸、ペンタデカンジオン酸、ヘキサデカンジオン酸、オクタデカンジオン酸、エイコサンジオン酸などの直鎖状脂肪族ジカルボン酸；ジメチルマロン酸、３，３−ジメチルコハク酸、２，２−ジメチルグルタル酸、２−メチルアジピン酸、３−メチルアジピン酸、トリメチルアジピン酸、２−ブチルオクタジオン酸、２，３−ジブチルブタンジオン酸、８−エチルオクタデカンジオン酸、８，１３−ジメチルエイコサジオン酸、２−オクチルウンデカンジオン酸、２−ノニルデカンジオン酸などの分岐状脂肪族カルボン酸が挙げられ、これらからなる群から選択される少なくとも１種が好ましく、直鎖状脂肪族ジカルボン酸から選択される少なくとも１種がより好ましい。
芳香環構造を有するジカルボン酸以外のジカルボン酸は１種類で使用してもよいし、２種類以上を適宜組み合わせて使用してもよい。Examples of dicarboxylic acids other than dicarboxylic acids having an aromatic ring structure include adipic acid, pimelli acid, suberic acid, azelaic acid, sebacic acid, undecandic acid, dodecandioic acid, tridecandic acid, tetradecandonic acid, pentadecandic acid, Linear aliphatic dicarboxylic acids such as hexadecandionic acid, octadecandionic acid, eikosandionic acid; dimethylmalonic acid, 3,3-dimethylsuccinic acid, 2,2-dimethylglutaric acid, 2-methyladipic acid, 3- Methyladipic acid, trimethyladiponic acid, 2-butyloctadioic acid, 2,3-dibutylbutandioic acid, 8-ethyloctadecandioic acid, 8,13-dimethyleicosadioic acid, 2-octylundecandioic acid, 2- Branched aliphatic carboxylic acids such as nonyldecandionic acid are mentioned, and at least one selected from the group consisting of these is preferable, and at least one selected from the linear aliphatic dicarboxylic acid is more preferable.
One type of dicarboxylic acid other than the dicarboxylic acid having an aromatic ring structure may be used, or two or more types may be used in combination as appropriate.
（Ｂ−２）芳香環構造を有する単位
ポリアミド樹脂に含まれる（Ｂ−２）芳香環構造を有する単位は、ジアミン及びジカルボン酸の等モル塩又は等モル混合物に由来し、ジアミン及びジカルボン酸の少なくとも一方に芳香環構造を有する単位であり、例えば、ジカルボン酸及び芳香環構造を有するジアミンの等モル塩若しくは等モル混合物、又はジアミン及び芳香環構造を有するジカルボン酸の等モル塩若しくは等モル混合物を重合することで形成される。(B-2) Unit having an aromatic ring structure The unit having an aromatic ring structure contained in the polyamide resin (B-2) is derived from an isomorphic salt or an isomol mixture of a diamine and a dicarboxylic acid, and is derived from a diamine and a dicarboxylic acid. A unit having an aromatic ring structure on at least one of them, for example, an equimolar salt or an equimolar mixture of a dicarboxylic acid and a diamine having an aromatic ring structure, or an equimolar salt or an isomol mixture of a diamine and a dicarboxylic acid having an aromatic ring structure. Is formed by polymerizing.
芳香環構造を有するジアミンとしては、ｐ−フェニレンジアミン、ｍ−フェニレンジアミン、ｐ−キシリレンジアミン、ｍ−キシリレンジアミン、２，４−トリレンジアミン、２，６−トリレンジアミン、１，４−ジアミノナフタレン、１，８−ジアミノナフタレン、２，３−ジアミノナフタレン、２，６−ジアミノナフタレン、３，３’−ジアミノジフェニルメタン、３，４’−ジアミノジフェニルメタン、４，４’−ジアミノジフェニルメタン、４，４’−ジアミノ−３，３’−ジメチルジフェニルメタン、４，４’−ジアミノ−３，３’−ジエチルジフェニルメタン、４，４’−ジアミノ−３，３’，５，５’−テトラメチルジフェニルメタン、４，４’−ジアミノ−３，３’，５，５’−テトラエチルジフェニルメタン、４，４’−ジアミノ−３，３’−ジメチル−５，５’−ジエチルジフェニルメタン、２，２’−ビス（３−アミノフェニル）プロパン、２，２’−ビス（４−アミノフェニル）プロパン、２，２’−ビス（４−アミノ−３−メチルフェニル）プロパン、２，２’−ビス（４−アミノ−３−エチルフェニル）プロパン、２，２’−ビス（４−アミノ−３，５−ジメチルフェニル）プロパン、２，２’−ビス（４−アミノ−３，５−ジエチルフェニル）プロパン、２，２’−ビス（４−アミノ−３−メチル−５−エチルフェニル）プロパンなどの芳香族ジアミンが挙げられ、これらからなる群から選択される少なくとも１種が好ましい。 Examples of diamines having an aromatic ring structure include p-phenylenediamine, m-phenylenediamine, p-xylylene diamine, m-xylylene diamine, 2,4-tolylene diamine, 2,6-tolylene diamine, and 1,4. -Diaminonaphthalene, 1,8-diaminonaphthalene, 2,3-diaminonaphthalene, 2,6-diaminonaphthalene, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4 , 4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane, 4,4'-diamino-3,3', 5,5'-tetramethyldiphenylmethane, 4,4'-Diamino-3,3', 5,5'-tetraethyldiphenylmethane, 4,4'-diamino-3,3'-dimethyl-5,5'-diethyldiphenylmethane, 2,2'-bis (3) -Aminophenyl) propane, 2,2'-bis (4-aminophenyl) propane, 2,2'-bis (4-amino-3-methylphenyl) propane, 2,2'-bis (4-amino-3) -Ethylphenyl) propane, 2,2'-bis (4-amino-3,5-dimethylphenyl) propane, 2,2'-bis (4-amino-3,5-diethylphenyl) propane, 2,2' Examples include aromatic diamines such as −bis (4-amino-3-methyl-5-ethylphenyl) propane, and at least one selected from the group consisting of these is preferable.
芳香環構造を有するジアミンは１種類で使用してもよいし、２種類以上を適宜組み合わせて使用してもよい。 One type of diamine having an aromatic ring structure may be used, or two or more types may be appropriately combined and used.
芳香環構造を有するジカルボン酸としては、イソフタル酸、テレフタル酸、１，４−ナフタレンジカルボン酸、１，８−ナフタレンジカルボン酸、２，６−ナフタレンジカルボン酸、２，７−ナフタレンジカルボン酸、４，４’−ビフェニルジカルボン酸、ジフェニルメタン−２，４−ジカルボン酸、ジフェニルメタン−３，３’−ジカルボン酸、ジフェニルメタン−３，４’−ジカルボン酸、ジフェニルメタン−４，４’−ジカルボン酸などの芳香族ジカルボン酸が挙げられ、イソフタル酸、テレフタル酸がより好ましい。 Examples of the dicarboxylic acid having an aromatic ring structure include isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4, Aromatic dicarboxylic acids such as 4'-biphenyldicarboxylic acid, diphenylmethane-2,4-dicarboxylic acid, diphenylmethane-3,3'-dicarboxylic acid, diphenylmethane-3,4'-dicarboxylic acid, diphenylmethane-4,4'-dicarboxylic acid Acids are mentioned, and isophthalic acid and terephthalic acid are more preferable.
芳香環構造を有するジカルボン酸は１種類で使用してもよいし、２種類以上を適宜組み合わせて使用してもよい。 One type of dicarboxylic acid having an aromatic ring structure may be used, or two or more types may be used in combination as appropriate.
ポリアミド樹脂の全単位中に含まれる（Ｂ）ジアミン及びジカルボン酸の等モル塩に由来する単位の総含有率は、例えば２〜５０重量％であり、好ましくは１０〜４５重量％であり、より好ましくは１２〜４０重量％、特に好ましくは３０〜４０重量％である。ジアミン及びジカルボン酸の等モル塩に由来する単位の総含有率が上記下限以上であると延伸性及び熱収縮性がより向上する傾向がある。上記上限以下であると結晶性及びフィルム物性がより向上し、工業的に有利な延伸フィルムを得ることがより容易になる傾向がある。
ポリアミド樹脂の全単位中における（Ａ）ラクタム及び／又はアミノカルボン酸に由来する単位の含有率と（Ｂ）ジアミン及びジカルボン酸の等モル塩に由来する単位の総含有率との合計は、実用的な物性の観点から、９０〜１００重量％となることが好ましく、９５〜１００重量％となることがより好ましく、９７〜１００重量％となることがさらに好ましい。The total content of the units derived from the equimolar salts of (B) diamine and dicarboxylic acid contained in all the units of the polyamide resin is, for example, 2 to 50% by weight, preferably 10 to 45% by weight, and more. It is preferably 12 to 40% by weight, particularly preferably 30 to 40% by weight. When the total content of units derived from equimolar salts of diamine and dicarboxylic acid is at least the above lower limit, stretchability and heat shrinkage tend to be further improved. When it is not more than the above upper limit, the crystallinity and the physical properties of the film are further improved, and it tends to be easier to obtain an industrially advantageous stretched film.
The sum of the content of the unit derived from (A) lactam and / or aminocarboxylic acid and the total content of the unit derived from the equimolar salt of diamine and dicarboxylic acid in all the units of the polyamide resin is practical. From the viewpoint of physical properties, it is preferably 90 to 100% by weight, more preferably 95 to 100% by weight, and even more preferably 97 to 100% by weight.
（Ｂ）ジアミン及びジカルボン酸の等モル塩に由来する単位の総含有率が、２〜５０重量％の場合、ポリアミド樹脂の全単位中に含まれる（Ｂ−１）芳香環構造を有さない単位の含有率は、１〜４９.９重量％であり、好ましくは１〜４９．５重量％であり、より好ましくは１〜４９重量％である。芳香環構造を有さない単位の含有率が、上記下限以上であると機械的強度など実用的な物性がより向上する傾向がある。上記上限以下であると延伸性及び熱収縮性がより向上する傾向がある。 (B) When the total content of the units derived from the equimolar salts of diamine and dicarboxylic acid is 2 to 50% by weight, it does not have the (B-1) aromatic ring structure contained in all the units of the polyamide resin. The content of the unit is 1 to 49.9% by weight, preferably 1 to 49.5% by weight, and more preferably 1 to 49% by weight. When the content of the unit having no aromatic ring structure is at least the above lower limit, practical physical properties such as mechanical strength tend to be further improved. When it is not more than the above upper limit, the stretchability and the heat shrinkage tend to be further improved.
（Ｂ）ジアミン及びジカルボン酸の等モル塩に由来する単位の総含有率が、２〜５０重量％の場合、ポリアミド樹脂の全単位中に含まれる（Ｂ−２）芳香環構造を有する単位の含有率は、例えば０．１〜４９重量％であり、好ましくは０．５〜４９重量％であり、より好ましくは１〜４９重量％であり、さらに好ましくは１．５〜２０重量％である。芳香環構造を有する単位の含有率が、上記下限以上であると延伸性及び熱収縮性がより向上する傾向がある。上記上限以下であると機械的強度など実用的な物性がより向上する傾向がある。 (B) When the total content of units derived from isomorphic salts of diamine and dicarboxylic acid is 2 to 50% by weight, the unit having an aromatic ring structure (B-2) contained in all the units of the polyamide resin. The content is, for example, 0.1 to 49% by weight, preferably 0.5 to 49% by weight, more preferably 1 to 49% by weight, still more preferably 1.5 to 20% by weight. .. When the content of the unit having an aromatic ring structure is not more than the above lower limit, the stretchability and the heat shrinkage tend to be further improved. If it is less than the above upper limit, practical physical properties such as mechanical strength tend to be further improved.
（Ｂ−２）芳香環構造を有する単位の含有率は、次のようにして求められる。
ポリアミド樹脂に含まれる芳香環構造を有する単位がジアミン単位のみの場合、（Ｂ−２）芳香環構造を有する単位の割合は、当該ジアミン単位の重量と等モルの芳香環構造を有しないジカルボン酸単位の重量との和（重量％）である。同様に、ポリアミド樹脂に含まれる芳香環構造を有する単位がジカルボン酸単位のみの場合、（Ｂ−２）芳香環構造を有する単位の割合は、当該ジカルボン酸単位の重量と等モルの芳香環構造を有しないジアミン単位の重量との和（重量％）である。ポリアミド樹脂に含まれる芳香環構造を有する単位がジアミン単位とジカルボン酸単位の両方である場合、（Ｂ−２）芳香環構造を有する単位の割合は、当該ジアミン単位の重量と当該ジカルボン酸単位の重量の等モルである部分の重量の和（重量％）である。ポリアミド樹脂に含まれる芳香環構造を有する単位がジアミン単位とジカルボン酸単位の両方である場合で、当該ジアミン単位と当該ジカルボン酸単位が等モルでない場合、（Ｂ−２）芳香環構造を有する単位の割合は、両方の等モルである部分の重量の和（重量％）に、残余の芳香環構造を有する単位の重量とこれと等モルの芳香環構造を有しない単位の重量との和（重量％）を加えたものである。 (B-2) The content of the unit having an aromatic ring structure is determined as follows.
When the unit having an aromatic ring structure contained in the polyamide resin is only a diamine unit, (B-2) the proportion of the unit having an aromatic ring structure is a dicarboxylic acid having no aromatic ring structure equal to the weight of the diamine unit. It is the sum (% by weight) of the weight of the unit. Similarly, when the unit having an aromatic ring structure contained in the polyamide resin is only a dicarboxylic acid unit, (B-2) the ratio of the unit having an aromatic ring structure is equal to the weight of the dicarboxylic acid unit. It is the sum (% by weight) with the weight of the diamine unit having no. When the unit having an aromatic ring structure contained in the polyamide resin is both a diamine unit and a dicarboxylic acid unit, (B-2) the ratio of the unit having an aromatic ring structure is the weight of the diamine unit and the dicarboxylic acid unit. It is the sum of the weights (% by weight) of the parts that are equimolar of the weight. When the unit having an aromatic ring structure contained in the polyamide resin is both a diamine unit and a dicarboxylic acid unit, and the diamine unit and the dicarboxylic acid unit are not equimolar, (B-2) a unit having an aromatic ring structure. The ratio of is the sum of the weights of both equimolar portions (% by weight), the weight of the unit having the residual aromatic ring structure, and the weight of the unit having no equimolar aromatic ring structure (weight%). Weight%) is added.
（Ｂ）ジアミン及びジカルボン酸の等モル塩に由来する単位の総含有率が、１０〜４５重量％の場合、ポリアミド樹脂の全単位中に含まれる（Ｂ−１）芳香環構造を有さない単位の含有率は、１〜４４．９重量％であり、好ましくは１〜４４．５重量％であり、より好ましくは１〜４４重量％である。芳香環構造を有さない単位の含有率が、上記下限以上であると機械的強度など実用的な物性がより向上する傾向がある。上記上限以下であると延伸性及び熱収縮性がより向上する傾向がある。 (B) When the total content of the units derived from the equimolar salts of diamine and dicarboxylic acid is 10 to 45% by weight, it does not have the (B-1) aromatic ring structure contained in all the units of the polyamide resin. The content of the unit is 1 to 44.9% by weight, preferably 1 to 44.5% by weight, and more preferably 1 to 44% by weight. When the content of the unit having no aromatic ring structure is at least the above lower limit, practical physical properties such as mechanical strength tend to be further improved. When it is not more than the above upper limit, the stretchability and the heat shrinkage tend to be further improved.
（Ｂ）ジアミン及びジカルボン酸の等モル塩に由来する単位の総含有率が、１０〜４５重量％の場合、ポリアミド樹脂の全単位中に含まれる（Ｂ−２）芳香環構造を有する単位の含有率は、例えば０．１〜４４重量％であり、好ましくは０．５〜４４重量％であり、より好ましくは１〜４４重量％である。芳香環構造を有する単位の含有率が、上記下限以上であると延伸性及び熱収縮性がより向上する傾向がある。上記上限以下であると機械的強度など実用的な物性がより向上する傾向がある。 (B) When the total content of units derived from isomorphic salts of diamine and dicarboxylic acid is 10 to 45% by weight, the unit having an aromatic ring structure (B-2) contained in all the units of the polyamide resin. The content is, for example, 0.1 to 44% by weight, preferably 0.5 to 44% by weight, and more preferably 1 to 44% by weight. When the content of the unit having an aromatic ring structure is not more than the above lower limit, the stretchability and the heat shrinkage tend to be further improved. If it is less than the above upper limit, practical physical properties such as mechanical strength tend to be further improved.
（Ｂ）ジアミン及びジカルボン酸の等モル塩に由来する単位の総含有率が、１２〜４０重量％の場合、ポリアミド樹脂の全単位中に含まれる（Ｂ−１）芳香環構造を有さない単位の含有率は、１〜３９．９重量％であり、好ましくは１〜３９．５重量％であり、より好ましくは１〜３９重量％である。芳香環構造を有さない単位の含有率が、上記下限以上であると機械的強度など実用的な物性がより向上する傾向がある。上記上限以下であると延伸性及び熱収縮性がより向上する傾向がある。 (B) When the total content of the units derived from the equimolar salts of diamine and dicarboxylic acid is 12 to 40% by weight, it does not have the (B-1) aromatic ring structure contained in all the units of the polyamide resin. The content of the unit is 1 to 39.9% by weight, preferably 1 to 9.5% by weight, and more preferably 1 to 39% by weight. When the content of the unit having no aromatic ring structure is at least the above lower limit, practical physical properties such as mechanical strength tend to be further improved. When it is not more than the above upper limit, the stretchability and the heat shrinkage tend to be further improved.
（Ｂ）ジアミン及びジカルボン酸の等モル塩に由来する単位の総含有率が、１２〜４０重量％の場合、ポリアミド樹脂の全単位中に含まれる（Ｂ−２）芳香環構造を有する単位の含有率は、例えば０．１〜３９重量％であり、好ましくは０．５〜３９重量％であり、より好ましくは１〜３９重量％である。芳香環構造を有する単位の含有率が、上記下限以上であると延伸性及び熱収縮性がより向上する傾向がある。上記上限以下であると機械的強度など実用的な物性がより向上する傾向がある。 (B) When the total content of the unit derived from the equimolar salt of diamine and dicarboxylic acid is 12 to 40% by weight, the unit having an aromatic ring structure (B-2) contained in all the units of the polyamide resin. The content is, for example, 0.1 to 39% by weight, preferably 0.5 to 39% by weight, and more preferably 1 to 39% by weight. When the content of the unit having an aromatic ring structure is not more than the above lower limit, the stretchability and the heat shrinkage tend to be further improved. If it is less than the above upper limit, practical physical properties such as mechanical strength tend to be further improved.
（Ａ）ラクタム及び／又はアミノカルボン酸に由来する単位及び（Ｂ−１）芳香環構造を有さない単位の総含有量に対する、（Ｂ−２）芳香環構造を有する単位の含有率［（Ｂ−２）／｛（Ａ）＋（Ｂ−１）｝×１００]は、例えば、０．１〜９７重量％であり、好ましくは０．５〜９７重量％であり、より好ましくは１〜９７重量％である。芳香環構造を有する単位の百分率が、上記下限以上であると延伸性及び熱収縮性がより向上する傾向がある。上記上限以下であると機械的強度など実用的な物性がより向上する傾向がある。 Ratio of (B-2) units having an aromatic ring structure to the total content of (A) units derived from lactam and / or aminocarboxylic acid and (B-1) units not having an aromatic ring structure [( B-2) / {(A) + (B-1)} × 100] is, for example, 0.1 to 97% by weight, preferably 0.5 to 97% by weight, and more preferably 1 to 1. It is 97% by weight. When the percentage of the unit having an aromatic ring structure is at least the above lower limit, the stretchability and heat shrinkage tend to be further improved. If it is less than the above upper limit, practical physical properties such as mechanical strength tend to be further improved.
また、（Ｂ）ジアミン及びジカルボン酸の等モル塩に由来する単位の総含有率が、３０〜４０重量％の場合、ポリアミド樹脂の全単位中に含まれる（Ｂ−１）芳香環構造を有さない単位の含有率は２５〜３９重量％が好ましく、ポリアミド樹脂の全単位中に含まれる（Ｂ−２）芳香環構造を有する単位の含有率は１〜１５重量％が好ましい。
即ち、本発明のポリアミド樹脂は、特に、
ポリアミド樹脂の全単位中に、
（Ａ）ラクタム及び／又はアミノカルボン酸に由来する単位を６０〜７０重量％及び（Ｂ）ジアミン及びジカルボン酸の等モル塩に由来する単位を３０〜４０重量％含み、かつ、（Ｂ−１）芳香環構造を有さない単位を２５〜３９重量％及び前記（Ｂ−２）芳香環構造を有する単位を１〜１５重量％含むポリアミド樹脂が好ましい。このような組成を有するポリアミド樹脂は、特に、熱収縮性、耐ピンホール性等に優れるフィルムを提供することができるため、好ましい。Further, when the total content of the units derived from the equimolar salts of (B) diamine and dicarboxylic acid is 30 to 40% by weight, the (B-1) aromatic ring structure contained in all the units of the polyamide resin is present. The content of the non-units is preferably 25 to 39% by weight, and the content of the unit having the (B-2) aromatic ring structure contained in all the units of the polyamide resin is preferably 1 to 15% by weight.
That is, the polyamide resin of the present invention is particularly
In all units of polyamide resin,
It contains 60 to 70% by weight of units derived from (A) lactam and / or aminocarboxylic acid and 30 to 40% by weight of units derived from (B) equimolar salts of diamine and dicarboxylic acid, and (B-1). ) A polyamide resin containing 25 to 39% by weight of a unit having no aromatic ring structure and 1 to 15% by weight of a unit having the (B-2) aromatic ring structure is preferable. A polyamide resin having such a composition is particularly preferable because it can provide a film having excellent heat shrinkage and pinhole resistance.
さらには、前記（Ａ）ラクタム及び／又はアミノカルボン酸に由来する単位は、（Ａ）ε−カプロラクタム及び／又は６−アミノカプロン酸に由来する単位が好ましい。前記（Ｂ−１）芳香環構造を有さない単位は、ヘキサメチレンジアミン及びアジピン酸の等モル塩に由来する単位が好ましい。また、前記（Ｂ−２）芳香環構造を有する単位は、ヘキサメチレンジアミンと、イソフタル酸及び／またはテレフタル酸の等モル塩に由来する単位が好ましい。 Furthermore, the unit derived from (A) lactam and / or aminocarboxylic acid is preferably a unit derived from (A) ε-caprolactam and / or 6-aminocaproic acid. The unit having no aromatic ring structure (B-1) is preferably a unit derived from an equimolar salt of hexamethylenediamine and adipic acid. The unit having the aromatic ring structure (B-2) is preferably a unit derived from hexamethylenediamine and an isophthalic acid and / or terephthalic acid isomorphic salt.
ポリアミド樹脂の製造は回分式でも、連続式でも実施でき、バッチ式反応釜、一槽式又は多槽式の連続反応装置、管状連続反応装置、一軸型混練押出機、二軸型混練押出機などの混練反応押出機など、公知のポリアミド製造装置を用いることができる。重合方法としては溶融重合、溶液重合や固相重合などの公知の方法を用いることができる。これらの重合方法は単独で、あるいは適宜、組み合わせて用いることができる。 Polyamide resin can be manufactured by batch type or continuous type, such as batch type reaction kettle, single-tank or multi-tank continuous reaction device, tubular continuous reaction device, uniaxial kneading extruder, twin-screw kneading extruder, etc. A known polyamide production apparatus such as a kneading reaction extruder of the above can be used. As the polymerization method, known methods such as melt polymerization, solution polymerization and solid phase polymerization can be used. These polymerization methods can be used alone or in combination as appropriate.
ポリアミド樹脂の製造方法は、例えば、（Ａ）ラクタム及び／又はアミノカルボン酸と、（Ｂ）ジアミン及びジカルボン酸の等モル塩と、水とを耐圧容器に仕込み、密封状態で２００〜３５０℃の温度範囲で、加圧下において重縮合した後、圧力を下げて、大気圧下又は減圧下で２００〜３５０℃の温度範囲で重縮合反応を続け、高分子量化することにより、目的のポリアミド樹脂を製造することができる。この際（Ｂ）ジアミン及びジカルボン酸の等モル塩は、ほぼ等モルのジアミンとジカルボン酸を水、アルコール等と混合して、溶解させた後、ナイロン塩を生成させ、そのままの溶液状態、濃縮した溶液状態、又は、再結晶により得られる固体状のナイロン塩として仕込んでもよい。また、ジアミン及びジカルボン酸の等モル塩の代わりに、ほぼ等モルのジアミン及びジカルボン酸をそのまま耐圧容器に仕込んでもよい。例えば（Ｂ−１）芳香環構造を有しない単位を構成するジアミンとジカルボン酸とをこれらの等モル塩として仕込み、（Ｂ−２）芳香環構造を有する単位を構成するジアミンとジカルボン酸とをそのまま耐圧容器仕込んでもよい。なお、ほぼ等モルのジアミン及びジカルボン酸の等モル混合物は実質的に等モル塩に相当する。
ポリアミド樹脂の製造方法で使用する水は、酸素を除去したイオン交換水、蒸留水等を使用することが望ましく、その使用量はポリアミド樹脂を構成する原料１００重量部に対して、例えば１〜１５０重量部である。As a method for producing a polyamide resin, for example, (A) lactam and / or aminocarboxylic acid, (B) equimolar salts of diamine and dicarboxylic acid, and water are charged in a pressure-resistant container and sealed at 200 to 350 ° C. After polycondensation under pressure in the temperature range, the pressure is lowered, and the polycondensation reaction is continued in the temperature range of 200 to 350 ° C. under atmospheric pressure or reduced pressure to increase the molecular weight of the target polyamide resin. Can be manufactured. At this time, (B) the equimolar salt of diamine and dicarboxylic acid is prepared by mixing approximately equimolar diamine and dicarboxylic acid with water, alcohol, etc. to dissolve them, and then producing a nylon salt, and concentrating the solution as it is. It may be charged in a solution state or as a solid nylon salt obtained by recrystallization. Further, instead of the equimolar salt of diamine and dicarboxylic acid, substantially equimolar diamine and dicarboxylic acid may be charged in the pressure-resistant container as they are. For example, (B-1) a diamine and a dicarboxylic acid constituting a unit having an aromatic ring structure are charged as these equimolar salts, and (B-2) a diamine and a dicarboxylic acid constituting a unit having an aromatic ring structure are charged. The pressure-resistant container may be charged as it is. An equimolar mixture of approximately equimolar diamine and dicarboxylic acid substantially corresponds to an equimolar salt.
As the water used in the method for producing the polyamide resin, it is desirable to use ion-exchanged water from which oxygen has been removed, distilled water, etc., and the amount used is, for example, 1 to 150 with respect to 100 parts by weight of the raw material constituting the polyamide resin. It is a part by weight.
ポリアミド樹脂を製造する際、必要ならば、重合促進や酸化防止のため、リン酸、亜リン酸、次亜リン酸、ポリリン酸及びこれらのアルカリ金属塩などのリン系化合物を添加することができる。これらリン系化合物の添加量は、通常、得ようとするポリアミド樹脂に対して５０〜３，０００ｐｐｍである。また、分子量調節や成形加工時の溶融粘度安定化のため、ラウリルアミン、ステアリルアミンなどのモノアミン；ヘキサメチレンジアミン、メタキシリレンジアミンなどのジアミン；酢酸、ステアリン酸、安息香酸などのモノカルボン酸；アジピン酸、イソフタル酸、テレフタル酸などのジカルボン酸からなる群から選択される少なくとも１種の分子量調節剤を添加してポリアミド樹脂を製造してもよい。これらの分子量調節剤は１種類を添加してもよいし、２種類以上を適宜組み合わせて添加してもよい。分子量調節剤を使用する場合、その使用量は、分子量調節剤の反応性や重合条件により異なるが、最終的に得ようとするポリアミドの相対粘度が、１．５〜５．０の範囲になるように適宜決められる。 When producing a polyamide resin, if necessary, phosphorus-based compounds such as phosphoric acid, phosphite, hypophosphoric acid, polyphosphoric acid and alkali metal salts thereof can be added to promote polymerization and prevent oxidation. .. The amount of these phosphorus compounds added is usually 50 to 3,000 ppm with respect to the polyamide resin to be obtained. In addition, for adjusting the molecular weight and stabilizing the melt viscosity during molding, monoamines such as laurylamine and stearylamine; diamines such as hexamethylenediamine and m-xylylenediamine; monocarboxylic acids such as acetic acid, stearic acid and benzoic acid; A polyamide resin may be produced by adding at least one molecular weight modifier selected from the group consisting of dicarboxylic acids such as adipic acid, isophthalic acid, and terephthalic acid. One type of these molecular weight modifiers may be added, or two or more types may be added in appropriate combinations. When a molecular weight modifier is used, the amount used varies depending on the reactivity of the molecular weight modifier and the polymerization conditions, but the relative viscosity of the polyamide to be finally obtained is in the range of 1.5 to 5.0. It is decided as appropriate.
ポリアミド樹脂の分子量は、ＪＩＳ Ｋ６８１０に記載の方法で測定される相対粘度（ηr）が１．５〜５．０の範囲、好ましくは２．０〜４．５のものである。なお、ポリアミド樹脂の末端基の種類及びその濃度や分子量分布には特別の制約は無い。 The molecular weight of the polyamide resin is such that the relative viscosity (ηr) measured by the method described in JIS K6810 is in the range of 1.5 to 5.0, preferably 2.0 to 4.5. There are no particular restrictions on the type of terminal group of the polyamide resin, its concentration, or the molecular weight distribution.
高分子量化されたポリアミド樹脂は、通常、溶融状態で反応容器から抜き出され、水などで冷却された後、ペレット状に加工される。ナイロン６など未反応モノマーを多く含有するポリアミド樹脂が主成分のペレットの場合、さらに、熱水洗浄などにより未反応モノマーなどを除去した後、フィルムの製造等に使用することが好ましい。 The high molecular weight polyamide resin is usually extracted from the reaction vessel in a molten state, cooled with water or the like, and then processed into pellets. When the pellet is mainly composed of a polyamide resin containing a large amount of unreacted monomers such as nylon 6, it is preferable to use it for film production or the like after removing the unreacted monomers by washing with hot water or the like.
ポリアミド樹脂はフィルム製造に好適に用いることができる。すなわち、本発明はポリアミド樹脂のフィルムの製造における使用を包含する。
ポリアミド樹脂からのフィルムの製造方法には、公知のフィルム製造方法、例えば、溶融押出機を用いたＴダイ法、インフレーション法、チューブラー法、溶剤キャスト法、熱プレス法などの製造方法を適用することができる。溶融押出機を用いた方法でのポリアミドの溶融温度は、例えば、使用するポリアミドの融点以上３２０℃以下である。The polyamide resin can be suitably used for film production. That is, the present invention includes the use of polyamide resin in the production of films.
As a method for producing a film from a polyamide resin, a known film production method, for example, a T-die method using a melt extruder, an inflation method, a tubular method, a solvent casting method, a hot press method, or the like is applied. be able to. The melting temperature of the polyamide by the method using a melt extruder is, for example, not more than the melting point of the polyamide used and not more than 320 ° C.
ポリアミド樹脂からなるフィルムは延伸フィルムであってもよい。すなわち、本発明はポリアミド樹脂の延伸フィルムの製造における使用を包含する。延伸フィルムは例えば、上記フィルムを延伸することで製造することができる。 The film made of a polyamide resin may be a stretched film. That is, the present invention includes the use in the production of stretched films of polyamide resins. The stretched film can be produced, for example, by stretching the above film.
延伸については、少なくとも一軸方向であればよく、フィルムの使用用途に合わせて適宜、一軸延伸法、同時二軸延伸法、逐次二軸延伸法など選択することができる。中でも逐次二軸延伸法でフィルムを製造する場合、ポリアミド樹脂に必要に応じてステアリン酸カルシウム、ビスアミド化合物、シリカ、タルクなどの滑剤、スリップ剤、核剤などを添加して樹脂組成物を得た後、Ｔダイを備えた押出機で樹脂組成物を溶融押出して、未延伸フィルムを成形する。未延伸フィルムは引き続き、連続した工程で延伸してもよいし、一旦巻き取ってから延伸してもよい。 The stretching may be at least in the uniaxial direction, and a uniaxial stretching method, a simultaneous biaxial stretching method, a sequential biaxial stretching method, or the like can be appropriately selected according to the intended use of the film. Above all, when the film is produced by the sequential biaxial stretching method, after adding calcium stearate, bisamide compound, lubricant such as silica and talc, slip agent, nucleating agent, etc. to the polyamide resin as necessary to obtain a resin composition. , The resin composition is melt-extruded with an extruder equipped with a T-die to form an unstretched film. The unstretched film may be continuously stretched in a continuous step, or may be wound once and then stretched.
延伸は使用するポリアミド樹脂のガラス転移温度（以下、Ｔｇと記載する）以上の温度で実施される。逐次二軸延伸の一段目の延伸（一次延伸）はフィルムの押出方向へ、Ｔｇ以上（Ｔｇ＋５０）℃以下の温度範囲で延伸倍率２〜５倍、好ましくは２．５〜４倍に延伸され、次いでフィルムの押出方向と直角の方向に行う二段目の延伸（二次延伸）は、一次延伸と同じ温度かやや高い温度で、延伸倍率２〜５倍、好ましくは２．５〜４倍に延伸される。その後、１５０℃以上の温度で熱固定する工程を経て、逐次二軸延伸フィルムは製造される。 Stretching is carried out at a temperature equal to or higher than the glass transition temperature (hereinafter referred to as Tg) of the polyamide resin used. The first-stage stretching (primary stretching) of the sequential biaxial stretching is carried out in the extrusion direction of the film in a temperature range of Tg or more (Tg + 50) ° C. and a stretching ratio of 2 to 5 times, preferably 2.5 to 4 times. Next, the second-stage stretching (secondary stretching) performed in the direction perpendicular to the extrusion direction of the film is performed at the same temperature as the primary stretching or slightly higher temperature, and the stretching ratio is 2 to 5 times, preferably 2.5 to 4 times. It is stretched. Then, the biaxially stretched film is manufactured sequentially through a step of heat-fixing at a temperature of 150 ° C. or higher.
本発明のポリアミド樹脂からなる延伸フィルムは、好ましくは２０〜６０％、より好ましくは２２〜６０％、さらに好ましくは２５〜６０％の熱水収縮率を有する。本発明のポリアミド樹脂からなる延伸フィルムは、高い熱水収縮率を生かして、包装用材料、特に、食品包装用材料として好適に使用できる。 The stretched film made of the polyamide resin of the present invention preferably has a hot water shrinkage rate of 20 to 60%, more preferably 22 to 60%, still more preferably 25 to 60%. The stretched film made of the polyamide resin of the present invention can be suitably used as a packaging material, particularly a food packaging material, by taking advantage of its high hot water shrinkage rate.
ポリアミド樹脂には、本発明の効果が阻害されない範囲で、熱安定剤、紫外線吸収剤、光安定剤、酸化防止剤、帯電防止剤、粘着性付与剤、シール性改良剤、防曇剤、離型剤、耐衝撃性改良剤、可塑剤、顔料、染料、香料、補強材などを添加することができる。 Polyamide resins include heat stabilizers, ultraviolet absorbers, light stabilizers, antioxidants, antistatic agents, tackifiers, sealability improvers, antifogging agents, and release agents, as long as the effects of the present invention are not impaired. Molds, impact resistance improvers, plasticizers, pigments, dyes, fragrances, reinforcing materials and the like can be added.
以下、実施例及び比較例により本発明を具体的に説明するが、本発明はその要旨を超えない限り、以下の実施例等により何等の限定を受けるものではない。尚、実施例及び比較例中に示した測定値は以下の方法で測定した。 Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not subject to any limitation by the following Examples and the like as long as the gist of the present invention is not exceeded. The measured values shown in Examples and Comparative Examples were measured by the following methods.
（１）ポリアミド樹脂のηｒ（相対粘度）の測定
ＪＩＳ Ｋ６８１０に準じ、９６重量％の濃硫酸を溶媒として、１重量／容量％のポリアミド濃度で、ウベローデ粘度計を用い、２５℃の温度で測定した。(1) Measurement of ηr (relative viscosity) of polyamide resin According to JIS K6810, measurement was performed at a temperature of 25 ° C. using a Ubbelohde viscous meter at a polyamide concentration of 1% by weight / volume% using 96% by weight of concentrated sulfuric acid as a solvent. did.
（２）熱水収縮率の測定
フィルムに記した標線間距離（＝Ｌ）を測定後、無緊張状態で６０℃又は９０℃の熱水中に１分間放置し、標線間の縮み量（＝ΔＬ）を測定し、収縮率（％）＝ΔＬ／Ｌ×１００として算出した。(2) Measurement of hot water shrinkage rate After measuring the distance between marked lines (= L) marked on the film, leave it in hot water at 60 ° C or 90 ° C for 1 minute in a non-tensioned state, and the amount of shrinkage between marked lines. (= ΔL) was measured and calculated as shrinkage rate (%) = ΔL / L × 100.
（３）突刺し強度
ＪＡＳ Ｐ１０１９に準じて、ＴＯＹＯ ＢＡＬＤＷＩＮ社製テンシロンＵＴＭ−III−２００を使用して、突刺速度５０ｍｍ／ｍｉｎ、２３℃、５０％ＲＨの条件下で測定した。 (3) Puncture strength According to JAS P1019, measurement was performed using Tensilon UTM-III-200 manufactured by TOYO BALDWIN under the conditions of puncture speed of 50 mm / min, 23 ° C., and 50% RH.
（４）ゲルボフレックス（耐ピンホール性）
理学工業（株）製恒温槽付ゲルボフレックステスターにより、ＭＩＬ−Ｂ−１３１Ｃに従い、２３℃下で１０００回の屈曲テストを未延伸ポリアミドフィルムＡに対して行った後、そのフィルムを記録紙上に設置後、墨汁を塗り、記録紙上に記録された黒点の数を測定した。(4) Gelboflex (pinhole resistance)
Using a gelboflex tester with a constant temperature bath manufactured by Rigaku Kogyo Co., Ltd., a bending test was performed 1000 times at 23 ° C. on the unstretched polyamide film A according to MIL-B-131C, and then the film was placed on a recording paper. After installation, ink was applied and the number of black spots recorded on the recording paper was measured.
（５）酸素透過度
ＡＳＴＭ Ｄ−３９８５−８１に準じて、モダンコントロール社製ＭＯＣＯＮ−ＯＸ−ＴＲＡＮ２／２０を使用して、２３℃、０％ＲＨの条件下で、５０μｍの未延伸フィルムの酸素透過係数を測定した。(5) Oxygen permeability According to ASTM D-3985-81, using MOCON-OX-TRAN2 / 20 manufactured by Modern Control Co., Ltd., oxygen in a 50 μm unstretched film under the conditions of 23 ° C. and 0% RH. The transmission coefficient was measured.
（実施例１）
攪拌機、温度計、トルクメーター、圧力計、窒素ガス導入口、放圧口、圧力調整装置及びポリマー取り出し口を備えた５リットルの圧力容器にε−カプロラクタム９１０．０１ｇ（７０重量％）、ヘキサメチレンジアミン（ＨＭＤ）とアジピン酸（ＡＡ）との等モル塩５０％水溶液５２０．００ｇ（ＨＭＤとＡＡとの等モル塩：２０重量％）、ＨＭＤ８０％水溶液６７．１９ｇ、イソフタル酸（ＩＰＡ：東京化成工業株式会社製）７６．５１ｇ（ＨＭＤとＩＰＡのモル比が１：１）（１０重量％）、次亜リン酸ナトリウム０．０６５ｇを仕込み、窒素加圧と放圧を数回繰り返し、圧力容器内を窒素置換してから徐々に加熱を行った。撹拌は速度５０ｒｐｍで行った。１．５時間かけて室温から２４０℃まで昇温し、２４０℃で２時間重合させた後、ゲージ圧力０ＭＰａまで放圧し、引き続き、窒素ガスを２６０ｍｌ／分で流しながら、２４０℃で６．０時間重合を行い、ポリアミドを得た。重合終了後、撹拌を停止し、ポリマー取り出し口から溶融状態の無色透明のポリアミドを紐状に抜き出し、水冷した後、ペレタイズしてペレットを得た。このペレットを熱水中、６時間撹拌洗浄し、未反応モノマーを除去した後、１１０℃で７２時間真空乾燥した。得られたポリアミドのηrは３．５であった。
得られたポリアミド約２ｇを使用して２６０℃の条件でプレス成型機を用いて、厚さ１００μｍの未延伸フィルムを作製した。
この未延伸フィルムから切り出した縦９０ｍｍ、横１０ｍｍの試料に標線（５０ｍｍ間隔）を引いて引張試験機（株式会社オリエンテック製テンシロンＲＴＡ−１０ＫＮ）に取り付け、８０℃の雰囲気温度（延伸時温度）で約１分間予熱した後、同温度下、変形速度１５０ｍｍ／分でフィルムの縦方向に２．７倍に延伸した。この延伸フィルムを２３℃、５０％ＲＨの雰囲気中に一昼夜放置した後、９０℃の熱水中に１分間放置して熱水収縮率を測定したところ、３２％であった。その結果を表１に示す。(Example 1)
Ε-caprolactam 910.01 g (70% by weight), hexamethylene in a 5 liter pressure vessel equipped with a stirrer, thermometer, torque meter, pressure gauge, nitrogen gas inlet, pressure release port, pressure regulator and polymer outlet. 520.00 g of 50% equimolar salt aqueous solution of diamine (HMD) and adipic acid (AA) (isomolar salt of HMD and AA: 20% by weight), 67.19 g of HMD 80% aqueous solution, isophthalic acid (IPA: Tokyo Kasei) (Manufactured by Kogyo Co., Ltd.) 76.51 g (molar ratio of HMD to IPA 1: 1) (10 wt%), 0.065 g of sodium hypophosphate was charged, nitrogen pressurization and release pressure were repeated several times, and a pressure vessel was used. After replacing the inside with nitrogen, heating was gradually performed. Stirring was performed at a speed of 50 rpm. The temperature was raised from room temperature to 240 ° C. over 1.5 hours, polymerized at 240 ° C. for 2 hours, then released to a gauge pressure of 0 MPa, and subsequently, while flowing nitrogen gas at 260 ml / min, 6.0 at 240 ° C. Polyamide was obtained by time polymerization. After completion of the polymerization, stirring was stopped, and the colorless and transparent polyamide in a molten state was extracted in a string shape from the polymer outlet, cooled with water, and then pelletized to obtain pellets. The pellet was washed with stirring in hot water for 6 hours to remove unreacted monomers, and then vacuum dried at 110 ° C. for 72 hours. The ηr of the obtained polyamide was 3.5.
Using about 2 g of the obtained polyamide, an unstretched film having a thickness of 100 μm was prepared using a press molding machine under the condition of 260 ° C.
A 90 mm long and 10 mm wide sample cut out from this unstretched film is attached to a tensile tester (Tensilon RTA-10KN manufactured by Orientec Co., Ltd.) by drawing marked lines (at intervals of 50 mm) and having an atmospheric temperature of 80 ° C. ), Then the film was stretched 2.7 times in the longitudinal direction at a deformation rate of 150 mm / min at the same temperature. The stretched film was left in an atmosphere of 23 ° C. and 50% RH for a whole day and night, and then left in hot water at 90 ° C. for 1 minute to measure the hot water shrinkage rate. It was 32%. The results are shown in Table 1.
（実施例２）
プレス成型機により作製した未延伸フィルムから試料を切り出し、１２０℃の雰囲気温度で予熱、延伸したことを除き、実施例１と同様にして得られた延伸フィルムの熱水収縮率を測定したところ、３６％であった。その結果を表１に示す。(Example 2)
A sample was cut out from the unstretched film produced by the press molding machine, and the hot water shrinkage rate of the stretched film obtained in the same manner as in Example 1 was measured except that the sample was preheated and stretched at an atmospheric temperature of 120 ° C. It was 36%. The results are shown in Table 1.
（実施例３）
プレス成型機により作製した未延伸フィルムから試料を切り出し、１５０℃の雰囲気温度で予熱、延伸したことを除き、実施例１と同様にして得られた延伸フィルムの熱水収縮率を測定したところ、３９％であった。その結果を表１に示す。(Example 3)
A sample was cut out from the unstretched film produced by the press molding machine, and the hot water shrinkage rate of the stretched film obtained in the same manner as in Example 1 was measured except that the sample was preheated and stretched at an atmospheric temperature of 150 ° C. It was 39%. The results are shown in Table 1.
（実施例４）
攪拌機、温度計、圧力計、圧力制御装置、窒素ガス導入口、放圧口及びポリマー取り出し口を備えた７０リットルの耐圧容器にε−カプロラクタム１６．１０ｋｇ（７０重量％）、ＨＭＤとＡＡとの等モル塩５０％水溶液９．２０ｋｇ（ＨＭＤとＡＡとの等モル塩：２０重量％）、ＨＭＤ８０％水溶液１．１８３ｋｇ、テレフタル酸（ＴＰＡ：東京化成工業株式会社製）１．３５３ｋｇ（ＨＭＤとＴＡのモル比が１：１）（１０重量％）、次亜リン酸ナトリウム１．１５ｇを仕込み、窒素加圧と放圧を数回繰り返し、耐圧容器内を窒素置換してから２４０℃まで昇温した。２４０℃で２時間重合させた後、ゲージ圧力０ＭＰａまで放圧し、引き続き、窒素ガスを２６０Ｌ／ｈで流しながら、２４０℃で３．５時間重合を行い、ポリアミドを得た。重合終了後、撹拌を停止し、ポリマー取り出し口から溶融状態の無色透明のポリアミドを紐状に抜き出し、水冷した後、ペレタイズしてペレットを得た。このペレットを熱水流通下、１２時間洗浄し、未反応モノマーを除去した後、１１０℃で１２時間真空乾燥した。得られたポリアミドのηrは４．０であった。
得られたポリアミドをＰＬＡＢＯ製φ４０ｍｍＴダイキャスティング装置にて、成形温度２６０℃でＴダイより溶融押出しし、第一ロール温度４０℃で冷却後、フィルム厚み１００μｍの未延伸フィルムを作製した。得られた未延伸フィルムの突刺し強度、ゲルボフレックス、酸素透過度は、それぞれ、１２．１Ｎ、２４個／０．０３ｍ２、２６．９ｃｃ／ｍ２・ｄａｙであった。
プレス成型機により作製した未延伸フィルムを実施例１と同様に延伸して得られた延伸フィルムの熱水収縮率を測定したところ、３３％であった。その結果を表１に示す。(Example 4)
Ε-caprolactam 16.10 kg (70% by weight), HMD and AA in a 70 liter pressure vessel equipped with a stirrer, thermometer, pressure gauge, pressure controller, nitrogen gas inlet, pressure release port and polymer outlet. 9.20 kg of 50% isomorphic salt aqueous solution (20% by weight of HMD and AA), 1.183 kg of HMD 80% aqueous solution, 1.353 kg of terephthalic acid (TPA: manufactured by Tokyo Kasei Kogyo Co., Ltd.) (HMD and TA) The molar ratio of 1: 1) (10% by weight), 1.15 g of sodium hypophosphite was charged, nitrogen pressurization and release pressure were repeated several times, nitrogen was replaced in the pressure resistant container, and then the temperature was raised to 240 ° C. did. After polymerization at 240 ° C. for 2 hours, the pressure was released to a gauge pressure of 0 MPa, and then polymerization was carried out at 240 ° C. for 3.5 hours while flowing nitrogen gas at 260 L / h to obtain a polyamide. After completion of the polymerization, stirring was stopped, and the colorless and transparent polyamide in a molten state was extracted in a string shape from the polymer outlet, cooled with water, and then pelletized to obtain pellets. The pellet was washed with hot water for 12 hours to remove unreacted monomers, and then vacuum dried at 110 ° C. for 12 hours. The ηr of the obtained polyamide was 4.0.
The obtained polyamide was melt-extruded from a T-die at a molding temperature of 260 ° C. using a PLABO φ40 mm T-die casting apparatus, cooled at a first roll temperature of 40 ° C., and then an unstretched film having a film thickness of 100 μm was prepared. Puncture strength of the unstretched film obtained, Gelbo flex, oxygen permeability, respectively, 12.1 N, was 24 /0.03m 2, 26.9cc / m 2 · day.
The hot water shrinkage rate of the stretched film obtained by stretching the unstretched film produced by the press molding machine in the same manner as in Example 1 was measured and found to be 33%. The results are shown in Table 1.
（実施例５）
実施例４で得られたポリアミドによりプレス成型機を用いて未延伸フィルムを作製し、切り出した試料を１２０℃の雰囲気温度で予熱、延伸したことを除き、実施例１と同様にして得られた延伸フィルムの熱水収縮率を測定したところ、３７％であった。その結果を表１に示す。(Example 5)
An unstretched film was prepared from the polyamide obtained in Example 4 using a press molding machine, and the cut sample was preheated and stretched at an atmospheric temperature of 120 ° C., and was obtained in the same manner as in Example 1. The hot water shrinkage rate of the stretched film was measured and found to be 37%. The results are shown in Table 1.
（実施例６）
実施例４で得られたポリアミドによりプレス成型機を用いて未延伸フィルムを作製し、切り出した試料を１５０℃の雰囲気温度で予熱、延伸したことを除き、実施例１と同様にして得られた延伸フィルムの熱水収縮率を測定したところ、３９％であった。その結果を表１に示す。(Example 6)
An unstretched film was prepared from the polyamide obtained in Example 4 using a press molding machine, and the cut sample was preheated and stretched at an atmospheric temperature of 150 ° C., and was obtained in the same manner as in Example 1. The hot water shrinkage rate of the stretched film was measured and found to be 39%. The results are shown in Table 1.
（比較例１）
ε−カプロラクタム９７５．００ｇ（７５重量％）、ＨＭＤとＡＡとの等モル塩５０％水溶液６５０．００ｇ（ＨＭＤとＡＡとの等モル塩：２５重量％）を仕込み、芳香環構造を有するジアミン及びジカルボン酸を使用しない以外は、実施例１と同様の方法で実施し、ポリアミドを得た。このポリアミドのηrは４．４であった。
このポリアミドから実施例１と同様の方法で未延伸フィルム、次いで延伸フィルムを作製し熱水収縮率を測定したところ、２２％であった。その結果を表１に示す。(Comparative Example 1)
975.00 g (75% by weight) of ε-caprolactam, 650.00 g (75% by weight) of a 50% aqueous solution of an equimolar salt of HMD and AA (isomolar salt of HMD and AA: 25% by weight) are charged, and a diamine having an aromatic ring structure and The same method as in Example 1 was carried out except that a dicarboxylic acid was not used to obtain a polyamide. The ηr of this polyamide was 4.4.
An unstretched film and then a stretched film were prepared from this polyamide by the same method as in Example 1, and the hot water shrinkage rate was measured and found to be 22%. The results are shown in Table 1.
（実施例７）
実施例４で得られたポリアミドをＰＬＡＢＯ製φ４０ｍｍＴダイキャスティング装置にて、成形温度２６０℃でＴダイより溶融押出しし、第一ロール温度４０℃で冷却後、フィルム厚み１００μｍの未延伸フィルムを作製した。得られた未延伸フィルムは、岩本製作所製ＢＩＸ７０３ラボ延伸機を使用して、延伸速度１５０ｍｍ／ｓｅｃ、延伸温度８０℃、延伸倍率３．０×３．０倍に同時二軸延伸した後、１２０℃の加熱空気で熱処理を行い、厚み２５μｍの二軸延伸フィルムを作製した。この延伸フィルムを２３℃、５０％ＲＨの雰囲気中に一昼夜放置した後、９０℃の熱水中に１分間放置して熱水収縮率を測定したところ、４９％であった。その結果を表２に示す。(Example 7)
The polyamide obtained in Example 4 was melt-extruded from a T-die at a molding temperature of 260 ° C. using a PLABO φ40 mm T-die casting apparatus, cooled at a first roll temperature of 40 ° C., and then an unstretched film having a film thickness of 100 μm was prepared. .. The obtained unstretched film was simultaneously biaxially stretched at a stretching speed of 150 mm / sec, a stretching temperature of 80 ° C., and a stretching ratio of 3.0 × 3.0 times using a BIX703 laboratory stretching machine manufactured by Iwamoto Seisakusho, and then 120. Heat treatment was performed with heated air at ° C. to prepare a biaxially stretched film having a thickness of 25 μm. The stretched film was left in an atmosphere of 23 ° C. and 50% RH for a whole day and night, and then left in hot water at 90 ° C. for 1 minute to measure the hot water shrinkage rate. It was 49%. The results are shown in Table 2.
（実施例８）
実施例７で得られた未延伸フィルムを、延伸温度１００℃で同時二軸延伸した後、１００℃の加熱空気で熱処理を行ったことを除き、実施例７と同様にして得られた延伸フィルムの熱水収縮率を測定したところ、５０％であった。その結果を表２に示す。また、得られた延伸フィルムの突刺し強度は１５．４Ｎであった。(Example 8)
The stretched film obtained in the same manner as in Example 7 except that the unstretched film obtained in Example 7 was simultaneously biaxially stretched at a stretching temperature of 100 ° C. and then heat-treated with heated air at 100 ° C. When the hot water shrinkage rate was measured, it was 50%. The results are shown in Table 2. The puncture strength of the obtained stretched film was 15.4N.
（実施例９）
実施例７で得られた未延伸フィルムを、延伸温度１２０℃で同時二軸延伸した後、１２０℃の加熱空気で熱処理を行ったことを除き、実施例７と同様にして得られた延伸フィルムの熱水収縮率を測定したところ、５１％であった。その結果を表２に示す。(Example 9)
The stretched film obtained in the same manner as in Example 7 except that the unstretched film obtained in Example 7 was simultaneously biaxially stretched at a stretching temperature of 120 ° C. and then heat-treated with heated air at 120 ° C. When the hot water shrinkage rate was measured, it was 51%. The results are shown in Table 2.
（実施例１０）
ε−カプロラクタム１６．１０ｋｇ（７０重量％）、ＨＭＤとＡＡとの等モル塩５０％水溶液１１．５０ｋｇ（ＨＭＤとＡＡとの等モル塩：２５重量％）、ＨＭＤ８０％水溶液０．５９２ｋｇ、テレフタル酸（ＴＰＡ：東京化成工業株式会社製）０．６７７ｋｇ（ＨＭＤとＴＡのモル比が１：１）（５重量％）に変更したことを除き、実施例４と同様にしてポリアミドを得た。このポリアミドのηｒは３．９であった。このポリアミドから実施例７と同様に得られた未延伸フィルムの突刺し強度、ゲルボフレックス、酸素透過度は、それぞれ、１１．８Ｎ、８個／０．０３ｍ２、２６．０ｃｃ／ｍ２・ｄａｙであった。
得られた未延伸フィルムを用い、実施例７と同様にして得られた延伸フィルムの熱水収縮率を測定したところ、４８％であった。その結果を表２に示す。(Example 10)
ε-caprolactam 16.10 kg (70% by weight), HMD and AA 50% aqueous isobaric salt 11.50 kg (HMD and AA equimolar salt: 25% by weight), HMD 80% aqueous solution 0.592 kg, terephthalic acid (TPA: manufactured by Tokyo Kasei Kogyo Co., Ltd.) Polyamide was obtained in the same manner as in Example 4 except that the molar ratio of HMD to TA was changed to 0.677 kg (5% by weight). The ηr of this polyamide was 3.9. Puncture strength of unstretched film obtained in the same manner as in Example 7 from the polyamide, Gelbo flex, oxygen permeability, respectively, 11.8 N, 8 pieces /0.03m 2, 26.0cc / m 2 · It was a day.
Using the obtained unstretched film, the hot water shrinkage rate of the stretched film obtained in the same manner as in Example 7 was measured and found to be 48%. The results are shown in Table 2.
（実施例１１）
実施例１０で得られたポリアミドを用い、実施例８と同様にして得られた延伸フィルムの熱水収縮率を測定したところ、５０％であった。その結果を表２に示す。また、得られた延伸フィルムの突刺し強度は、１５．１Ｎであった。(Example 11)
Using the polyamide obtained in Example 10, the hot water shrinkage rate of the stretched film obtained in the same manner as in Example 8 was measured and found to be 50%. The results are shown in Table 2. The puncture strength of the obtained stretched film was 15.1N.
（比較例２）
ε−カプロラクタム１７．２５ｋｇ（７５重量％）、ＨＭＤとＡＡとの等モル塩５０％水溶液１１．５ｋｇ（ＨＭＤとＡＡとの等モル塩：２５重量％）を仕込み、芳香環構造を有するジアミン及びジカルボン酸を使用しないことを除き、実施例４と同様の方法で実施し、ポリアミドを得た。このポリアミドのηrは４．４であった。このポリアミドから実施例７と同様の方法で未延伸フィルム、次いで延伸フィルムを作製し熱水収縮率を測定したところ、４１％であった。その結果を表２に示す。(Comparative Example 2)
17.25 kg (75% by weight) of ε-caprolactam and 11.5 kg (25% by weight) of a 50% aqueous solution of an equimolar salt of HMD and AA are charged, and a diamine having an aromatic ring structure and The same method as in Example 4 was carried out except that a dicarboxylic acid was not used to obtain a polyamide. The ηr of this polyamide was 4.4. An unstretched film and then a stretched film were prepared from this polyamide by the same method as in Example 7, and the hot water shrinkage rate was measured and found to be 41%. The results are shown in Table 2.
（実施例１２）
ε−カプロラクタム１３．８０ｋｇ（６０重量％）、ＨＭＤとＡＡとの等モル塩５０％水溶液１６．１０ｋｇ（ＨＭＤとＡＡとの等モル塩：３５重量％）、ＨＭＤ８０％水溶液０．５９２ｋｇ、テレフタル酸（ＴＡ：東京化成工業株式会社製）０．６７７ｋｇ（ＨＭＤとＴＡのモル比が１：１）（５重量％）に変更したことを除き、実施例４と同様にしてポリアミドを得た。このポリアミドのηｒは３．１５であった。このポリアミドから実施例７と同様に得られた未延伸フィルムの突刺し強度、ゲルボフレックスは、それぞれ、９．４Ｎ、５個／０．０３ｍ２であった。
得られた未延伸フィルムを用い、実施例７と同様にして得られた延伸フィルムを６０℃の熱水中に１分間放置して熱水収縮率を測定したところ、４０％であった。その結果を表２に示す。(Example 12)
13.80 kg (60% by weight) of ε-caprolactam, 16.10 kg (35% by weight) of an equimolar salt solution of HMD and AA, 0.592 kg of HMD 80% aqueous solution, terephthalic acid (TA: manufactured by Tokyo Kasei Kogyo Co., Ltd.) Polyamide was obtained in the same manner as in Example 4 except that the molar ratio of HMD to TA was changed to 0.677 kg (5% by weight). The ηr of this polyamide was 3.15. The puncture strength and gelboflex of the unstretched film obtained from this polyamide in the same manner as in Example 7 were 9.4 N, 5 pieces / 0.03 m 2 , respectively.
Using the obtained unstretched film, the stretched film obtained in the same manner as in Example 7 was left in hot water at 60 ° C. for 1 minute, and the hot water shrinkage rate was measured and found to be 40%. The results are shown in Table 2.
（実施例１３）
ε−カプロラクタム１３．８０ｋｇ（６０重量％）、ＨＭＤとＡＡとの等モル塩５０％水溶液１１．５０ｋｇ（ＨＭＤとＡＡとの等モル塩：２５重量％）、ＨＭＤ８０％水溶液１．７７５ｋｇ、テレフタル酸（ＴＡ：東京化成工業株式会社製）２．０３１ｋｇ（ＨＭＤとＴＡのモル比が１：１）（１５重量％）に変更したことを除き、実施例４と同様にしてポリアミドを得た。このポリアミドのηｒは２．９８であった。このポリアミドから実施例７と同様に得られた未延伸フィルムの突刺し強度、ゲルボフレックスは、それぞれ、９．３Ｎ、１７個／０．０３ｍ２であった。
得られた未延伸フィルムを用い、実施例７と同様にして得られた延伸フィルムを６０℃の熱水中に１分間放置して熱水収縮率を測定したところ、４０％であった。その結果を表２に示す。(Example 13)
13.80 kg (60% by weight) of ε-caprolactam, 11.50 kg (25% by weight) of an equimolar salt solution of HMD and AA, 1.775 kg of HMD 80% aqueous solution, terephthalic acid (TA: manufactured by Tokyo Kasei Kogyo Co., Ltd.) Polyamide was obtained in the same manner as in Example 4 except that it was changed to 2.031 kg (molar ratio of HMD to TA was 1: 1) (15% by weight). The ηr of this polyamide was 2.98. The puncture strength and gelboflex of the unstretched film obtained from this polyamide in the same manner as in Example 7 were 9.3 N and 17 / 0.03 m 2 , respectively.
Using the obtained unstretched film, the stretched film obtained in the same manner as in Example 7 was left in hot water at 60 ° C. for 1 minute, and the hot water shrinkage rate was measured and found to be 40%. The results are shown in Table 2.
Claims (10)
（Ａ）ラクタム及び／又はアミノカルボン酸に由来する単位並びに
（Ｂ）ジアミン及びジカルボン酸の等モル塩に由来する単位を含み、
前記（Ｂ）ジアミン及びジカルボン酸の等モル塩に由来する単位は、
（Ｂ−１）芳香環構造を有さない単位及び
（Ｂ−２）芳香環構造を有する単位
を含むシュリンクフィルム用ポリアミド樹脂。A polyamide resin containing 3 or more units.
Includes (A) units derived from lactam and / or aminocarboxylic acids and (B) units derived from equimolar salts of diamines and dicarboxylic acids.
The unit derived from the equimolar salt of (B) diamine and dicarboxylic acid is
Polyamide resin for shrink film containing (B-1) a unit having no aromatic ring structure and (B-2) a unit having an aromatic ring structure.
前記（Ａ）ラクタム及び／又はアミノカルボン酸に由来する単位を５０〜９８重量％、
前記（Ｂ−２）芳香環構造を有する単位を１〜４９重量％含む請求項１に記載のシュリンクフィルム用ポリアミド樹脂。In all units of polyamide resin,
Units derived from (A) lactam and / or aminocarboxylic acid are 50 to 98% by weight.
The polyamide resin for a shrink film according to claim 1, which contains 1 to 49% by weight of the unit having the aromatic ring structure (B-2).
前記（Ａ）ラクタム及び／又はアミノカルボン酸に由来する単位を６０〜７０重量％及び前記（Ｂ）ジアミン及びジカルボン酸の等モル塩に由来する単位を３０〜４０重量％含み、かつ、前記（Ｂ−１）芳香環構造を有さない単位を２５〜３９重量％及び前記（Ｂ−２）芳香環構造を有する単位を１〜１５重量％含む、請求項１〜４のいずれかに記載のシュリンクフィルム用ポリアミド樹脂。In all units of polyamide resin,
It contains 60 to 70% by weight of the unit derived from the (A) lactam and / or aminocarboxylic acid and 30 to 40% by weight of the unit derived from the equimolar salt of the (B) diamine and dicarboxylic acid. B-1. The invention according to any one of claims 1 to 4, wherein 25 to 39% by weight of the unit does not have an aromatic ring structure and 1 to 15% by weight of the unit having the (B-2) aromatic ring structure. Polyamide resin for shrink film.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54152098A (en) * | 1978-05-22 | 1979-11-29 | Unitika Ltd | Copolyamide |
| JPS63268744A (en) * | 1987-04-28 | 1988-11-07 | Mitsubishi Kasei Corp | Heat-shrinkable polyamide film |
| WO2013002069A1 (en) * | 2011-06-27 | 2013-01-03 | 三菱瓦斯化学株式会社 | Multi-layer film and film packaging container |
| JP2017505364A (en) * | 2014-01-28 | 2017-02-16 | ラディシフィル エス．ピー．エー． | Ternary copolymer having high transparency and low gas permeability and method for producing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54152098A (en) * | 1978-05-22 | 1979-11-29 | Unitika Ltd | Copolyamide |
| JPS63268744A (en) * | 1987-04-28 | 1988-11-07 | Mitsubishi Kasei Corp | Heat-shrinkable polyamide film |
| WO2013002069A1 (en) * | 2011-06-27 | 2013-01-03 | 三菱瓦斯化学株式会社 | Multi-layer film and film packaging container |
| JP2017505364A (en) * | 2014-01-28 | 2017-02-16 | ラディシフィル エス．ピー．エー． | Ternary copolymer having high transparency and low gas permeability and method for producing the same |
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