JP2006348057A - Polyamide resin - Google Patents
Polyamide resin Download PDFInfo
- Publication number
- JP2006348057A JP2006348057A JP2005145847A JP2005145847A JP2006348057A JP 2006348057 A JP2006348057 A JP 2006348057A JP 2005145847 A JP2005145847 A JP 2005145847A JP 2005145847 A JP2005145847 A JP 2005145847A JP 2006348057 A JP2006348057 A JP 2006348057A
- Authority
- JP
- Japan
- Prior art keywords
- polyamide resin
- units
- pentamethylenediamine
- hexamethylenediamine
- resin composition
- 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 165
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical group NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 claims abstract description 59
- 239000011342 resin composition Substances 0.000 claims abstract description 49
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid group Chemical group C(CCCCC(=O)O)(=O)O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims abstract description 45
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical group NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims abstract description 37
- 125000004427 diamine group Chemical group 0.000 claims abstract description 10
- 125000001142 dicarboxylic acid group Chemical group 0.000 claims abstract description 8
- -1 aliphatic diamine Chemical class 0.000 claims description 18
- 239000001361 adipic acid Substances 0.000 claims description 17
- 235000011037 adipic acid Nutrition 0.000 claims description 17
- 239000003365 glass fiber Substances 0.000 claims description 16
- 229920002647 polyamide Polymers 0.000 claims description 13
- 238000006068 polycondensation reaction Methods 0.000 claims description 13
- 239000004952 Polyamide Substances 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 12
- 108010048581 Lysine decarboxylase Proteins 0.000 claims description 10
- 239000011256 inorganic filler Substances 0.000 claims description 10
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 10
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 claims description 8
- 239000004472 Lysine Substances 0.000 claims description 8
- 239000000470 constituent Substances 0.000 claims description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 5
- 238000005259 measurement Methods 0.000 claims description 4
- 239000002994 raw material Substances 0.000 abstract description 29
- 238000000465 moulding Methods 0.000 abstract description 26
- 239000002028 Biomass Substances 0.000 abstract description 14
- 238000003466 welding Methods 0.000 description 57
- 238000012360 testing method Methods 0.000 description 37
- 239000000047 product Substances 0.000 description 36
- 239000004677 Nylon Substances 0.000 description 30
- 229920001778 nylon Polymers 0.000 description 30
- 238000000034 method Methods 0.000 description 26
- 238000002844 melting Methods 0.000 description 18
- 230000008018 melting Effects 0.000 description 18
- 238000011156 evaluation Methods 0.000 description 15
- 229920005989 resin Polymers 0.000 description 13
- 239000011347 resin Substances 0.000 description 13
- 238000001746 injection moulding Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 238000005452 bending Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000002216 antistatic agent Substances 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 238000000113 differential scanning calorimetry Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000003484 crystal nucleating agent Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 239000000454 talc Substances 0.000 description 6
- 229910052623 talc Inorganic materials 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000007334 copolymerization reaction Methods 0.000 description 4
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 4
- 239000003063 flame retardant Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 3
- 229910052582 BN Inorganic materials 0.000 description 3
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 235000012211 aluminium silicate Nutrition 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000000498 cooling water Substances 0.000 description 3
- 238000006114 decarboxylation reaction Methods 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 230000002255 enzymatic effect Effects 0.000 description 3
- 239000012760 heat stabilizer Substances 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 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 3
- 239000000314 lubricant Substances 0.000 description 3
- 238000002074 melt spinning Methods 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 238000009864 tensile test Methods 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- PBLZLIFKVPJDCO-UHFFFAOYSA-N 12-aminododecanoic acid Chemical compound NCCCCCCCCCCCC(O)=O PBLZLIFKVPJDCO-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- IPRJXAGUEGOFGG-UHFFFAOYSA-N N-butylbenzenesulfonamide Chemical compound CCCCNS(=O)(=O)C1=CC=CC=C1 IPRJXAGUEGOFGG-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- BTZVDPWKGXMQFW-UHFFFAOYSA-N Pentadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCC(O)=O BTZVDPWKGXMQFW-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 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
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 238000000071 blow moulding Methods 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 229920006017 homo-polyamide Polymers 0.000 description 2
- 229920001519 homopolymer Polymers 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
- 125000003588 lysine group Chemical group [H]N([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(N([H])[H])C(*)=O 0.000 description 2
- 239000006082 mold release agent Substances 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- BNJOQKFENDDGSC-UHFFFAOYSA-N octadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCCC(O)=O BNJOQKFENDDGSC-UHFFFAOYSA-N 0.000 description 2
- GPCKFIWBUTWTDH-UHFFFAOYSA-N pentane-3,3-diamine Chemical compound CCC(N)(N)CC GPCKFIWBUTWTDH-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 230000001012 protector Effects 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- LWBHHRRTOZQPDM-UHFFFAOYSA-N undecanedioic acid Chemical compound OC(=O)CCCCCCCCCC(O)=O LWBHHRRTOZQPDM-UHFFFAOYSA-N 0.000 description 2
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 description 1
- DGZQEAKNZXNTNL-UHFFFAOYSA-N 1-bromo-4-butan-2-ylbenzene Chemical class CCC(C)C1=CC=C(Br)C=C1 DGZQEAKNZXNTNL-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- GUOSQNAUYHMCRU-UHFFFAOYSA-N 11-Aminoundecanoic acid Chemical compound NCCCCCCCCCCC(O)=O GUOSQNAUYHMCRU-UHFFFAOYSA-N 0.000 description 1
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 1
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 1
- FWLHAQYOFMQTHQ-UHFFFAOYSA-N 2-N-[8-[[8-(4-aminoanilino)-10-phenylphenazin-10-ium-2-yl]amino]-10-phenylphenazin-10-ium-2-yl]-8-N,10-diphenylphenazin-10-ium-2,8-diamine hydroxy-oxido-dioxochromium Chemical compound O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.Nc1ccc(Nc2ccc3nc4ccc(Nc5ccc6nc7ccc(Nc8ccc9nc%10ccc(Nc%11ccccc%11)cc%10[n+](-c%10ccccc%10)c9c8)cc7[n+](-c7ccccc7)c6c5)cc4[n+](-c4ccccc4)c3c2)cc1 FWLHAQYOFMQTHQ-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
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 description 1
- 239000004114 Ammonium polyphosphate Substances 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-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
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000005700 Putrescine Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- GKXVJHDEWHKBFH-UHFFFAOYSA-N [2-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC=C1CN GKXVJHDEWHKBFH-UHFFFAOYSA-N 0.000 description 1
- RJDOZRNNYVAULJ-UHFFFAOYSA-L [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] RJDOZRNNYVAULJ-UHFFFAOYSA-L 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 150000008431 aliphatic amides Chemical class 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 229960002684 aminocaproic acid Drugs 0.000 description 1
- QCTBMLYLENLHLA-UHFFFAOYSA-N aminomethylbenzoic acid Chemical compound NCC1=CC=C(C(O)=O)C=C1 QCTBMLYLENLHLA-UHFFFAOYSA-N 0.000 description 1
- 229960003375 aminomethylbenzoic acid Drugs 0.000 description 1
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 1
- 229920001276 ammonium polyphosphate Polymers 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 229960003237 betaine Drugs 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000009172 bursting Effects 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- YMHQVDAATAEZLO-UHFFFAOYSA-N cyclohexane-1,1-diamine Chemical compound NC1(N)CCCCC1 YMHQVDAATAEZLO-UHFFFAOYSA-N 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 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 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- FBKBMXXJECMLCQ-UHFFFAOYSA-N disodium;hydrogen phosphite;pentahydrate Chemical compound O.O.O.O.O.[Na+].[Na+].OP([O-])[O-] FBKBMXXJECMLCQ-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
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical class C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- CHSILQAFIZTLJN-UHFFFAOYSA-N heptadecane-1,17-diamine Chemical compound NCCCCCCCCCCCCCCCCCN CHSILQAFIZTLJN-UHFFFAOYSA-N 0.000 description 1
- PWSKHLMYTZNYKO-UHFFFAOYSA-N heptane-1,7-diamine Chemical compound NCCCCCCCN PWSKHLMYTZNYKO-UHFFFAOYSA-N 0.000 description 1
- ATJCASULPHYKHT-UHFFFAOYSA-N hexadecane-1,16-diamine Chemical compound NCCCCCCCCCCCCCCCCN ATJCASULPHYKHT-UHFFFAOYSA-N 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- POIZGMCHYSVWDU-UHFFFAOYSA-N icosane-1,20-diamine Chemical compound NCCCCCCCCCCCCCCCCCCCCN POIZGMCHYSVWDU-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 150000002497 iodine compounds Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- VCAISILSXYFPGO-UHFFFAOYSA-N nonadecane-1,19-diamine Chemical compound NCCCCCCCCCCCCCCCCCCCN VCAISILSXYFPGO-UHFFFAOYSA-N 0.000 description 1
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 description 1
- 229920006118 nylon 56 Polymers 0.000 description 1
- CJYCVQJRVSAFKB-UHFFFAOYSA-N octadecane-1,18-diamine Chemical compound NCCCCCCCCCCCCCCCCCCN CJYCVQJRVSAFKB-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 239000001818 polyoxyethylene sorbitan monostearate Substances 0.000 description 1
- 235000010989 polyoxyethylene sorbitan monostearate Nutrition 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 229920000638 styrene acrylonitrile Polymers 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
- MSVPBWBOFXVAJF-UHFFFAOYSA-N tetradecane-1,14-diamine Chemical compound NCCCCCCCCCCCCCCN MSVPBWBOFXVAJF-UHFFFAOYSA-N 0.000 description 1
- HQHCYKULIHKCEB-UHFFFAOYSA-N tetradecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCC(O)=O HQHCYKULIHKCEB-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- BPSKTAWBYDTMAN-UHFFFAOYSA-N tridecane-1,13-diamine Chemical compound NCCCCCCCCCCCCCN BPSKTAWBYDTMAN-UHFFFAOYSA-N 0.000 description 1
- KLNPWTHGTVSSEU-UHFFFAOYSA-N undecane-1,11-diamine Chemical compound NCCCCCCCCCCCN KLNPWTHGTVSSEU-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Images
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- Polyamides (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Artificial Filaments (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
Description
本発明はポリアミド樹脂に関する。詳しくは、本発明は、構成成分としてアジピン酸単位、ペンタメチレンジアミン単位およびヘキサメチレンジアミン単位を含有し、地球温暖化の原因となる二酸化炭素（ＣＯ２）の発生を抑制する原料を使用したポリアミド樹脂に関する。本発明は、更に、上記ポリアミド樹脂を使用した振動溶着強度に優れた振動溶着成形品、低温靭性に優れたヒンジ付き成形品および結束バンド、ならびに透明性に優れたフィラメントにも関する。 The present invention relates to a polyamide resin. Specifically, the present invention relates to a polyamide using a raw material containing adipic acid units, pentamethylenediamine units and hexamethylenediamine units as constituents and suppressing the generation of carbon dioxide (CO 2 ) causing global warming. It relates to resin. The present invention further relates to a vibration welded molded article excellent in vibration weld strength using the polyamide resin, a hinged molded article and a binding band excellent in low temperature toughness, and a filament excellent in transparency.
６ナイロンや６６ナイロンは、成型性、耐熱性、耐薬品性、機械的特性などに優れた樹脂であり、自動車・車両関連部品、電気・電子関連部品、家庭・事務用電気製品関連部品、コンピューター関連部品、ファクシミリ・複写機関連部品、機械関連部品、包装用資材、漁業関連資材などの幅広い用途に使用されている。特に、自動車・車両関連部品としてインテークマニホールド、ヒンジ付きクリップ（ヒンジ付き成形品）、結束バンド、レゾネーター、エアークリーナー、エンジンカバー、ロッカーカバー、シリンダーヘッドカバー、タイミングベルトカバー、ガソリンタンク、ガソリンサブタンク、ラジエータータンク、インタークーラータンク、オイルリザーバータンク、オイルパン、電動パワステギヤ、オイルストレーナー、キャニスター、エンジンマウント、ジャンクションブロック、リレーブロック、コネクター、コルゲートチューブ、プロテクター等の自動車用アンダーフード部品への応用が検討されている。 6 Nylon and 66 Nylon are resins with excellent moldability, heat resistance, chemical resistance, mechanical properties, etc., automobile / vehicle related parts, electrical / electronic related parts, home / office electrical product related parts, computer Used in a wide range of applications such as related parts, facsimile / copier-related parts, machine-related parts, packaging materials, and fishery-related materials. In particular, intake manifold, hinged clip (molded product with hinge), cable tie, resonator, air cleaner, engine cover, rocker cover, cylinder head cover, timing belt cover, gasoline tank, gasoline sub tank, radiator tank as automotive / vehicle related parts Application to automotive underhood parts such as intercooler tanks, oil reservoir tanks, oil pans, electric power steering gears, oil strainers, canisters, engine mounts, junction blocks, relay blocks, connectors, corrugated tubes, and protectors are being studied.
これらの自動車用アンダーフード部品は、部品の複雑化や軽量化目的の薄肉化に対応するために、より高い部品強度が要求されている。自動車用アンダーフード部品の中でも、寸法の大きい部類であるインテークマニホールド等は薄肉化による軽量化効果が高い。しかしながら、エンジンのバックファイア等によって内圧が増大した際に、破損せず安全性を維持する必要があるため、薄肉化に制限を受けているのが実状である。 These underhood parts for automobiles are required to have higher part strength in order to cope with complication of parts and thinning for the purpose of weight reduction. Among the underhood parts for automobiles, the intake manifold, which is a large size class, is highly effective in reducing the weight by reducing the thickness. However, when the internal pressure increases due to the engine backfire or the like, it is necessary to maintain safety without being damaged.
近年、樹脂インテークマニホールド用の材料として、主にガラス繊維強化６ナイロンが使用されており、工法としては振動溶着法が主流である。また、樹脂インテークマニホールド用の材料として、６ナイロンの代わり５６ナイロンを使用することが提案されている（例えば、特許文献１参照）。しかしながら、５６ナイロンでは振動溶着強度が不十分である。さらに、５６ナイロンは滞留熱安定性に劣るため、インテークマニホールドの様に成形サイクルが長い大型成形品には不向きである。従って、５６ナイロンよりも優れた振動溶着強度と滞留熱安定性を有するポリアミド樹脂が要求されている。 In recent years, glass fiber reinforced 6 nylon is mainly used as a material for a resin intake manifold, and a vibration welding method is mainly used as a construction method. In addition, it has been proposed to use 56 nylon instead of 6 nylon as a material for the resin intake manifold (see, for example, Patent Document 1). However, 56 nylon is insufficient in vibration welding strength. Furthermore, since 56 nylon is inferior in staying heat stability, it is not suitable for a large molded product having a long molding cycle such as an intake manifold. Accordingly, there is a demand for a polyamide resin having vibration welding strength and residence heat stability superior to 56 nylon.
また、少量の５６ナイロン単位を含有する６６ナイロン単位の多い５６／６６ナイロン（５６／６６＝０．５／９９．５〜４０／６０モル％、好ましくは０．５／９９．５〜１０／９０モル％）も知られている（例えば、特許文献２参照）。この種のポリアミド樹脂は、６６ナイロンの機能を維持したまま６６ナイロンのゲル化を抑制することを目的としているため、５６ナイロンの添加量は少量である。そのため、振動溶着強度については不明なものの、６６ナイロンと同程度であると考えられ、大型薄肉成形品に使用するためには更なる改良が要求される。 Further, 56/66 nylon having a large amount of 66 nylon units containing a small amount of 56 nylon units (56/66 = 0.5 / 99.5 to 40/60 mol%, preferably 0.5 / 99.5 to 10 / 90 mol%) is also known (see, for example, Patent Document 2). Since this type of polyamide resin is intended to suppress the gelation of 66 nylon while maintaining the function of 66 nylon, the amount of 56 nylon added is small. Therefore, although the vibration welding strength is unknown, it is considered to be the same as 66 nylon, and further improvement is required for use in large thin molded products.
ヒンジ付き成形品としては、自動車用アンダーフード部品において多数使用されている。現状では、高い耐熱性を要求される場合には６６ナイロン、高い靭性が要求される場合には６ナイロンと使い分けられている。６６ナイロンは融点が２６４℃と高いが、結晶性が高いため靭性がやや低く、ヒンジ部折り曲げ時に割れやすい。一方、６ナイロンは６６ナイロンより結晶性が低いため靭性が良好であるが、融点が２２４℃と６６ナイロンより４０℃も低い。 As a molded article with a hinge, many are used in underhood parts for automobiles. At present, 66 nylon is used when high heat resistance is required, and 6 nylon is used when high toughness is required. 66 nylon has a high melting point of 264 ° C., but its toughness is somewhat low due to its high crystallinity, and it is easily broken when the hinge part is bent. On the other hand, nylon 6 has better toughness due to lower crystallinity than 66 nylon, but its melting point is 224 ° C. and 40 ° C. lower than 66 nylon.
ヒンジ付き成形品のヒンジ性の改良手段としては、ポリアミド樹脂に窒化ホウ素粉末と脂肪族カルボン酸誘導体とを配合する方法が知られている（例えば、特許文献３参照）。しかしながら、この種の樹脂組成物において、耐熱性（融点）の向上は無いと考えられる。 As a means for improving the hinge property of a molded article with a hinge, a method is known in which a boron nitride powder and an aliphatic carboxylic acid derivative are blended with a polyamide resin (see, for example, Patent Document 3). However, this type of resin composition is considered to have no improvement in heat resistance (melting point).
また、ポリアミド樹脂にポリプロピレンやポリエチレン等のポリオレフィンを配合する方法も知られている（例えば、特許文献４参照）。しかしながら、この種のポリアミド樹脂組成物では、耐熱性（融点）や曲げ弾性率などの機械物性が、ポリアミド樹脂よりも低下する。 A method of blending a polyamide resin with a polyolefin such as polypropylene or polyethylene is also known (see, for example, Patent Document 4). However, in this type of polyamide resin composition, mechanical properties such as heat resistance (melting point) and flexural modulus are lower than that of polyamide resin.
上記のヒンジ性と耐熱性（熱変形温度）とを同時に満足するポリアミド樹脂組成物としては、芳香族ポリアミド樹脂と、変性ポリオレフィンと、エポキシ基を含有する重合体またはエポキシ化ジエン系ブロック共重合体とから成るポリアミド樹脂組成物が知られている（例えば、特許文献５及び６参照）。しかしながら、この種のポリアミド樹脂組成物の曲げ弾性率は１５００〜１９００ＭＰａ程度であり、通常の６ナイロンの曲げ弾性率（約２５５０ＭＰａ）及び６６ナイロンの曲げ弾性率（約２９４０ＭＰａ）に比べて大きく劣り、機械物性として重要な剛性が不足している。従って、６ナイロンよりも優れたヒンジ性と耐熱性（融点）を有し、同時に６ナイロンと同等以上の剛性（曲げ弾性率）を有するポリアミド樹脂が望まれている。 The polyamide resin composition satisfying both the hinge property and the heat resistance (thermal deformation temperature) at the same time includes an aromatic polyamide resin, a modified polyolefin, a polymer containing an epoxy group, or an epoxidized diene block copolymer. (See, for example, Patent Documents 5 and 6). However, the bending elastic modulus of this type of polyamide resin composition is about 1500 to 1900 MPa, which is greatly inferior to the bending elastic modulus of ordinary 6 nylon (about 2550 MPa) and 66 nylon (about 2940 MPa), Rigidity important as mechanical properties is insufficient. Therefore, there is a demand for a polyamide resin having hinge properties and heat resistance (melting point) superior to 6 nylon, and at the same time having a rigidity (flexural modulus) equal to or higher than 6 nylon.
また、ポリアミドの原料としては、ナフサ、いわゆる化石原料が使用されているが、二酸化炭素排出抑制による地球温暖化防止および循環型社会の形成に向けて、ポリアミドの製造原料をバイオマス由来の原料に代替することが嘱望されている。すなわち、ポリアミドの原料として、バイオマス比率（ポリアミド樹脂の使用原料中に占めるバイオマス由来原料の割合）を高くすることが望まれている。 In addition, naphtha, a so-called fossil raw material, is used as a raw material for polyamide. However, in order to prevent global warming by suppressing carbon dioxide emissions and to create a recycling-oriented society, the raw material for polyamide production is replaced with a raw material derived from biomass. It is envied to do. That is, it is desired to increase the biomass ratio (ratio of biomass-derived raw material in the used raw material of polyamide resin) as a raw material for polyamide.
バイオマス由来の原料が望まれている分野は、自動車分野に限らず、電気電子分野、フィルム分野、フィラメント分野と多様であるが、具体的な部品としては、上記の振動溶着強度に優れたインテークマニホールド等の振動溶着成形品、低温靭性に優れたヒンジ付き成形品および結束バンド、透明性に優れたフィラメント等が挙げられる。 The fields where biomass-derived raw materials are desired are not limited to the automotive field, but there are various fields such as the electrical and electronic field, the film field, and the filament field. Specific parts include intake manifolds with excellent vibration welding strength as described above. And the like, vibration molded articles such as hinged molded articles excellent in low temperature toughness and binding bands, and filaments excellent in transparency.
バイオマス由来の原料を使用して重合し、製造されるポリアミド樹脂として、５６ナイロンが知られている。５６ナイロンは、６ナイロンや６６ナイロンと比較して、ほぼ同等の耐熱性や機械物性を有する。５６ナイロンの製造方法としては、ジアミノペンタンとアジピン酸を加熱重縮合する方法（例えば、特許文献７参照）、ジアミノペンタンとアジピン酸との塩を調製し、加熱重縮合する方法（例えば、特許文献８参照）等が知られている。しかしながら、上述の様に、５６ナイロンは振動溶着強度と滞留熱安定性に劣る。そのため、バイオマス由来の原料を使用して重合製造でき、低温靭性に優れたヒンジ付き成形品、結束バンドや透明性に優れたフィラメントを提供し得るポリアミド樹脂が望まれている。 Nylon 56 is known as a polyamide resin produced by polymerization using biomass-derived raw materials. 56 nylon has substantially the same heat resistance and mechanical properties as compared with 6 nylon and 66 nylon. 56 Nylon is produced by heating polycondensation of diaminopentane and adipic acid (see, for example, Patent Document 7), or preparing a salt of diaminopentane and adipic acid and heating polycondensation (for example, Patent Document). 8) etc. are known. However, as described above, 56 nylon is inferior in vibration welding strength and residence heat stability. Therefore, there is a demand for a polyamide resin that can be polymerized using biomass-derived raw materials and can provide a hinged molded article excellent in low-temperature toughness, a binding band, and a filament excellent in transparency.
本発明は、上記の実情に鑑みなされたものであり、その目的は、振動溶着強度、滞留熱安定性、低温靭性および透明性に優れ、バイオマス由来の原料を使用して製造できるポリアミド樹脂を提供することである。 The present invention has been made in view of the above circumstances, and its purpose is to provide a polyamide resin that is excellent in vibration welding strength, residence heat stability, low temperature toughness, and transparency, and can be produced using biomass-derived raw materials. It is to be.
本発明の他の目的は、上記ポリアミド樹脂を含有するポリアミド樹脂組成物を提供することである。 Another object of the present invention is to provide a polyamide resin composition containing the polyamide resin.
本発明の更に他の目的は、上記ポリアミド樹脂またはポリアミド樹脂組成物を含有する振動溶着成形品、ヒンジ付き成形品、結束バンド及びフィラメントを提供することである。 Still another object of the present invention is to provide a vibration welded molded article, a hinged molded article, a binding band and a filament containing the polyamide resin or polyamide resin composition.
上記課題を解決するために、本発明者らは鋭意検討した結果、アジピン酸単位、ペンタメチレンジアミン単位およびヘキサメチレンジアミン単位を含有する構成成分を有し、ペンタメチレンジアミン単位とキサメチレンジアミン単位との含有比率が特定範囲内であるポリアミド樹脂により、上記の目的を達成できることを見出し、本発明を完成させるに至った。 In order to solve the above problems, the present inventors have intensively studied, and as a result, have a constituent component containing an adipic acid unit, a pentamethylenediamine unit and a hexamethylenediamine unit, and a pentamethylenediamine unit, a xamethylenediamine unit, It has been found that the above object can be achieved by a polyamide resin having a content ratio of within the specified range, and the present invention has been completed.
本発明の第１の要旨は、ジカルボン酸単位としてアジピン酸単位を含有し、ジアミン単位としてペンタメチレンジアミン単位およびヘキサメチレンジアミン単位を含有する構成成分を有するポリアミド樹脂であって、ペンタメチレンジアミン単位とヘキサメチレンジアミン単位との重量比が９５：５〜５：９５であり、上記ペンタメチレンジアミン単位が、リジン脱炭酸酵素、リジン脱炭酸酵素を産生する細胞または当該細胞の処理物を使用してリジンから産出されているペンタメチレンジアミンを使用して形成されていることを特徴とするポリアミド樹脂に存する。 A first gist of the present invention is a polyamide resin having a component containing an adipic acid unit as a dicarboxylic acid unit and a pentamethylenediamine unit and a hexamethylenediamine unit as a diamine unit, The weight ratio with respect to the hexamethylenediamine unit is 95: 5 to 5:95, and the pentamethylenediamine unit is lysine using lysine decarboxylase, cells producing lysine decarboxylase, or a treated product of the cell. The polyamide resin is characterized in that it is formed using pentamethylenediamine produced from
本発明の第２の要旨は、ジカルボン酸単位としてアジピン酸単位を含有し、ジアミン単位としてペンタメチレンジアミン単位およびヘキサメチレンジアミン単位を含有する構成成分を有するポリアミド樹脂であって、ペンタメチレンジアミン単位とヘキサメチレンジアミン単位との重量比が９５：５〜６０：４０であることを特徴とするポリアミド樹脂に存する。 The second gist of the present invention is a polyamide resin containing adipic acid units as dicarboxylic acid units and having constituents containing pentamethylenediamine units and hexamethylenediamine units as diamine units, It exists in the polyamide resin characterized by weight ratio with a hexamethylenediamine unit being 95: 5-60: 40.
本発明の第３の要旨は、上記のポリアミド樹脂と無機充填材とを含有し、ポリアミド樹脂１００重量部に対する無機充填材の含有量が０．０１〜１５０重量部であることを特徴とするポリアミド樹脂組成物に存する。 A third gist of the present invention is a polyamide comprising the above polyamide resin and an inorganic filler, wherein the content of the inorganic filler with respect to 100 parts by weight of the polyamide resin is 0.01 to 150 parts by weight. Resists in resin composition.
本発明の第４の要旨は、上記のポリアミド樹脂または上記のポリアミド樹脂組成物を含有する振動溶着成形品に存する。 The fourth gist of the present invention resides in a vibration welding molded article containing the above polyamide resin or the above polyamide resin composition.
本発明の第５の要旨は、上記のポリアミド樹脂または上記のポリアミド樹脂組成物を含有するヒンジ付き成形品に存する。 The fifth gist of the present invention resides in a hinged molded article containing the above polyamide resin or the above polyamide resin composition.
本発明の第６の要旨は、上記のポリアミド樹脂または上記のポリアミド樹脂組成物を含有する結束バンドに存する。 The sixth gist of the present invention resides in a binding band containing the above polyamide resin or the above polyamide resin composition.
本発明の第７の要旨は、上記のポリアミド樹脂または上記のポリアミド樹脂組成物を含有するフィラメントに存する。 The seventh gist of the present invention resides in a filament containing the above polyamide resin or the above polyamide resin composition.
本発明のポリアミド樹脂またはポリアミド樹脂組成物は、振動溶着強度、滞留熱安定性、低温靭性、透明性に優れる。また、本発明のポリアミド樹脂またはポリアミド樹脂組成物を使用して、振動溶着成形品、ヒンジ付き成形品、結束バンド、フィラメントを提供することが可能であり、特に本発明のポリアミド樹脂から成るヒンジ付き成形品は極めて高いヒンジ特性を発現する。さらに、本発明のポリアミド樹脂はバイオマス由来の原料から製造でき、様々な産業において環境負荷低減への著しい効果が期待でき、本発明の工業的価値は高い。 The polyamide resin or polyamide resin composition of the present invention is excellent in vibration welding strength, residence heat stability, low temperature toughness, and transparency. Moreover, it is possible to provide a vibration welded molded article, a molded article with a hinge, a binding band, and a filament using the polyamide resin or the polyamide resin composition of the present invention, and in particular, with a hinge made of the polyamide resin of the present invention. The molded product exhibits extremely high hinge characteristics. Furthermore, the polyamide resin of the present invention can be produced from biomass-derived raw materials, and can be expected to have a significant effect on reducing the environmental burden in various industries. The industrial value of the present invention is high.
以下、本発明を詳細に説明するが、以下に記載する構成要件の説明は、本発明の実施態様の代表例であり、これらの内容に本発明は限定されるものではない。先ず、本発明の第１及び第２の要旨に記載のポリアミド樹脂について説明する。本発明の第１及び第２の要旨に記載のポリアミド樹脂は、ジカルボン酸単位としてアジピン酸単位を含有し、ジアミン単位としてペンタメチレンジアミン単位およびヘキサメチレンジアミン単位を含有する構成成分を有する。 Hereinafter, the present invention will be described in detail. However, the description of the constituent elements described below is a representative example of embodiments of the present invention, and the present invention is not limited to these contents. First, the polyamide resin described in the first and second aspects of the present invention will be described. The polyamide resin described in the first and second aspects of the present invention contains adipic acid units as dicarboxylic acid units, and has constituent components containing pentamethylenediamine units and hexamethylenediamine units as diamine units.
ポリアミド樹脂を構成するジカルボン酸単位中のアジピン酸単位の含有量は、通常９０重量％以上、好ましくは９５重量％以上であり、アジピン酸単位のみから成っていてもよい。ポリアミド樹脂を構成するジアミン単位中のペンタメチレンジアミン単位およびヘキサメチレンジアミン単位の合計の含有量は、通常９０重量％以上、好ましくは９５重量％以上であり、ペンタメチレンジアミン単位およびヘキサメチレンジアミン単位のみから成っていてもよい。 The content of adipic acid units in the dicarboxylic acid units constituting the polyamide resin is usually 90% by weight or more, preferably 95% by weight or more, and may be composed of only adipic acid units. The total content of pentamethylenediamine units and hexamethylenediamine units in the diamine units constituting the polyamide resin is usually 90% by weight or more, preferably 95% by weight or more. Only pentamethylenediamine units and hexamethylenediamine units are included. May consist of:
本発明の第１の要旨に記載のポリアミド樹脂の場合、ジアミン単位中のペンタメチレンジアミン単位とヘキサメチレンジアミン単位との重量比は、９５：５〜５：９５、好ましくは９５：５〜６０：４０、更に好ましくは９０：１０〜７０：３０である。本発明の第２の要旨に記載のポリアミド樹脂の場合、ジアミン単位中のペンタメチレンジアミン単位とヘキサメチレンジアミン単位との重量比は、９５：５〜６０：４０、好ましくは９２．５：７．５〜６５：３５、更に好ましくは９０：１０〜７０：３０である。ペンタメチレンジアミンの重量比が９５を超えて多い場合、振動溶着強度、滞留熱安定性およびフィラメントの透明性が低下する。一方、ペンタメチレンジアミンの含有量が上記の範囲より少ない場合、振動溶着強度、滞留熱安定性、低温靭性、フィラメントの透明性およびバイオマス比率が低下する。なお、ポリアミド樹脂中のペンタメチレンジアミン単位とヘキサメチレンジアミン単位との重量比は、例えば以下の方法によって求めることが出来る。すなわち、ポリアミド樹脂を酸またはアルカリによって加水分解して構成単位であるペンタメチレンジアミン、ヘキサメチレンジアミン及びアジピン酸に分解し、液体クロマトグラフィー等によって、予め作成した検量線を使用して各成分の含有比率を求める。 In the case of the polyamide resin described in the first aspect of the present invention, the weight ratio of the pentamethylenediamine unit to the hexamethylenediamine unit in the diamine unit is 95: 5 to 5:95, preferably 95: 5 to 60: 40, more preferably 90:10 to 70:30. In the case of the polyamide resin described in the second aspect of the present invention, the weight ratio of the pentamethylenediamine unit to the hexamethylenediamine unit in the diamine unit is 95: 5 to 60:40, preferably 92.5: 7. 5 to 65:35, more preferably 90:10 to 70:30. When the weight ratio of pentamethylenediamine exceeds 95, vibration welding strength, residence heat stability and filament transparency are lowered. On the other hand, when the content of pentamethylenediamine is less than the above range, vibration welding strength, residence heat stability, low temperature toughness, filament transparency and biomass ratio are lowered. In addition, the weight ratio of the pentamethylenediamine unit and the hexamethylenediamine unit in the polyamide resin can be obtained by, for example, the following method. That is, the polyamide resin is hydrolyzed with acid or alkali to be decomposed into the structural units pentamethylenediamine, hexamethylenediamine and adipic acid, and each component is contained using a calibration curve prepared in advance by liquid chromatography or the like. Find the ratio.
本発明のポリアミド樹脂は、上記の構成単位を有していれば、ホモポリアミドのブレンド物であっても、共重合体であってもよい。すなわち、ポリアミド５６ホモポリマーとポリアミド６６ホモポリマーのブレンド物であっても、ペンタメチレンジアミン、ヘキサメチレンジアミン、アジピン酸を構成単位とする共重合ポリアミドであってもよく、共重合ポリアミドが本発明の効果を達成する上で特に好ましい。 The polyamide resin of the present invention may be a homopolyamide blend or a copolymer as long as it has the above structural units. That is, it may be a blend of polyamide 56 homopolymer and polyamide 66 homopolymer, or may be a copolymer polyamide having pentamethylene diamine, hexamethylene diamine, or adipic acid as a structural unit. It is particularly preferable for achieving the effect.
本発明のポリアミド樹脂は、構成成分の通常１０重量％未満、好ましくは５重量％未満で、且つ、本発明の効果を損なわない範囲において、必須構成単位であるペンタメチレンジアミン、ヘキサメチレンジアミン及びアジピン酸以外の共重合成分が含有されていてもよい。共重合成分としては、６−アミノカプロン酸、１１−アミノウンデカン酸、１２−アミノドデカン酸、パラアミノメチル安息香酸などのアミノ酸、ε−カプロラクタム、ω−ラウロラクタム等のラクタムが挙げられる。 The polyamide resin of the present invention contains pentamethylenediamine, hexamethylenediamine, and adipine, which are essential structural units, as long as they are usually less than 10% by weight, preferably less than 5% by weight, and do not impair the effects of the present invention. Copolymerization components other than acid may be contained. Examples of the copolymer component include amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and paraaminomethylbenzoic acid, and lactams such as ε-caprolactam and ω-laurolactam.
共重合成分であるジカルボン酸としては、シュウ酸、マロン酸、コハク酸、グルタル酸、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、ウンデカン二酸、ドデカン二酸、ブラシリン酸、テトラデカン二酸、ペンタデカン二酸、オクタデカン二酸などの脂肪族ジカルボン酸、シクロヘキサンジカルボン酸などの脂環式ジカルボン酸、フタル酸、イソフタル酸、テレフタル酸、ナフタレンジカルボン酸などの芳香族ジカルボン酸が挙げられる。 Dicarboxylic acids that are copolymerization components include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassic acid, tetradecanediic acid. Examples thereof include aliphatic dicarboxylic acids such as acid, pentadecanedioic acid and octadecanedioic acid, alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, and aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid and naphthalenedicarboxylic acid.
共重合成分であるジアミンとしては、エチレンジアミン、１，３−ジアミノプロパン、１，４−ジアミノブタン、１，７−ジアミノヘプタン、１，８−ジアミノオクタン、１，９−ジアミノノナン、１，１０−ジアミノデカン、１，１１−ジアミノウンデカン、１，１２−ジアミノドデカン、１，１３−ジアミノトリデカン、１，１４−ジアミノテトラデカン、１，１５−ジアミノペンタデカン、１，１６−ジアミノヘキサデカン、１，１７−ジアミノヘプタデカン、１，１８−ジアミノオクタデカン、１，１９−ジアミノノナデカン、１，２０−ジアミノエイコサン、２−メチル−１，５−ジアミノペンタン等の脂肪族ジアミン、シクロヘキサンジアミン、ビス−（４−アミノヘキシル）メタン等の脂環式ジアミン、キシリレンジアミン等の芳香族ジアミンが挙げられる。 Examples of the diamine as a copolymerization component include ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, and 1,10-diamino. Decane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,13-diaminotridecane, 1,14-diaminotetradecane, 1,15-diaminopentadecane, 1,16-diaminohexadecane, 1,17-diamino Heptadecane, 1,18-diaminooctadecane, 1,19-diaminononadecane, 1,20-diaminoeicosane, aliphatic diamines such as 2-methyl-1,5-diaminopentane, cyclohexanediamine, bis- (4- Aminohexyl) Alicyclic diamines such as methane, xylylenediamine, etc. Aromatic diamines.
本発明のポリアミド樹脂の重合度は特に制限されず、２５℃におけるポリアミド樹脂の９８重量％硫酸溶液（ポリアミド樹脂の濃度：０．０１ｇ／ｍｌ）の相対粘度は、通常１．５〜８．０、好ましくは１．８〜５．０である。相対粘度が１．５未満の場合、実用的強度が不十分なことがあり、８．０を超えると、流動性が低下し、成型加工性が損なわれることがある。 The degree of polymerization of the polyamide resin of the present invention is not particularly limited, and the relative viscosity of a 98% by weight sulfuric acid solution of polyamide resin (concentration of polyamide resin: 0.01 g / ml) at 25 ° C. is usually 1.5 to 8.0. , Preferably 1.8 to 5.0. When the relative viscosity is less than 1.5, the practical strength may be insufficient, and when it exceeds 8.0, the fluidity may be lowered and the moldability may be impaired.
本発明のポリアミド樹脂は、ＤＳＣ測定により得られる吸熱ピーク面積において、２４０℃以上の吸熱ピーク面積の割合は、全吸熱ピーク面積に対し通常６０％以下、好ましくは５０％以下である。２４０℃以上の吸熱ピーク面積の割合が６０％を超えると、振動溶着強度、滞留熱安定性、低温靭性が低下する場合がある。ＤＳＣ測定は、セイコー電子工業社製「ロボットＤＳＣ」を使用して行う。具体的な操作方法としては、得られたポリアミド樹脂約５ｍｇを試料パンに入れ、窒素雰囲気下で２９０℃まで昇温して３分間保持した。その後、２０℃／ｍｉｎの降温速度で３０℃まで降温する。引続き３０℃で３分間保持した後に、２０℃／ｍｉｎの昇温速度で３０℃から２９０℃まで昇温した際に観測される吸熱ピークを測定し、吸熱ピーク面積を求める。 In the endothermic peak area obtained by DSC measurement, the ratio of the endothermic peak area of 240 ° C. or higher is usually 60% or less, preferably 50% or less, with respect to the total endothermic peak area. When the ratio of the endothermic peak area of 240 ° C. or higher exceeds 60%, vibration welding strength, residence heat stability, and low temperature toughness may be deteriorated. The DSC measurement is performed using “Robot DSC” manufactured by Seiko Denshi Kogyo. As a specific operation method, about 5 mg of the obtained polyamide resin was put in a sample pan, heated to 290 ° C. in a nitrogen atmosphere, and held for 3 minutes. Thereafter, the temperature is decreased to 30 ° C. at a temperature decreasing rate of 20 ° C./min. Subsequently, after holding at 30 ° C. for 3 minutes, an endothermic peak observed when the temperature is raised from 30 ° C. to 290 ° C. at a temperature rising rate of 20 ° C./min is determined to determine the endothermic peak area.
図１及び図２を使用して吸熱ピーク面積の求め方を説明する。２００℃以上２９０℃以下で発現した吸熱ピークにおいて、最低の温度で発現した吸熱ピーク温度をａ（℃）、最高の温度で発現した吸熱ピーク温度をｂ（℃）とし、ａ−５０（℃）の吸熱点をＸ１、ｂ＋１０（℃）の吸熱点をＸ２とする。そして、吸熱点Ｘ１及びＸ２を結んだ直線（Ｌ）と吸熱曲線とで囲まれた部分の面積を吸熱ピーク面積とする（図１の斜線部分参照）。なお、図２に示す様に、吸熱点Ｘ１とＸ２とを結んだ直線（Ｌ）（１点鎖線で表示）がＸ１とＸ２との間で吸熱曲線と交わる場合、吸熱ピークの間の最も吸熱の少ない点ｃを経由する折れ線（Ｘ１−Ｃ−Ｘ２）と吸熱曲線で囲まれた部分（図２の斜線部分）の面積を吸熱ピーク面積とする。 The method for obtaining the endothermic peak area will be described with reference to FIGS. In the endothermic peak expressed at 200 ° C. or higher and 290 ° C. or lower, the endothermic peak temperature expressed at the lowest temperature is a (° C.), the endothermic peak temperature expressed at the highest temperature is b (° C.), and a-50 (° C.). The endothermic point is X1, and the endothermic point of b + 10 (° C.) is X2. Then, the area surrounded by the straight line (L) connecting the endothermic points X1 and X2 and the endothermic curve is defined as the endothermic peak area (see the hatched portion in FIG. 1). As shown in FIG. 2, when the straight line (L) connecting the endothermic points X1 and X2 (indicated by a one-dot chain line) intersects the endothermic curve between X1 and X2, the most endothermic between the endothermic peaks. The area of the part surrounded by the polygonal line (X1-C-X2) passing through the point c with a small amount and the endothermic curve (the hatched part in FIG. 2) is defined as the endothermic peak area.
本発明のポリアミド樹脂の高温側の融点（Ｔｍ）は、通常２２５〜２５５℃、好ましくは２３０〜２５３℃である。なお、融点は、上記のＤＳＣ測定における吸熱ピークを融点とし、吸熱ピークが２つ以上検出される場合は、複数の融点とする。 The melting point (Tm) on the high temperature side of the polyamide resin of the present invention is usually 225 to 255 ° C, preferably 230 to 253 ° C. Note that the melting point is the endothermic peak in the above DSC measurement, and when two or more endothermic peaks are detected, the melting point is a plurality of melting points.
本発明のポリアミド樹脂には、ポリアミド樹脂の製造（重縮合）から成形までの任意の段階で、本発明の効果を損なわない範囲で他の成分を配合することが出来る。他の成分としては、酸化防止剤および／または熱安定剤、耐候剤、結晶核剤、離型剤および／または滑剤、顔料、染料、可塑剤、帯電防止剤、難燃剤、他の重合体が挙げられる。 In the polyamide resin of the present invention, other components can be blended at any stage from the production (polycondensation) of the polyamide resin to the molding as long as the effects of the present invention are not impaired. Other components include antioxidants and / or heat stabilizers, weathering agents, crystal nucleating agents, mold release agents and / or lubricants, pigments, dyes, plasticizers, antistatic agents, flame retardants, and other polymers. Can be mentioned.
酸化防止剤および／または熱安定剤としては、ヒンダードフェノール系、ヒドロキノン系、ホスファイト系およびこれらの置換体、ハロゲン化銅、ヨウ素化合物などが挙げられる。耐候剤としては、レゾルシノール系、サリシレート系、ベンゾトリアゾール系、ベンゾフェノン系、ヒンダードアミン系などが挙げられる。結晶核剤としては、タルク、カオリン、シリカ、窒化ホウ素などの無機質微粒子や金属酸化物、高融点ナイロン等が挙げられる。離型剤および／または滑剤としては、脂肪族アルコール、脂肪族アミド、脂肪族ビスアミド、ビス尿素およびポリエチレンワックス等が挙げられる。顔料としては、硫化カドミウム、フタロシアニン、カーボンブラック等が挙げられる。染料としては、ニグロシン、アニリンブラック等が挙げられる。可塑剤としては、ｐ−オキシ安息香酸オクチル、Ｎ−ブチルベンゼンスルホンアミド等が挙げられる。 Examples of the antioxidant and / or heat stabilizer include hindered phenols, hydroquinones, phosphites, and substituted products thereof, copper halides, iodine compounds, and the like. Examples of the weathering agent include resorcinol, salicylate, benzotriazole, benzophenone, hindered amine and the like. Examples of the crystal nucleating agent include inorganic fine particles such as talc, kaolin, silica, and boron nitride, metal oxides, high melting point nylon, and the like. Examples of release agents and / or lubricants include aliphatic alcohols, aliphatic amides, aliphatic bisamides, bisureas, and polyethylene waxes. Examples of the pigment include cadmium sulfide, phthalocyanine, carbon black and the like. Examples of the dye include nigrosine and aniline black. Examples of the plasticizer include octyl p-oxybenzoate and N-butylbenzenesulfonamide.
帯電防止剤としては、アルキルサルフェート型アニオン系帯電防止剤、４級アンモニウム塩型カチオン系帯電防止剤、ポリオキシエチレンソルビタンモノステアレート等の非イオン系帯電防止剤、ベタイン系両性帯電防止剤が挙げられる。難燃剤としては、メラミンシアヌレート、水酸化マグネシウム、水酸化アルミニウム等の水酸化物、ポリリン酸アンモニウム、臭素化ポリスチレン、臭素化ポリフェニレンオキシド、臭素化ポリカーボネート、臭素化エポキシ樹脂あるいはこれらの臭素系難燃剤と三酸化アンチモンとの組合せが挙げられる。他の重合体としては、他のポリアミド、ポリエチレン、ポリプロピレン、ポリエステル、ポリカーボネート、ポリフェニレンエーテル、ポリフェニレンスルフィド、液晶ポリマー、ポリスルホン、ポリエーテルスルホン、ＡＢＳ樹脂、ＳＡＮ樹脂、ポリスチレン等が挙げられる。 Examples of the antistatic agent include an alkyl sulfate type anionic antistatic agent, a quaternary ammonium salt type cationic antistatic agent, a nonionic antistatic agent such as polyoxyethylene sorbitan monostearate, and a betaine amphoteric antistatic agent. It is done. Flame retardants include hydroxides such as melamine cyanurate, magnesium hydroxide, aluminum hydroxide, ammonium polyphosphate, brominated polystyrene, brominated polyphenylene oxide, brominated polycarbonate, brominated epoxy resins or brominated flame retardants thereof. And a combination of antimony trioxide and the like. Other polymers include other polyamides, polyethylene, polypropylene, polyester, polycarbonate, polyphenylene ether, polyphenylene sulfide, liquid crystal polymer, polysulfone, polyethersulfone, ABS resin, SAN resin, polystyrene, and the like.
中でも、ヒンジ付き成形品や結束バンド等の射出成形用非強化用にポリアミド樹脂を使用する場合、成形性向上のために、本発明を損なわない範囲で結晶核剤や離型剤をドライブレンドにより配合することが好ましい。 Above all, when using a polyamide resin for non-strengthening for injection molding such as hinged molded articles and binding bands, crystal nucleating agents and mold release agents are dry blended within the range that does not impair the present invention in order to improve moldability. It is preferable to mix.
本発明のポリアミド樹脂（ホモポリアミド及びポリアミド共重合体）の製造方法としては、公知の方法が使用でき、具体的には「ポリアミド樹脂ハンドブック」（日刊工業社出版：福本修編）等に開示されている。ポリアミド５６共重合体の製造方法としては、ペンタメチレンジアミンとヘキサメチレンジアミンとを通常９０重量％以上、好ましくは９５重量％以上含有する脂肪族ジアミンと、アジピン酸を通常９０重量％以上、好ましくは９５重量％以上含有するジカルボン酸とを重縮合して得る方法が好ましい。更に具体的には、ペンタメチレンジアミンとアジピン酸の塩、ヘキサメチレンジアミンとアジピン酸の塩を調製し、水の共存下、これらを混合し、加熱して脱水反応を進行させる方法（加熱重縮合）が好ましい。この場合、ペンタメチレンジアミンとアジピン酸との塩、ヘキサメチレンジアミンとアジピン酸との塩の混合比を変化させることによって、ポリアミド中の共重合組成比を変化させることが出来、この混合比は、脂肪族ジアミンとジカルボン酸とのモル比が通常１．００〜１．０５：１の範囲となる様にすることが好ましい。 As a method for producing the polyamide resin (homopolyamide and polyamide copolymer) of the present invention, known methods can be used, and specifically disclosed in “Polyamide Resin Handbook” (published by Nikkan Kogyo Co., Ltd .: Osamu Fukumoto). ing. As a method for producing the polyamide 56 copolymer, an aliphatic diamine containing pentamethylenediamine and hexamethylenediamine is usually 90% by weight or more, preferably 95% by weight or more, and adipic acid is usually 90% by weight or more, preferably A method obtained by polycondensation with 95% by weight or more of a dicarboxylic acid is preferred. More specifically, a method of preparing a salt of pentamethylene diamine and adipic acid, a salt of hexamethylene diamine and adipic acid, mixing them in the presence of water, and heating them to advance the dehydration reaction (heat polycondensation) ) Is preferred. In this case, by changing the mixing ratio of the salt of pentamethylenediamine and adipic acid and the mixing ratio of the salt of hexamethylenediamine and adipic acid, the copolymerization composition ratio in the polyamide can be changed. It is preferable that the molar ratio of the aliphatic diamine to the dicarboxylic acid is usually in the range of 1.00 to 1.05: 1.
なお、本発明において、上記の加熱重縮合とは、ポリアミド樹脂の製造時における重合反応混合物の最高到達温度を２００℃以上に上昇させる製造プロセスとする方法である。最高到達温度の上限としては、重合反応時のポリアミド樹脂の熱安定性を考慮して、通常３００℃以下である。重合方式は回分式であっても連続方式であってもよい。 In the present invention, the above-mentioned heat polycondensation is a method in which the maximum reached temperature of the polymerization reaction mixture during the production of the polyamide resin is increased to 200 ° C. or higher. The upper limit of the maximum temperature reached is usually 300 ° C. or lower in consideration of the thermal stability of the polyamide resin during the polymerization reaction. The polymerization method may be a batch method or a continuous method.
上記の方法で製造されたポリアミド樹脂は、加熱重縮合後に、更に固相重合させることが出来る。これにより、ポリアミド樹脂の分子量を高くすることが出来る。固相重合は、例えば１００℃以上融点以下の温度で、真空中、あるいは不活性ガス中で加熱することにより行うことが出来る。 The polyamide resin produced by the above method can be further subjected to solid phase polymerization after heat polycondensation. Thereby, the molecular weight of the polyamide resin can be increased. The solid phase polymerization can be performed by heating in a vacuum or an inert gas at a temperature of 100 ° C. or higher and a melting point or lower, for example.
本発明の第１の要旨に記載のポリアミド樹脂において、原料成分であるペンタメチレンジアミンは、リジン脱炭酸酵素、リジン脱炭酸酵素を産生する細胞または当該細胞の処理物を使用してリジンから産出される。また、本発明の第２の要旨に記載のポリアミド樹脂においても、原料成分であるペンタメチレンジアミンは、リジン脱炭酸酵素、リジン脱炭酸酵素を産生する細胞または当該細胞の処理物を使用してリジンから産出されることが好ましい。これによりバイオマス比率（ポリアミド樹脂の使用原料中に占めるバイオマス由来原料の割合）を高く出来る。本発明のポリアミド樹脂は、バイオマス比率（ポリアミド樹脂の使用原料中に占めるバイオマス由来原料の割合）が５％以上であることが好ましい。５％未満の場合、地球温暖化の原因となる二酸化炭素の発生を抑制する効果が得られなくなる。 In the polyamide resin described in the first aspect of the present invention, pentamethylenediamine as a raw material component is produced from lysine using lysine decarboxylase, a cell that produces lysine decarboxylase, or a processed product of the cell. The Also in the polyamide resin described in the second aspect of the present invention, pentamethylenediamine as a raw material component is lysine using lysine decarboxylase, a cell producing lysine decarboxylase, or a treated product of the cell. Is preferably produced from Thereby, the biomass ratio (the ratio of the biomass-derived raw material in the used raw material of the polyamide resin) can be increased. The polyamide resin of the present invention preferably has a biomass ratio (ratio of biomass-derived raw material in the used raw material of the polyamide resin) of 5% or more. If it is less than 5%, the effect of suppressing the generation of carbon dioxide causing global warming cannot be obtained.
上記のペンタメチレンジアミンは、具体的には、例えば以下の方法によって製造することが出来る。すなわち、リジン溶液に、同溶液のｐＨが酵素的脱炭酸反応に適したｐＨに維持される様に酸を加えながらリジンの酵素的脱炭酸反応を行う。ここで使用する酸としては、塩酸、硫酸、リン酸などの無機酸や、酢酸などの有機酸が挙げられる。通常の分離精製方法により、得られた反応生成液から遊離ペンタメチレンジアミンを採取することが出来る。また、上記の酸として、アジピン酸などのジカルボン酸を使用すれば、直接ポリアミドの製造原料となるペンタメチレンジアミン・ジカルボン酸塩を採取することも出来る。なお、酸としてアジピン酸を使用し、リジンの酵素的脱炭酸反応によりペンタメチレンジアミン・アジピン酸塩を製造する方法は、特開２００５−６６５０号公報に記載されている。 Specifically, the above pentamethylenediamine can be produced, for example, by the following method. That is, lysine is subjected to enzymatic decarboxylation while adding an acid to the lysine solution so that the pH of the solution is maintained at a pH suitable for enzymatic decarboxylation. Examples of the acid used here include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, and organic acids such as acetic acid. Free pentamethylene diamine can be collected from the obtained reaction product solution by an ordinary separation and purification method. In addition, when a dicarboxylic acid such as adipic acid is used as the acid, pentamethylenediamine dicarboxylic acid salt as a raw material for producing polyamide can be directly collected. A method for producing pentamethylenediamine / adipate by enzymatic decarboxylation of lysine using adipic acid as an acid is described in JP-A-2005-6650.
次に、本発明の第３の要旨であるポリアミド樹脂組成物について説明する。本発明のポリアミド樹脂組成物は、本発明の第１又は第２の要旨のポリアミド樹脂と無機充填材とを含有する。 Next, the polyamide resin composition which is the 3rd summary of this invention is demonstrated. The polyamide resin composition of the present invention contains the polyamide resin of the first or second aspect of the present invention and an inorganic filler.
無機充填材としては、グラファイト、硫酸バリウム、硫酸マグネシウム、炭酸カルシウム、炭酸マグネシウム、酸化アンチモン、酸化チタン、酸化アルミニウム、酸化亜鉛、酸化鉄、硫化亜鉛、亜鉛、鉛、ニッケル、アルミニウム、銅、鉄、ステンレス、ガラス繊維、ガラスフレーク、ガラスビーズ、炭素繊維、タルク、シリカ、カオリン、クレー、ワラストナイト、マイカ、窒化硼素、チタン酸カリウム、硼酸アルミニウム、ベントナイト、モンモリロナイト、合成雲母などが挙げられ、中でも補強効果が高く、比較的安価なガラス繊維が好ましい。 Inorganic fillers include graphite, barium sulfate, magnesium sulfate, calcium carbonate, magnesium carbonate, antimony oxide, titanium oxide, aluminum oxide, zinc oxide, iron oxide, zinc sulfide, zinc, lead, nickel, aluminum, copper, iron, Stainless steel, glass fiber, glass flake, glass bead, carbon fiber, talc, silica, kaolin, clay, wollastonite, mica, boron nitride, potassium titanate, aluminum borate, bentonite, montmorillonite, synthetic mica, etc. Glass fiber having a high reinforcing effect and relatively inexpensive is preferable.
ガラス繊維としては、熱可塑性樹脂に通常使用されるガラス繊維が使用でき、中でもＥガラス（無アルカリガラス）から製造されるチョップドストランドが好ましい。繊維径は、通常１〜２０μｍ、好ましくは５〜１５μｍである。ガラス繊維は、ポリアミド樹脂との接着性向上のために、シランカップリング剤などで表面処理されていることが好ましい。 As a glass fiber, the glass fiber normally used for a thermoplastic resin can be used, Especially the chopped strand manufactured from E glass (non-alkali glass) is preferable. The fiber diameter is usually 1 to 20 μm, preferably 5 to 15 μm. The glass fiber is preferably surface-treated with a silane coupling agent or the like in order to improve adhesion with the polyamide resin.
無機充填材のポリアミド樹脂への配合は、ポリアミド樹脂の製造（重縮合）から成形までの任意の段階で実施できるが、ポリアミド樹脂成形中の押出機を使用して溶融混練することが好ましい。 The blending of the inorganic filler into the polyamide resin can be carried out at any stage from the production (polycondensation) of the polyamide resin to the molding, but it is preferable to melt and knead using an extruder during the polyamide resin molding.
ポリアミド樹脂１００重量部に対する無機充填材の配合量は０．０１〜１５０重量部、好ましくは０．０１〜１００重量部である。無機充填材の配合量が１５０重量部を超えると流動性が損なわれることがある。 The compounding amount of the inorganic filler with respect to 100 parts by weight of the polyamide resin is 0.01 to 150 parts by weight, preferably 0.01 to 100 parts by weight. If the blending amount of the inorganic filler exceeds 150 parts by weight, fluidity may be impaired.
本発明のポリアミド樹脂組成物には、ポリアミド樹脂の製造（重縮合）から成形までの任意の段階で、本発明の効果を損なわない範囲で他の成分を配合することが出来る。他の成分としては、本発明の第１及び第２の要旨で説明した酸化防止剤および／または熱安定剤、耐候剤、結晶核剤、離型剤および／または滑剤、顔料、染料、可塑剤、帯電防止剤、難燃剤、他の重合体が使用できる。 In the polyamide resin composition of the present invention, other components can be blended at any stage from the production (polycondensation) of the polyamide resin to molding within a range not impairing the effects of the present invention. As other components, antioxidants and / or heat stabilizers, weathering agents, crystal nucleating agents, release agents and / or lubricants described in the first and second aspects of the present invention, pigments, dyes, plasticizers Antistatic agents, flame retardants, and other polymers can be used.
次に、本発明の第４の要旨である振動溶着成形品、本発明の第５の要旨であるヒンジ付き成形品、本発明の第６の要旨である結束バンド及び本発明の第７の要旨であるフィラメントについて説明する。本発明の振動溶着成形品、ヒンジ付き成形品、結束バンド及びフィラメントは、本発明の第１又は第２の要旨のポリアミド樹脂あるいは本発明の第３の要旨のポリアミド樹脂組成物を含有する。 Next, a vibration welded molded product that is the fourth gist of the present invention, a molded product with a hinge that is the fifth gist of the present invention, a binding band that is the sixth gist of the present invention, and a seventh gist of the present invention. The filament which is is demonstrated. The vibration welding molded product, hinged molded product, binding band and filament of the present invention contain the polyamide resin of the first or second aspect of the present invention or the polyamide resin composition of the third aspect of the present invention.
本発明における振動溶着成形品は以下の方法によって得られる。先ず、ポリアミド樹脂またはポリアミド樹脂組成物を使用して、複数の部品をそれぞれ一次成形する。当該一次成形品の成型方法は特に制限されず、射出成形、フィルム成型、溶融紡糸、ブロー成型、真空成型などの任意の成型方法が使用できるが、中でも射出成形が好ましい。一次成形品の形状は特に制限されず、所望の形状が可能である。また、複数の一次成形品は、お互いに同じ形状であっても異なる形状であってもよい。 The vibration welding molded product in the present invention is obtained by the following method. First, a plurality of parts are each primary molded using a polyamide resin or a polyamide resin composition. The molding method of the primary molded product is not particularly limited, and any molding method such as injection molding, film molding, melt spinning, blow molding, vacuum molding, or the like can be used, and among these, injection molding is preferable. The shape of the primary molded product is not particularly limited, and a desired shape is possible. The plurality of primary molded products may have the same shape or different shapes.
次に、一次成形された複数の成形品を振動溶着により接合して、振動溶着成形品を得る。振動溶着における、振動の周波数は通常１００〜３００Ｈｚであり、振幅は通常０．５〜２．０ｍｍ、好ましくは０．８〜１．６ｍｍである。溶着圧力は、通常０．５〜１０ＭＰａ、好ましくは０．８〜６ＭＰａである。溶着圧力が、高過ぎる場合および低過ぎる場合、溶着強度が低下することがある。特に溶着圧力が低過ぎる場合、溶着不十分な箇所が生じ、成形品が中空体の場合は気密不良の原因となる。所定の圧力下における溶着時間は、目的とする溶け代が得られる様に設定し、振動を停止した後の保持時間は、溶着部が十分固化する様に設定する。 Next, a plurality of primary molded products are joined by vibration welding to obtain a vibration welding molded product. In vibration welding, the frequency of vibration is usually 100 to 300 Hz, and the amplitude is usually 0.5 to 2.0 mm, preferably 0.8 to 1.6 mm. The welding pressure is usually 0.5 to 10 MPa, preferably 0.8 to 6 MPa. If the welding pressure is too high or too low, the welding strength may decrease. In particular, when the welding pressure is too low, there are places where welding is insufficient, and when the molded product is a hollow body, it causes a hermetic failure. The welding time under a predetermined pressure is set so that a desired welding allowance is obtained, and the holding time after the vibration is stopped is set so that the welded portion is sufficiently solidified.
本発明のヒンジ付き成形品および結束バンドは、本発明のポリアミド樹脂またはポリアミド樹脂組成物を使用して、振動溶着成形品における一次成形品の成型方法と同様に任意の成形方法により所望の形状に成形を行うことによって得られる。成形方法としては、特に射出成形が好ましい。 The hinged molded product and the binding band of the present invention are formed into a desired shape by an arbitrary molding method in the same manner as the molding method of the primary molded product in the vibration welded molded product, using the polyamide resin or the polyamide resin composition of the present invention. It can be obtained by molding. As the molding method, injection molding is particularly preferable.
ヒンジ付き成形品および結束バンドの具体例としては、ヒンジ付きクリップ、ヒンジ付きコネクター、ヒンジ付き結束バンド等が挙げられ、ヒンジ部の肉厚は、通常０．２〜０．８ｍｍ、好ましくは０．３〜０．６ｍｍである。ヒンジ部の肉厚が０．２ｍｍ未満の場合、ヒンジ部におけるポリアミド樹脂の流動性が悪くなることがある。ヒンジ部の肉厚が０．８ｍｍを超えると、ヒンジ部における結晶化度が高くなり、ヒンジ部折り曲げ時に割れやすくなることがある。 Specific examples of the hinged molded article and the binding band include a hinged clip, a hinged connector, a hinged binding band, and the like. The thickness of the hinge part is usually 0.2 to 0.8 mm, preferably 0. 3 to 0.6 mm. When the thickness of the hinge part is less than 0.2 mm, the fluidity of the polyamide resin in the hinge part may deteriorate. If the thickness of the hinge part exceeds 0.8 mm, the crystallinity in the hinge part increases, and the hinge part may be easily broken when bent.
本発明のフィラメントは、本発明のポリアミド樹脂またはポリアミド樹脂組成物を使用して、溶融紡糸成型方法により、フィラメントの形状に成型することにより得られる。本発明のフィラメントは、マットの構成層（基布、パイル糸およびパッキング層）におけるパイル糸の部分に使用されることが好ましい。特に、防汚性が要求されるマットでは、本発明のフィラメントに、タルク、シリカ、カオリン、クレー等の結晶核剤を添加することが好ましい。本発明のフィラメントは、マットの構成層以外でも、家庭用カーペット、オフィス用カーペット、自動車用カーペット、衣料品などの原糸としても好適に使用される。 The filament of the present invention is obtained by molding the filament resin or polyamide resin composition of the present invention into a filament shape by a melt spinning molding method. The filament of the present invention is preferably used in a pile yarn portion in a constituent layer (base fabric, pile yarn and packing layer) of the mat. In particular, in a mat that requires antifouling properties, it is preferable to add a crystal nucleating agent such as talc, silica, kaolin, or clay to the filament of the present invention. The filament of the present invention can be suitably used as a raw yarn for household carpets, office carpets, automobile carpets, clothing, etc., in addition to the mat layer.
上述の様に、本発明のポリアミド樹脂およびポリアミド樹脂組成物は、射出成形、フィルム成型、溶融紡糸、ブロー成型、真空成型などの任意の成型方法により、所望の形状に成型でき、例えば射出成形品、フィルム、シート、フィラメント、テーパードフィラメント、繊維などに使用でき、さらに、接着剤、塗料などにも使用できる。 As described above, the polyamide resin and the polyamide resin composition of the present invention can be molded into a desired shape by any molding method such as injection molding, film molding, melt spinning, blow molding, vacuum molding, for example, an injection molded product. It can be used for films, sheets, filaments, tapered filaments, fibers and the like, and can also be used for adhesives, paints, and the like.
具体的な用途例としては、自動車・車両関連部品として、インテークマニホールド、ヒンジ付きクリップ（ヒンジ付き成形品）、結束バンド、レゾネーター、エアークリーナー、エンジンカバー、ロッカーカバー、シリンダーヘッドカバー、タイミングベルトカバー、ガソリンタンク、ガソリンサブタンク、ラジエータータンク、インタークーラータンク、オイルリザーバータンク、オイルパン、電動パワステギヤ、オイルストレーナー、キャニスター、エンジンマウント、ジャンクションブロック、リレーブロック、コネクター、コルゲートチューブ、プロテクター等の自動車用アンダーフード部品、ドアハンドル、フェンダー、フードバルジ、ルーフレールレグ、ドアミラーステー、バンパー、スポイラー、ホイールカバー等の自動車用外装部品、カップホルダー、コンソールボックス、アクセルペダル、クラッチペダル、シフトレバー台座、シフトレバーノブ等の自動車用内装部品が挙げられる。 Specific application examples include intake manifolds, hinged clips (molds with hinges), cable ties, resonators, air cleaners, engine covers, rocker covers, cylinder head covers, timing belt covers, gasoline as automobile / vehicle related parts. Tanks, gasoline sub tanks, radiator tanks, intercooler tanks, oil reservoir tanks, oil pans, electric power steering gears, oil strainers, canisters, engine mounts, junction blocks, relay blocks, connectors, corrugated tubes, protector and other automotive underhood parts, doors Handles, fenders, hood bulges, roof rail legs, door mirror stays, bumpers, spoilers, wheel covers, etc. Instrumentation components, cup holders, console boxes, accelerator pedals, clutch pedals, shift lever pedestals, automobile interior parts such as a shift lever knob and the like.
さらに、本発明のポリアミド樹脂およびポリアミド樹脂組成物は、釣り糸、漁網などの漁業関連資材、スイッチ類、超小型スライドスイッチ、ＤＩＰスイッチ、スイッチのハウジング、ランプソケット、結束バンド、コネクタ、コネクタのハウジング、コネクタのシェル、ＩＣソケット類、コイルボビン、ボビンカバー、リレー、リレーボックス、コンデンサーケース、モーターの内部部品、小型モーターケース、ギヤ・カム、ダンシングプーリー、スペーサー、インシュレーター、キャスター、端子台、電動工具のハウジング、スターターの絶縁部分、ヒューズボックス、ターミナルのハウジング、ベアリングリテーナー、スピーカー振動板、耐熱容器、電子レンジ部品、炊飯器部品、プリンタリボンガイド等に代表される電気・電子関連部品、家庭・事務電気製品部品、コンピューター関連部品、ファクシミリ・複写機関連部品、機械関連部品など各種用途に使用できる。 Furthermore, the polyamide resin and the polyamide resin composition of the present invention include fishing-related materials such as fishing lines and fishing nets, switches, ultra-small slide switches, DIP switches, switch housings, lamp sockets, binding bands, connectors, connector housings, Connector shell, IC socket, coil bobbin, bobbin cover, relay, relay box, condenser case, motor internal parts, small motor case, gear cam, dancing pulley, spacer, insulator, caster, terminal block, power tool housing , Insulation parts of starters, fuse boxes, terminal housings, bearing retainers, speaker diaphragms, heat-resistant containers, microwave oven parts, rice cooker parts, printer ribbon guides, etc. Goods, household and office electric appliances parts, computer-related parts, facsimile-copier-related parts, can be used in various applications such as machine-related parts.
以下、本発明を実施例により更に詳細に説明するが、本発明は、その要旨を超えない限り、以下の実施例に限定されるものではない。以下にポリアミド樹脂、ポリアミド樹脂組成物およびその成形品の各種特性の評価方法について説明する。 EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to a following example, unless the summary is exceeded. Below, the evaluation method of the various characteristics of a polyamide resin, a polyamide resin composition, and its molded article is demonstrated.
（１）相対粘度（ηｒ）：
ポリアミド樹脂の９８％硫酸溶液（濃度：０．０１ｇ／ｍｌ）を調製し、２５℃で、オストワルド式粘度計を使用して測定した。
(1) Relative viscosity (ηr):
A 98% sulfuric acid solution of polyamide resin (concentration: 0.01 g / ml) was prepared and measured at 25 ° C. using an Ostwald viscometer.
（２）ＤＳＣ（示差走査熱量測定）：
セイコー電子工業社製「ロボットＤＳＣ」を使用して行った。先ず、ポリアミド樹脂約５ｍｇを試料パンに入れ、窒素雰囲気下で２９０℃に昇温して３分間保持して完全に融解させた後に、２０℃／ｍｉｎの降温速度で３０℃まで降温した際に観測される発熱ピークの温度を降温結晶化温度（Ｔｃ［℃］）とする。引続き３０℃で３分間保持した後に、２０℃／ｍｉｎの昇温速度で３０℃から２９０度まで昇温した際に観測される吸熱ピークを測定し、吸熱ピーク面積を求めた。観測された吸熱ピークの温度を融点（Ｔｍ）とし、吸熱ピークが複数検出される場合は、複数の融点とした。
(2) DSC (differential scanning calorimetry):
This was performed using a “Robot DSC” manufactured by Seiko Denshi Kogyo. First, about 5 mg of polyamide resin was placed in a sample pan, heated to 290 ° C. in a nitrogen atmosphere, held for 3 minutes and completely melted, and then cooled to 30 ° C. at a rate of 20 ° C./min. The temperature of the observed exothermic peak is defined as the cooling crystallization temperature (Tc [° C.]). Subsequently, after holding at 30 ° C. for 3 minutes, an endothermic peak observed when the temperature was raised from 30 ° C. to 290 ° C. at a temperature rising rate of 20 ° C./min was measured to obtain an endothermic peak area. The temperature of the observed endothermic peak was defined as the melting point (Tm), and when a plurality of endothermic peaks were detected, the melting point was defined as a plurality of melting points.
（３）滞留熱安定性：
容量１８ｃｃの試験管にポリアミド樹脂７ｇを入れ、窒素雰囲気で密閉下、融点＋３０℃の温度のオイルバスに試験管を浸漬した。９時間後に試料を回収して相対粘度を測定した。滞留試験前後の相対粘度から粘度保持率を算出した。
(3) Stability thermal stability:
7 g of polyamide resin was put into a test tube having a capacity of 18 cc, and the test tube was immersed in an oil bath having a melting point + 30 ° C. in a sealed atmosphere in a nitrogen atmosphere. The sample was collected after 9 hours and the relative viscosity was measured. The viscosity retention was calculated from the relative viscosity before and after the residence test.
（４）振動溶着試験：
（４−１）中空体の耐圧試験：
(4) Vibration welding test:
(4-1) Pressure resistance test of hollow body:
＜中空体部品の一次成形＞
ガラス繊維強化ポリアミド樹脂組成物を使用し、図３−（ａ）及び（ｂ）に示す一次成形品である一対の中空体部品（肉厚：２ｍｍ、溶着面の幅：４ｍｍ）を得た。成形は、東芝機械社製ＩＳ３５０型射出成形機を使用し、樹脂温度２７０℃、金型温度８０℃で行った。
<Primary molding of hollow body parts>
A glass fiber reinforced polyamide resin composition was used to obtain a pair of hollow body parts (thickness: 2 mm, welded surface width: 4 mm), which are primary molded products shown in FIGS. Molding was performed using an IS350 type injection molding machine manufactured by Toshiba Machine Co., Ltd. at a resin temperature of 270 ° C. and a mold temperature of 80 ° C.
＜中空体部品の振動溶着＞
日本エマソン社製の振動溶着機「ＶＩＢＲＡＴＩＯＮ ＷＥＬＤＥＲ Ｍｏｄｅｌ２８００」を使用して、上記の一対の中空体部品の振動溶着を行った。振動溶着条件は、表１に示す溶着圧力、周波数２４０Ｈｚ、振幅１．５ｍｍ、溶け代１．５ｍｍ、保持圧力は振動停止直前の溶着圧力と同等、保持時間５．０秒とし、図４に示す振動溶着成形品（中空体）を得た。この際、溶け代をコントロールするため、日本エマソン社製ＣＸ１３２型非接触ＷＤＣ溶着寸法制御装置を使用した。
<Vibration welding of hollow body parts>
Using a vibration welding machine “VIBRATION WELDER Model 2800” manufactured by Emerson Japan, the above-mentioned pair of hollow body parts was vibration welded. The vibration welding conditions are the welding pressure shown in Table 1, the frequency 240 Hz, the amplitude 1.5 mm, the welding allowance 1.5 mm, the holding pressure is the same as the welding pressure immediately before the vibration stop, the holding time 5.0 seconds, and shown in FIG. A vibration welding molded product (hollow body) was obtained. At this time, a CX132 non-contact WDC welding size control device manufactured by Nippon Emerson Co., Ltd. was used to control the melting allowance.
＜中空体の耐圧試験＞
得られた中空体について耐圧試験を行った。東洋精機製作所製耐圧試験機を使用し、中空体の上部開口部（１）及び（１’）（開口部：３２ｍｍφ）の２カ所を塞ぎ、下部開口部（２）（開口部：３２ｍｍφ）より加圧傾斜速度９８０ｋＰａ／ｍｉｎの水圧により加圧し、振動溶着成形品破裂時の圧力を測定した。試験は、各溶着圧力毎に３回行い、その平均値を耐圧強度とした。
<Pressure test of hollow body>
The obtained hollow body was subjected to a pressure resistance test. Using a pressure tester manufactured by Toyo Seiki Seisakusho, close the upper opening (1) and (1 ') (opening: 32 mmφ) of the hollow body, and from the lower opening (2) (opening: 32 mmφ) Pressurization was performed with a water pressure of a pressure ramp rate of 980 kPa / min, and the pressure at the time of bursting of the vibration welded product was measured. The test was performed three times for each welding pressure, and the average value was taken as the pressure strength.
（４−２）短冊型テストピースの振動溶着強度試験： (4-2) Vibration welding strength test of strip type test piece:
＜短冊型テストピースの一次成形＞
ガラス繊維強化ポリアミド樹脂組成物を使用し、２５ｍｍ×４ｍｍの底面を有し、高さが６０ｍｍである直方体形状の一次成形品を２つ作成した。成形は、日本製鋼所社製Ｊ７５−ＥＤ型射出成形機を使用し、樹脂温度２７０℃、金型温度８０℃で行った。
<Primary molding of strip-shaped test pieces>
Two primary molded products having a rectangular parallelepiped shape having a bottom of 25 mm × 4 mm and a height of 60 mm were prepared using a glass fiber reinforced polyamide resin composition. Molding was performed using a J75-ED type injection molding machine manufactured by Nippon Steel Works, at a resin temperature of 270 ° C. and a mold temperature of 80 ° C.
＜短冊型テストピースの振動溶着＞
日本エマソン社製の振動溶着機「ＶＩＢＲＡＴＩＯＮ ＷＥＬＤＥＲ Ｍｏｄｅｌ２８００」を使用して、上記の２つの一次成形品の底面同士の振動溶着を行った。振動溶着条件は、表１に示す溶着圧力、周波数２４０Ｈｚ、振幅１．５ｍｍ、溶け代１．５ｍｍ、保持圧力は振動停止直前の溶着圧力と同等、保持時間５．０秒とし、２つの一次成形品が底面同士で溶着した振動溶着成形品を得た。この際、溶け代をコントロールするため、日本エマソン社製ＣＸ１３２型非接触ＷＤＣ溶着寸法制御装置を使用した。
<Vibration welding of strip type test piece>
Using the vibration welding machine “VIBRATION WELDER Model 2800” manufactured by Emerson Japan, the vibration welding between the bottom surfaces of the two primary molded products was performed. The vibration welding conditions are as follows: welding pressure shown in Table 1, frequency 240 Hz, amplitude 1.5 mm, welding allowance 1.5 mm, holding pressure is the same as the welding pressure just before vibration stop, holding time 5.0 seconds, and two primary moldings A vibration welding molded product was obtained in which the products were welded at the bottom. At this time, a CX132 non-contact WDC welding size control device manufactured by Nippon Emerson Co., Ltd. was used to control the melting allowance.
＜短冊型テストピースの振動溶着強度試験＞
得られた振動溶着成形品について振動溶着強度試験を行った。エーアンドディー社製「テンシロンＵＴＭ−III−２５００」を使用し、チャック間距離６０ｍｍ、引張速度５ｍｍ／ｍｉｎにて引張試験を行い、破断時の強度を測定した。試験は、各溶着圧力毎に６本の成形品に対して行い、その平均値を振動溶着強度とした。
<Vibration welding strength test of strip type test piece>
The vibration welding strength test was performed on the obtained vibration welding molded product. Using “Tensilon UTM-III-2500” manufactured by A & D, a tensile test was performed at a distance between chucks of 60 mm and a tensile speed of 5 mm / min, and the strength at break was measured. The test was performed on six molded articles for each welding pressure, and the average value was defined as the vibration welding strength.
（５）機械物性評価（引張試験、曲げ試験、ノッチ付きシャルピー試験）：
ガラス繊維強化ポリアミド樹脂組成物および非強化ポリアミド樹脂組成物を使用し、それぞれＩＳＯ規格に準じてＩＳＯ試験片を成形した。成形は、日本製鋼所社製Ｊ７５ＥＩＩ型射出成形機を使用し、ガラス繊維強化ポリアミド樹脂組成物の場合は樹脂温度２７０℃、金型温度８０℃で、非強化ポリアミド樹脂組成物の場合では樹脂温度２６５℃、金型温度８０℃でそれぞれ行った。得られたＩＳＯ試験片を使用し、それぞれＩＳＯ規格に準じて、引張試験、曲げ試験、ノッチ付きシャルピー試験を行った。
(5) Mechanical property evaluation (tensile test, bending test, notched Charpy test):
Glass fiber reinforced polyamide resin compositions and non-reinforced polyamide resin compositions were used, and ISO test pieces were molded in accordance with ISO standards. For the molding, a J75EII type injection molding machine manufactured by Nippon Steel Co., Ltd. is used. In the case of a glass fiber reinforced polyamide resin composition, the resin temperature is 270 ° C., the mold temperature is 80 ° C., and in the case of an unreinforced polyamide resin composition, the resin temperature. Each was performed at 265 ° C. and a mold temperature of 80 ° C. Using the obtained ISO test pieces, a tensile test, a bending test, and a notched Charpy test were performed in accordance with ISO standards.
（６）低温ヒンジ性：
非強化ポリアミド樹脂組成物を使用し、図５に示すヒンジ付き成形品、図６に示す結束バンドを成形した。ヒンジ付き成形品の成形は、日精樹脂工業社製ＰＳ４０型射出成形機使用し、樹脂温度２６５℃、金型温度８０℃で行った。結束バンドの成形は、住友重機械工業社製ＳＥ５０Ｄ型射出成形機を使用し、樹脂温度２６５℃、金型温度８０℃で行った。ヒンジ部は長さ２ｍｍ、幅４０ｍｍ、肉厚０．４ｍｍであった。
(6) Low temperature hinge property:
Using the non-reinforced polyamide resin composition, a molded article with a hinge shown in FIG. 5 and a binding band shown in FIG. 6 were molded. The molded article with the hinge was molded using a PS40 type injection molding machine manufactured by Nissei Plastic Industry Co., Ltd. at a resin temperature of 265 ° C. and a mold temperature of 80 ° C. The binding band was molded using a SE50D injection molding machine manufactured by Sumitomo Heavy Industries, Ltd. at a resin temperature of 265 ° C. and a mold temperature of 80 ° C. The hinge part had a length of 2 mm, a width of 40 mm, and a wall thickness of 0.4 mm.
恒温槽内において表２に示す温度でヒンジ付き成形品を２時間冷却した。なお、恒温槽は、測定者が入室して中で試験が出来る大きなものを使用した。２時間冷却後に測定者が入室し、入室時の温度変化の影響を完全になくすために恒温槽内で１０分間待機した後、図７に示す様に、ヒンジ部の角度を９０度（直角に曲がっている状態）から１８０度（床面に対して平らな状態）にする試験を行った。具体的には、成形品の水平な面を片手で押さえ、成形品の垂直な面をもう一方の手ですばやく折り曲げる試験を行った。試験は、各温度毎に２０本のヒンジ付き成形品に対して行い、ヒンジ部が割れなかった本数を測定値とした。 The hinged molded product was cooled for 2 hours at the temperature shown in Table 2 in a thermostatic bath. In addition, the thermostat used the big thing which a tester entered and can test in. After cooling for 2 hours, the measurer enters the room, waits for 10 minutes in the thermostatic bath to completely eliminate the influence of the temperature change at the time of entry, and then, as shown in FIG. The test was performed from a bent state) to 180 degrees (a flat state with respect to the floor surface). Specifically, a test was performed in which the horizontal surface of the molded product was held with one hand and the vertical surface of the molded product was quickly bent with the other hand. The test was performed on 20 hinged molded articles at each temperature, and the number of hinge parts that did not break was used as a measured value.
（７）低温バンド折れ性：
恒温槽内において表２に示す温度で結束バンドを２時間冷却した。なお、恒温槽は、測定者が入室して中で試験が出来る大きなものを使用した。２時間冷却後に測定者が入室し、入室時の温度変化の影響を完全になくすために恒温槽内で１０分間待機した後、図８に示す様に、バンドの一端を他端に設けた挿入孔に挿入し、他端を片手で保持しながら、一端を強く引く試験を行った。試験は、各温度毎に２０本のヒンジ付き成形品に対して行い、割れなかった本数を数えた。
(7) Low temperature band foldability:
The binding band was cooled for 2 hours at the temperature shown in Table 2 in a thermostatic bath. In addition, the thermostat used the big thing which a tester entered and can test in. After cooling for 2 hours, the measurer enters the room, waits for 10 minutes in the thermostat to completely eliminate the influence of temperature change at the time of entry, and then inserts one end of the band provided at the other end as shown in FIG. A test was conducted in which one end was pulled strongly while inserting into the hole and holding the other end with one hand. The test was performed on 20 hinged molded articles at each temperature, and the number of cracked parts was counted.
（８）モノフィラメントの透明性：
ユニプラス社製４０ｍｍφ単軸押出機の先端に、ギヤポンプ及び直径０．６ｍｍで穴数１８のノズルを装着して紡糸用押出機とした。ポリアミド樹脂の融点＋２０℃の温度でポリアミド樹脂を溶融し、ポリアミド樹脂の溶融紡糸を行い、２０℃の冷却水槽に通して冷却固化させた後、９８℃にて湿熱延伸を施し、１７２℃熱風延伸槽にて２段目の延伸を行い、１６８℃熱風延伸槽にて熱固定を行い、直径０．０７９ｍｍのモノフィラメントを得た。得られたモノフィラメントの透明性を目視にて評価した。
(8) Transparency of monofilament:
A gear pump and a nozzle with a diameter of 0.6 mm and a number of holes of 18 were attached to the tip of a Uniplus 40 mmφ single-screw extruder to obtain a spinning extruder. The polyamide resin is melted at a temperature of the melting point of the polyamide resin + 20 ° C., the polyamide resin is melt-spun, passed through a 20 ° C. cooling water bath, cooled and solidified, subjected to wet heat stretching at 98 ° C., and hot air stretching at 172 ° C. Second-stage stretching was performed in a tank, and heat setting was performed in a hot air stretching tank at 168 ° C. to obtain a monofilament having a diameter of 0.079 mm. The transparency of the obtained monofilament was visually evaluated.
以下の実施例および比較例において、ヘキサメチレンジアミンとアジピン酸の等モル塩はＲｈｏｄｉａ社「ＡＨ塩」を使用した。また、ペンタメチレンジアミンとアジピン酸の等モル塩は、特開２００５−６６５０号公報の実施例１〜３に記載された方法に従って調製した。 In the following examples and comparative examples, Rhodia “AH salt” was used as an equimolar salt of hexamethylenediamine and adipic acid. Further, an equimolar salt of pentamethylenediamine and adipic acid was prepared according to the method described in Examples 1 to 3 of JP-A-2005-6650.
実施例１（ポリアミド樹脂組成物および振動溶着成形品）：
ペンタメチレンジアミンとアジピン酸の等モル塩およびヘキサメチレンジアミンとアジピン酸の等モル塩の混合物（重量比は表１を参照）２５ｋｇに水２５ｋｇを添加した後、亜燐酸１．２５ｇを添加し、窒素雰囲気下で混合物を完全に溶解させ、原料水溶液を得た。プランジャーポンプにて予め窒素置換したオートクレーブに、上記の原料水溶液を移送した。ジャケット温度を２８０℃に、オートクレーブの圧力を１．４７ＭＰａにそれぞれ調節し、内容物を２７０℃に昇温した。次に、オートクレーブ内の圧力を除々に放圧した後、更に減圧して所定の攪拌動力に到達した時点で反応終了とした。反応終了後に窒素にて復圧し、内容物をストランド状に冷却水槽へ導入した後、回転式カッターでペレット化した。得られたペレットは、１２０℃、１ｔｏｒｒ（０．１３ｋＰａ）の条件で、水分量が０．１％以下となる迄乾燥を行い、ポリアミド樹脂を得た。得られたポリアミド樹脂に対し、各種特性評価を行った。
Example 1 (Polyamide resin composition and vibration welded article):
After adding 25 kg of water to 25 kg of a mixture of equimolar salts of pentamethylenediamine and adipic acid and equimolar salts of hexamethylenediamine and adipic acid (see Table 1 for weight ratio), 1.25 g of phosphorous acid is added, The mixture was completely dissolved under a nitrogen atmosphere to obtain a raw material aqueous solution. The raw material aqueous solution was transferred to an autoclave which had been previously purged with nitrogen by a plunger pump. The jacket temperature was adjusted to 280 ° C., the autoclave pressure was adjusted to 1.47 MPa, and the contents were heated to 270 ° C. Next, after gradually releasing the pressure in the autoclave, the pressure was further reduced and the reaction was terminated when a predetermined stirring power was reached. After completion of the reaction, the pressure was restored with nitrogen, and the contents were introduced into a cooling water tank in the form of a strand and then pelletized with a rotary cutter. The obtained pellets were dried under the conditions of 120 ° C. and 1 torr (0.13 kPa) until the water content became 0.1% or less to obtain a polyamide resin. Various characteristics evaluation was performed with respect to the obtained polyamide resin.
得られたポリアミド樹脂１００重量部に、ガラス繊維として日本電気硝子社製「Ｔ２４９Ｈ」４３重量部を配合し、ガラス繊維強化ポリアミド樹脂組成物を得た。配合には、東芝機械社製ＴＥＭ−３５Ｂ型二軸混練機を使用した。折損抑制のため、ガラス繊維はサイドフィードし、溶融混練温度は２７０℃とした。得られたポリアミド樹脂組成物に対し、振動溶着試験および機械物性評価を行った。結果を表１に示す。 To 100 parts by weight of the obtained polyamide resin, 43 parts by weight of “T249H” manufactured by Nippon Electric Glass Co., Ltd. was blended as a glass fiber to obtain a glass fiber reinforced polyamide resin composition. A TEM-35B type twin screw kneader manufactured by Toshiba Machine Co., Ltd. was used for blending. In order to suppress breakage, the glass fibers were side-fed and the melt kneading temperature was 270 ° C. The obtained polyamide resin composition was subjected to vibration welding test and mechanical property evaluation. The results are shown in Table 1.
比較例１：
実施例１において、原料塩の仕込みモノマー組成を表１に示す様に変更した以外は、実施例１と同様の操作でポリアミド樹脂を得た。得られたポリアミド樹脂に対し、実施例１と同様にガラス繊維を配合し、ガラス繊維強化ポリアミド樹脂組成物を得た。得られたポリアミド樹脂組成物に対し、振動溶着試験および機械物性評価を行った。結果を表１に示す。
Comparative Example 1:
A polyamide resin was obtained in the same manner as in Example 1 except that the monomer composition of the raw material salt was changed as shown in Table 1 in Example 1. Glass fibers were blended into the obtained polyamide resin in the same manner as in Example 1 to obtain a glass fiber reinforced polyamide resin composition. The obtained polyamide resin composition was subjected to vibration welding test and mechanical property evaluation. The results are shown in Table 1.
実施例２（ポリアミド樹脂組成物、ヒンジ付き成形品および結束バンド）：
実施例１において得られたポリアミド樹脂１００重量部に、結晶核剤として平均粒子径が３．０μｍのタルクを０．０２重量部配合した後にドライブレンドし、非強化ポリアミド樹脂組成物を得た。得られたポリアミド樹脂組成物に対し、低温ヒンジ性、低温バンド折れ性および機械物性の各評価を行った。結果を表２に示す。
Example 2 (Polyamide resin composition, molded article with hinge and binding band):
Into 100 parts by weight of the polyamide resin obtained in Example 1, 0.02 part by weight of talc having an average particle size of 3.0 μm as a crystal nucleating agent was blended and then dry blended to obtain an unreinforced polyamide resin composition. Each evaluation of low temperature hinge property, low temperature band bending property, and mechanical property was performed with respect to the obtained polyamide resin composition. The results are shown in Table 2.
比較例２：
実施例１において、原料水溶液の仕込みモノマー組成を表１に示す様に変更した以外は、実施例１と同様の操作でポリアミド樹脂を得た。得られたポリアミド樹脂に対し、実施例２と同様にタルクを配合した後にドライブレンドし、非強化ポリアミド樹脂組成物を得た。得られたポリアミド樹脂組成物に対し、低温ヒンジ性、低温バンド折れ性および機械物性の各評価を行った。結果を表２に示す。
Comparative Example 2:
A polyamide resin was obtained in the same manner as in Example 1, except that the monomer composition of the raw material aqueous solution was changed as shown in Table 1 in Example 1. The obtained polyamide resin was blended with talc in the same manner as in Example 2 and then dry blended to obtain a non-reinforced polyamide resin composition. Each evaluation of low temperature hinge property, low temperature band bending property, and mechanical property was performed with respect to the obtained polyamide resin composition. The results are shown in Table 2.
比較例３：
三菱化学社製カプロラクタム２５Ｋｇ、水０．７５ｋｇ、亜リン酸水素２ナトリウム５水和物１．７４ｇを容器に入れ、窒素置換した後に１００℃にて溶解した。この原料水溶液をオートクレーブに移送し、ジャケット温度を２８０℃に設定して加熱を開始した。内容物を２７０℃迄昇温した後、オートクレーブの圧力を除々に放圧した後、更に減圧して所定の攪拌動力に到達した時点で重縮合反応を終了した。反応終了後、窒素にて復圧し、内容物をストランド状に冷却水槽へ導入後、回転式カッターでペレット化した。得られたペレットに対し、得られたペレットの１．５倍量の沸水を使用して未反応のモノマー、オリゴマーを抽出除去した。未反応物を除去したペレットは１２０℃、１ｔｏｒｒ（０．１３ｋＰａ）の条件で、水分量が０．１％以下となる迄乾燥を行い、ポリアミド樹脂を得た。得られたポリアミド樹脂に対し、各種特性評価を行った。
Comparative Example 3:
25 kg of caprolactam manufactured by Mitsubishi Chemical Co., Ltd., 0.75 kg of water, and 1.74 g of disodium hydrogen phosphite pentahydrate were put in a container, purged with nitrogen, and dissolved at 100 ° C. This raw material aqueous solution was transferred to an autoclave, the jacket temperature was set to 280 ° C., and heating was started. After the temperature of the contents was raised to 270 ° C., the pressure in the autoclave was gradually released, and then the pressure was further reduced and the polycondensation reaction was completed when the predetermined stirring power was reached. After completion of the reaction, the pressure was restored with nitrogen, and the contents were introduced into a cooling water tank in the form of a strand and then pelletized with a rotary cutter. Unreacted monomers and oligomers were extracted and removed from the obtained pellets using boiling water 1.5 times the amount of the obtained pellets. The pellets from which the unreacted substances had been removed were dried at 120 ° C. and 1 torr (0.13 kPa) until the water content became 0.1% or less to obtain a polyamide resin. Various characteristics evaluation was performed with respect to the obtained polyamide resin.
実施例２と同様にタルクを配合した後にドライブレンドし、非強化ポリアミド樹脂組成物を得た。得られたポリアミド樹脂組成物に対し、低温ヒンジ性、低温バンド折れ性および機械物性の各評価を行った。結果を表２に示す。 In the same manner as in Example 2, talc was blended and then dry blended to obtain a non-reinforced polyamide resin composition. Each evaluation of low temperature hinge property, low temperature band bending property, and mechanical property was performed with respect to the obtained polyamide resin composition. The results are shown in Table 2.
実施例３〜８（ポリアミド樹脂およびフィラメント）：
実施例１において、原料水溶液の仕込みモノマー組成を表３及び４に示す様に変更した以外は、実施例１と同様の操作でポリアミド樹脂を得た。得られたポリアミド樹脂に対し、各種特性評価を行った。さらに、得られたポリアミド樹脂に対し、透明性評価の項目で説明した様にモノフィラメントを作成し、その透明性を評価した。結果を表３及び４に示す。
Examples 3 to 8 (polyamide resin and filament):
A polyamide resin was obtained in the same manner as in Example 1, except that the monomer composition of the raw material aqueous solution was changed as shown in Tables 3 and 4 in Example 1. Various characteristics evaluation was performed with respect to the obtained polyamide resin. Furthermore, monofilaments were prepared for the obtained polyamide resin as described in the item of transparency evaluation, and the transparency was evaluated. The results are shown in Tables 3 and 4.
比較例４：
実施例１において、原料水溶液の仕込みモノマー組成を表５に示す様に変更した以外は、実施例１と同様の操作でポリアミド樹脂を得た。得られたポリアミド樹脂に対し、各種特性評価を行った。さらに、得られたポリアミド樹脂に対し、透明性評価の項目で説明した様にモノフィラメントを作成し、その透明性を評価した。結果を表５に示す。
Comparative Example 4:
A polyamide resin was obtained in the same manner as in Example 1, except that the monomer composition of the raw material aqueous solution was changed as shown in Table 5 in Example 1. Various characteristics evaluation was performed with respect to the obtained polyamide resin. Furthermore, monofilaments were prepared for the obtained polyamide resin as described in the item of transparency evaluation, and the transparency was evaluated. The results are shown in Table 5.
比較例５：
実施例１において、原料水溶液の仕込みモノマー組成を表５に示す様に変更した以外は、実施例１と同様の操作でポリアミド樹脂を得た。得られたポリアミド樹脂に対し、各種特性評価を行った。さらに、得られたポリアミド樹脂に対し、透明性評価の項目で説明した様にモノフィラメントを作成し、その透明性を評価した。結果を表５に示す。
Comparative Example 5:
A polyamide resin was obtained in the same manner as in Example 1, except that the monomer composition of the raw material aqueous solution was changed as shown in Table 5 in Example 1. Various characteristics evaluation was performed with respect to the obtained polyamide resin. Furthermore, monofilaments were prepared for the obtained polyamide resin as described in the item of transparency evaluation, and the transparency was evaluated. The results are shown in Table 5.
以上、現時点において、最も実践的であり、且つ、好ましいと思われる実施形態に関連して本発明を説明したが、本発明は、本願明細書中に開示された実施形態に限定されるものではなく、請求の範囲および明細書全体から読みとれる発明の要旨或いは思想に反しない範囲で適宜変更可能であり、その様な変更を伴う場合も本発明の技術的範囲であると理解されなければならない。なお、本出願は、２００４年５月２３日付で出願された日本特許出願（特願２００４−１５２０５９号）に基づいており、その全体が引用により援用される。 Although the present invention has been described with reference to the most practical and preferred embodiments at the present time, the invention is not limited to the embodiments disclosed herein. It should be understood that the present invention can be modified as appropriate without departing from the spirit or concept of the invention as read from the claims and the entire specification, and that such changes are also within the technical scope of the present invention. . In addition, this application is based on the Japanese patent application (Japanese Patent Application No. 2004-152059) for which it applied on May 23, 2004, The whole is used by reference.
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