JPH0812881A - Polyamide resin composition and method for producing the same - Google Patents
Polyamide resin composition and method for producing the sameInfo
- Publication number
- JPH0812881A JPH0812881A JP23174894A JP23174894A JPH0812881A JP H0812881 A JPH0812881 A JP H0812881A JP 23174894 A JP23174894 A JP 23174894A JP 23174894 A JP23174894 A JP 23174894A JP H0812881 A JPH0812881 A JP H0812881A
- Authority
- JP
- Japan
- Prior art keywords
- polyamide resin
- resin composition
- weight
- polymerization
- number average
- 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.)
- Pending
Links
- 229920006122 polyamide resin Polymers 0.000 title claims abstract description 87
- 239000011342 resin composition Substances 0.000 title claims abstract description 56
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 67
- 238000009830 intercalation Methods 0.000 claims abstract description 53
- 230000002687 intercalation Effects 0.000 claims abstract description 52
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 42
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 26
- 125000001453 quaternary ammonium group Chemical group 0.000 claims abstract description 26
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 22
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 18
- 238000005341 cation exchange Methods 0.000 claims abstract description 16
- 229920005672 polyolefin resin Polymers 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 20
- 239000011229 interlayer Substances 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000010008 shearing Methods 0.000 claims description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 230000004888 barrier function Effects 0.000 abstract description 2
- 229920002292 Nylon 6 Polymers 0.000 description 27
- 229920002647 polyamide Polymers 0.000 description 24
- 239000004952 Polyamide Substances 0.000 description 23
- -1 for example Substances 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 19
- 238000002156 mixing Methods 0.000 description 14
- 229920005989 resin Polymers 0.000 description 14
- 239000011347 resin Substances 0.000 description 14
- 238000004898 kneading Methods 0.000 description 13
- 238000009864 tensile test Methods 0.000 description 13
- 239000010410 layer Substances 0.000 description 10
- 239000010445 mica Substances 0.000 description 10
- 229910052618 mica group Inorganic materials 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 9
- 239000004594 Masterbatch (MB) Substances 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000004677 Nylon Substances 0.000 description 9
- 239000011737 fluorine Substances 0.000 description 9
- 229910052731 fluorine Inorganic materials 0.000 description 9
- 229920001778 nylon Polymers 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 8
- 238000000465 moulding Methods 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 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 6
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 6
- IPEHBUMCGVEMRF-UHFFFAOYSA-N pyrazinecarboxamide Chemical compound NC(=O)C1=CN=CC=N1 IPEHBUMCGVEMRF-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 150000004985 diamines Chemical class 0.000 description 5
- 150000001991 dicarboxylic acids Chemical class 0.000 description 5
- 238000009863 impact test Methods 0.000 description 5
- 239000000155 melt Substances 0.000 description 5
- 229910052901 montmorillonite Inorganic materials 0.000 description 5
- 230000035699 permeability Effects 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 230000008961 swelling Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 3
- 229920002302 Nylon 6,6 Polymers 0.000 description 3
- 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 3
- 239000001361 adipic acid Substances 0.000 description 3
- 235000011037 adipic acid Nutrition 0.000 description 3
- RLGQACBPNDBWTB-UHFFFAOYSA-N cetyltrimethylammonium ion Chemical compound CCCCCCCCCCCCCCCC[N+](C)(C)C RLGQACBPNDBWTB-UHFFFAOYSA-N 0.000 description 3
- 239000002734 clay mineral Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- SWSFKKWJEHRFFP-UHFFFAOYSA-N dihexadecyl(dimethyl)azanium Chemical compound CCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCC SWSFKKWJEHRFFP-UHFFFAOYSA-N 0.000 description 3
- OGQYPPBGSLZBEG-UHFFFAOYSA-N dimethyl(dioctadecyl)azanium Chemical compound CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC OGQYPPBGSLZBEG-UHFFFAOYSA-N 0.000 description 3
- CJBMLKNLJXFFGD-UHFFFAOYSA-N dimethyl-di(tetradecyl)azanium Chemical compound CCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCC CJBMLKNLJXFFGD-UHFFFAOYSA-N 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000000806 elastomer Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 150000003951 lactams Chemical class 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- WSNJABVSHLCCOX-UHFFFAOYSA-J trilithium;trimagnesium;trisodium;dioxido(oxo)silane;tetrafluoride Chemical compound [Li+].[Li+].[Li+].[F-].[F-].[F-].[F-].[Na+].[Na+].[Na+].[Mg+2].[Mg+2].[Mg+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O WSNJABVSHLCCOX-UHFFFAOYSA-J 0.000 description 3
- PDSVZUAJOIQXRK-UHFFFAOYSA-N trimethyl(octadecyl)azanium Chemical compound CCCCCCCCCCCCCCCCCC[N+](C)(C)C PDSVZUAJOIQXRK-UHFFFAOYSA-N 0.000 description 3
- PBLZLIFKVPJDCO-UHFFFAOYSA-N 12-aminododecanoic acid Chemical compound NCCCCCCCCCCCC(O)=O PBLZLIFKVPJDCO-UHFFFAOYSA-N 0.000 description 2
- CNPURSDMOWDNOQ-UHFFFAOYSA-N 4-methoxy-7h-pyrrolo[2,3-d]pyrimidin-2-amine Chemical compound COC1=NC(N)=NC2=C1C=CN2 CNPURSDMOWDNOQ-UHFFFAOYSA-N 0.000 description 2
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 229920000299 Nylon 12 Polymers 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229920000800 acrylic rubber Polymers 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 229960002684 aminocaproic acid Drugs 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- CSHHUPZZJWPKLG-UHFFFAOYSA-N didodecyl(diethyl)azanium Chemical compound CCCCCCCCCCCC[N+](CC)(CC)CCCCCCCCCCCC CSHHUPZZJWPKLG-UHFFFAOYSA-N 0.000 description 2
- QQJDHWMADUVRDL-UHFFFAOYSA-N didodecyl(dimethyl)azanium Chemical compound CCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCC QQJDHWMADUVRDL-UHFFFAOYSA-N 0.000 description 2
- MTMYNZJXHXNCTQ-UHFFFAOYSA-N diethyl(dihexadecyl)azanium Chemical compound CCCCCCCCCCCCCCCC[N+](CC)(CC)CCCCCCCCCCCCCCCC MTMYNZJXHXNCTQ-UHFFFAOYSA-N 0.000 description 2
- UIPRNZFLDHNPDH-UHFFFAOYSA-N diethyl(dioctadecyl)azanium Chemical compound CCCCCCCCCCCCCCCCCC[N+](CC)(CC)CCCCCCCCCCCCCCCCCC UIPRNZFLDHNPDH-UHFFFAOYSA-N 0.000 description 2
- IHCIQEWCIMHTBB-UHFFFAOYSA-N diethyl-di(tetradecyl)azanium Chemical compound CCCCCCCCCCCCCC[N+](CC)(CC)CCCCCCCCCCCCCC IHCIQEWCIMHTBB-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- DGJUONISEWDPFO-UHFFFAOYSA-N dodecyl(triethyl)azanium Chemical compound CCCCCCCCCCCC[N+](CC)(CC)CC DGJUONISEWDPFO-UHFFFAOYSA-N 0.000 description 2
- VICYBMUVWHJEFT-UHFFFAOYSA-N dodecyltrimethylammonium ion Chemical compound CCCCCCCCCCCC[N+](C)(C)C VICYBMUVWHJEFT-UHFFFAOYSA-N 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 2
- 229910000271 hectorite Inorganic materials 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000012784 inorganic fiber Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 2
- 229960000907 methylthioninium chloride Drugs 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000002667 nucleating agent Substances 0.000 description 2
- BNJOQKFENDDGSC-UHFFFAOYSA-N octadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCCC(O)=O BNJOQKFENDDGSC-UHFFFAOYSA-N 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920013716 polyethylene resin Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 150000004760 silicates Chemical class 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 229910021647 smectite Inorganic materials 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- ADBMSVFHVFJBFR-UHFFFAOYSA-N triethyl(hexadecyl)azanium Chemical compound CCCCCCCCCCCCCCCC[N+](CC)(CC)CC ADBMSVFHVFJBFR-UHFFFAOYSA-N 0.000 description 2
- CENIAFYRIODGSU-UHFFFAOYSA-N triethyl(octadecyl)azanium Chemical compound CCCCCCCCCCCCCCCCCC[N+](CC)(CC)CC CENIAFYRIODGSU-UHFFFAOYSA-N 0.000 description 2
- JXCCIZBMTUFJKN-UHFFFAOYSA-N triethyl(tetradecyl)azanium Chemical compound CCCCCCCCCCCCCC[N+](CC)(CC)CC JXCCIZBMTUFJKN-UHFFFAOYSA-N 0.000 description 2
- GLFDLEXFOHUASB-UHFFFAOYSA-N trimethyl(tetradecyl)azanium Chemical compound CCCCCCCCCCCCCC[N+](C)(C)C GLFDLEXFOHUASB-UHFFFAOYSA-N 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-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
- DPQHRXRAZHNGRU-UHFFFAOYSA-N 2,4,4-trimethylhexane-1,6-diamine Chemical compound NCC(C)CC(C)(C)CCN DPQHRXRAZHNGRU-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- JVPFOKXICYJJSC-UHFFFAOYSA-N 2-azaniumylnonanoate Chemical compound CCCCCCCC(N)C(O)=O JVPFOKXICYJJSC-UHFFFAOYSA-N 0.000 description 1
- FZZMTSNZRBFGGU-UHFFFAOYSA-N 2-chloro-7-fluoroquinazolin-4-amine Chemical compound FC1=CC=C2C(N)=NC(Cl)=NC2=C1 FZZMTSNZRBFGGU-UHFFFAOYSA-N 0.000 description 1
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- IGSBHTZEJMPDSZ-UHFFFAOYSA-N 4-[(4-amino-3-methylcyclohexyl)methyl]-2-methylcyclohexan-1-amine Chemical compound C1CC(N)C(C)CC1CC1CC(C)C(N)CC1 IGSBHTZEJMPDSZ-UHFFFAOYSA-N 0.000 description 1
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 1
- XDOLZJYETYVRKV-UHFFFAOYSA-N 7-Aminoheptanoic acid Chemical compound NCCCCCCC(O)=O XDOLZJYETYVRKV-UHFFFAOYSA-N 0.000 description 1
- GVNWZKBFMFUVNX-UHFFFAOYSA-N Adipamide Chemical compound NC(=O)CCCCC(N)=O GVNWZKBFMFUVNX-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910015243 LiMg Inorganic materials 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- BAVYZALUXZFZLV-UHFFFAOYSA-O Methylammonium ion Chemical compound [NH3+]C BAVYZALUXZFZLV-UHFFFAOYSA-O 0.000 description 1
- 229920000571 Nylon 11 Polymers 0.000 description 1
- 229920003189 Nylon 4,6 Polymers 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000004957 Zytel Substances 0.000 description 1
- 229920006102 Zytel® Polymers 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- QFNNDGVVMCZKEY-UHFFFAOYSA-N azacyclododecan-2-one Chemical compound O=C1CCCCCCCCCCN1 QFNNDGVVMCZKEY-UHFFFAOYSA-N 0.000 description 1
- YDLSUFFXJYEVHW-UHFFFAOYSA-N azonan-2-one Chemical compound O=C1CCCCCCCN1 YDLSUFFXJYEVHW-UHFFFAOYSA-N 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
- DEOSEFTVDAEGAD-UHFFFAOYSA-N benzyl-dihexadecyl-methylazanium Chemical compound CCCCCCCCCCCCCCCC[N+](C)(CCCCCCCCCCCCCCCC)CC1=CC=CC=C1 DEOSEFTVDAEGAD-UHFFFAOYSA-N 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- KKWVJXUQYDCFGB-UHFFFAOYSA-N butyl(tridodecyl)azanium Chemical compound CCCCCCCCCCCC[N+](CCCC)(CCCCCCCCCCCC)CCCCCCCCCCCC KKWVJXUQYDCFGB-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- VNSBYDPZHCQWNB-UHFFFAOYSA-N calcium;aluminum;dioxido(oxo)silane;sodium;hydrate Chemical compound O.[Na].[Al].[Ca+2].[O-][Si]([O-])=O VNSBYDPZHCQWNB-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- WGPYXAOHELDKCQ-UHFFFAOYSA-N dibenzyl(dihexadecyl)azanium Chemical compound C=1C=CC=CC=1C[N+](CCCCCCCCCCCCCCCC)(CCCCCCCCCCCCCCCC)CC1=CC=CC=C1 WGPYXAOHELDKCQ-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- NGZSKXNBTXMPPX-UHFFFAOYSA-N dimethyl-bis(octadec-1-enyl)azanium Chemical compound CCCCCCCCCCCCCCCCC=C[N+](C)(C)C=CCCCCCCCCCCCCCCCC NGZSKXNBTXMPPX-UHFFFAOYSA-N 0.000 description 1
- IHQUAEJPDHSYDS-UHFFFAOYSA-N dimethyl-bis(octadeca-1,3-dienyl)azanium Chemical compound CCCCCCCCCCCCCCC=CC=C[N+](C)(C)C=CC=CCCCCCCCCCCCCCC IHQUAEJPDHSYDS-UHFFFAOYSA-N 0.000 description 1
- ILRSCQWREDREME-UHFFFAOYSA-N dodecanamide Chemical compound CCCCCCCCCCCC(N)=O ILRSCQWREDREME-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 229910052621 halloysite Inorganic materials 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000006713 insertion reaction Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- XJPLVFCEZXTPJP-UHFFFAOYSA-N methyl-tri(tetradecyl)azanium Chemical compound CCCCCCCCCCCCCC[N+](C)(CCCCCCCCCCCCCC)CCCCCCCCCCCCCC XJPLVFCEZXTPJP-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000004010 onium ions Chemical class 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920006287 phenoxy resin Polymers 0.000 description 1
- 239000013034 phenoxy resin Substances 0.000 description 1
- 150000004986 phenylenediamines Chemical class 0.000 description 1
- 229920000412 polyarylene Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000003586 protic polar solvent Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910000275 saponite Inorganic materials 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- WIMCSFQYNXRDOM-UHFFFAOYSA-N tridodecyl(ethyl)azanium Chemical compound CCCCCCCCCCCC[N+](CC)(CCCCCCCCCCCC)CCCCCCCCCCCC WIMCSFQYNXRDOM-UHFFFAOYSA-N 0.000 description 1
- SBHRWOBHKASWGU-UHFFFAOYSA-M tridodecyl(methyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(CCCCCCCCCCCC)CCCCCCCCCCCC SBHRWOBHKASWGU-UHFFFAOYSA-M 0.000 description 1
- AUSVCTPDUJVUGB-UHFFFAOYSA-N trimethyl(octadec-1-enyl)azanium Chemical compound CCCCCCCCCCCCCCCCC=C[N+](C)(C)C AUSVCTPDUJVUGB-UHFFFAOYSA-N 0.000 description 1
- ZBMLLSYGUXEKLB-UHFFFAOYSA-N trimethyl(octadeca-1,3-dienyl)azanium Chemical compound CCCCCCCCCCCCCCC=CC=C[N+](C)(C)C ZBMLLSYGUXEKLB-UHFFFAOYSA-N 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- GKXVJHDEWHKBFH-UHFFFAOYSA-N xylylenediamine group Chemical group C=1(C(=CC=CC1)CN)CN GKXVJHDEWHKBFH-UHFFFAOYSA-N 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
(57)【要約】
【構成】 陽イオン交換容量が３０ミリ当量／１００ｇ
以上の層状珪酸塩をホストとし炭素数１２以上のアルキ
ル基を有する４級アンモニウムイオンをゲストとする層
間化合物を、無機灰分量として１〜２０重量％含有し、
ポリアミド樹脂の数平均重合度が７０〜５００であるポ
リアミド樹脂組成物及びその製造方法並びに該ポリアミ
ド樹脂と酸変性ポリオレフィン樹脂とからなるポリアミ
ド系樹脂組成物。
【効果】 強度、剛性が高く、かつ延性に優れ、しかも
成形品外観が良好である。又、ガスバリヤー性にも優れ
ている。(57) [Summary] [Constitution] Cation exchange capacity is 30 meq / 100g
1 to 20% by weight as an inorganic ash content of an intercalation compound having the above layered silicate as a host and a quaternary ammonium ion having an alkyl group having 12 or more carbon atoms as a guest,
A polyamide resin composition having a number average degree of polymerization of a polyamide resin of 70 to 500, a method for producing the same, and a polyamide resin composition comprising the polyamide resin and an acid-modified polyolefin resin. [Effect] The strength and rigidity are high, the ductility is excellent, and the appearance of the molded product is good. It also has excellent gas barrier properties.
Description
【０００１】[0001]
【産業上の利用分野】本発明は、特定の変性処理を施し
た層状珪酸塩とポリアミド樹脂からなるポリアミド樹脂
組成物とその製造方法に関する。また、本発明は、これ
らポリアミド樹脂組成物と酸変性ポリオレフィン樹脂と
からなるポリアミド系樹脂組成物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyamide resin composition comprising a layered silicate which has been subjected to a specific modification treatment and a polyamide resin, and a method for producing the same. The present invention also relates to a polyamide resin composition comprising these polyamide resin composition and an acid-modified polyolefin resin.
【０００２】[0002]
【従来の技術】従来、ポリアミド樹脂の強度や剛性を高
める目的で、様々な充填材、例えばガラス繊維、炭素繊
維等の無機繊維、炭酸カルシウム、雲母、タルク等の無
機微粉の配合が行われてきた。しかし、これらの手法は
強度や剛性を高めるものの、ポリアミド樹脂の特徴であ
る靱性を著しく損なう、比重が増す、表面外観が低下す
るといった種々の欠点を有していた。特に、射出成形品
やフィルム状成形品に引張応力が加わった場合の靱性、
すなわち延性は、こうした汎用の充填材配合樹脂組成物
では、一般に著しく低下する。2. Description of the Related Art Conventionally, various fillers, for example, inorganic fibers such as glass fibers and carbon fibers, and inorganic fine powders such as calcium carbonate, mica and talc have been blended for the purpose of increasing the strength and rigidity of polyamide resins. It was However, although these methods increase strength and rigidity, they have various drawbacks such as markedly impairing the toughness, which is a characteristic of polyamide resins, increasing specific gravity, and deteriorating the surface appearance. In particular, toughness when tensile stress is applied to injection molded products and film-shaped molded products,
That is, the ductility is generally significantly reduced in such a general-purpose filler-containing resin composition.
【０００３】延性の低下を初めとする充填材配合樹脂組
成物の欠点を改善すべく、一般に充填材の微細化や樹脂
マトリックス中での分散性の改良が行われてきている。
例えば、特公昭５０−３５５４４号公報には、有機塩基
類とモンモリロナイトを主成分とする層状珪酸塩との複
合体である有機ベントナイトを核剤として微量添加され
たポリアミド樹脂組成物により、フィルムにおける透明
性、表面光沢性を失うことなく初期弾性率が向上するこ
とが開示されている。In order to improve the drawbacks of the filler-containing resin composition including the decrease of ductility, the filler has generally been made finer and the dispersibility in the resin matrix has been improved.
For example, Japanese Patent Publication No. 50-35544 discloses a polyamide resin composition in which a small amount of an organic bentonite, which is a complex of organic bases and lamellar silicate containing montmorillonite as a main component, is added as a nucleating agent, so that a film is transparent. It is disclosed that the initial elastic modulus is improved without losing the properties and surface gloss.
【０００４】特開昭６２−７４９５７号公報には、ポリ
アミドを含む樹脂に均一に分散した厚さが７〜１２Åで
層間距離が３０Å以上の珪酸塩層が、ポリアミドの高分
子鎖の一部とイオン結合してなる複合材料により、機械
的強度が向上することが開示されている。第１回高分子
ＡＢＣ研究会講座（平成４年９月９日、高分子学会主
催）講演要旨集には、ポリアミド分子鎖と珪酸塩層との
イオン結合の存在の根拠として滴定法によるポリアミド
末端基分析においてカルボキシル基がアミノ基より多い
ことが示されている。また、特開昭６２−７４９５７号
公報には、イオン結合の生成を目的として、粘土鉱物と
実質的にカルボキシル基を有する陽イオンである膨潤化
剤とを接触させて得られる複合体をポリアミドモノマー
と混合し、加熱して重合する方法が開示されている。し
かし、これらの技術においては、珪酸塩層は極めて良好
に分散し機械的強度の向上が見られるものの、引張伸び
等の靱性は必らずしも満足できるものではなく、また、
溶融混合のような汎用的な方法による製造方法ではなか
った。In Japanese Patent Laid-Open No. 62-74957, a silicate layer having a thickness of 7 to 12 Å and an interlayer distance of 30 Å or more, which is uniformly dispersed in a resin containing polyamide, forms a part of a polymer chain of polyamide. It is disclosed that the composite material formed by ionic bonding improves the mechanical strength. The 1st Polymer ABC Study Group lecture (September 9, 1992, sponsored by Japan Society of Polymer Science) has a summary of the lectures as a basis for the existence of ionic bond between polyamide molecular chain and silicate layer. Group analysis has shown that there are more carboxyl groups than amino groups. Further, in JP-A-62-74957, a composite obtained by contacting a clay mineral with a swelling agent which is a cation substantially having a carboxyl group for the purpose of forming an ionic bond is disclosed as a polyamide monomer. A method of mixing with, heating and polymerizing is disclosed. However, in these techniques, although the silicate layer is extremely well dispersed and the mechanical strength is improved, the toughness such as tensile elongation is not always satisfactory, and,
The manufacturing method was not a general-purpose method such as melt mixing.
【０００５】[0005]
【本発明が解決しようとする課題】本発明の目的は、強
度や剛性及び表面外観に優れ、又、剛性と靱性特に延性
とのバランスに優れ、しかも汎用的な設備で製造可能な
ポリアミド樹脂組成物及びその製造方法を提供すること
にある。また、本発明の目的は、強度、剛性、靱性及び
平面衝撃強度に極めて優れたポリアミド樹脂と酸変性ポ
リオレフィン樹脂からなるポリアミド系樹脂組成物を提
供することにある。The object of the present invention is to provide a polyamide resin composition which is excellent in strength, rigidity and surface appearance, and has a good balance between rigidity and toughness, especially ductility, and which can be produced by general-purpose equipment. The object is to provide a product and a manufacturing method thereof. Another object of the present invention is to provide a polyamide resin composition comprising a polyamide resin and an acid-modified polyolefin resin, which are extremely excellent in strength, rigidity, toughness and plane impact strength.
【０００６】[0006]
【課題を解決するための手段】本発明は上述の問題を解
決するためになされたものであり、その要旨は、陽イオ
ン交換容量が３０ミリ当量／１００ｇ以上の層状珪酸塩
をホストとし炭素数１２以上のアルキル基を有する４級
アンモニウムイオンをゲストとする層間化合物を、無機
灰分量として１〜２０重量％含有し、ポリアミド樹脂の
数平均重合度が７０〜５００であることを特徴とするポ
リアミド樹脂組成物、及び少なくとも陽イオン交換容量
が３０ミリ当量／１００ｇ以上の層状珪酸塩をホストと
し炭素数１２以上のアルキル基を有する４級アンモニウ
ムイオンをゲストとする層間化合物と数平均重合度が７
０ないし５００であるポリアミド樹脂とを機械的剪断下
溶融混合し、該層間化合物を無機灰分量として１ないし
２０重量％含有するポリアミド樹脂組成物を製造するこ
とを特徴とするポリアミド樹脂組成物の製造方法に存す
る。The present invention has been made in order to solve the above-mentioned problems, and its gist is to use a layered silicate having a cation exchange capacity of 30 meq / 100 g or more as a host and a carbon number. A polyamide containing an intercalation compound having a quaternary ammonium ion as a guest having 12 or more alkyl groups as an inorganic ash content of 1 to 20% by weight, and having a number average degree of polymerization of a polyamide resin of 70 to 500. A resin composition and an intercalation compound having at least a cation exchange capacity of 30 meq / 100 g or more as a host and a quaternary ammonium ion having an alkyl group having 12 or more carbon atoms as a guest, and a number average degree of polymerization of 7
Production of a polyamide resin composition, characterized in that the polyamide resin of 0 to 500 is melt-mixed under mechanical shearing to produce a polyamide resin composition containing the intercalation compound as an inorganic ash content of 1 to 20% by weight. In the way.
【０００７】以下、本発明につき詳細に説明する。本発
明におけるポリアミド樹脂は主鎖中にアミド結合（−Ｎ
ＨＣＯ−）を含み加熱溶融できる重合体である。好適な
ポリアミド樹脂として、ポリテトラメチレンアジパミド
（ナイロン４６）、ポリカプロラクタム（ナイロン
６）、ポリヘキサメチレンアジパミド（ナイロン６
６）、ポリヘキサメチレンセバカミド（ナイロン６１
０）、ポリヘキサメチレンドデカミド（ナイロン６１
２）、ポリウンデカラクタム（ナイロン１１）、ポリド
デカラクタム（ナイロン１２）、テレフタル酸および／
またはイソフタル酸とヘキサメチレンジアミンとから得
られるポリアミド、アジピン酸とメタキシリレンジアミ
ンとから得られるポリアミド、テレフタル酸とアジピン
酸とヘキサメチレンジアミンとから得られるポリアミ
ド、共重合成分として二量体化脂肪酸を含む共重合ポリ
アミド、およびこれらのうち少なくとも２種の異なった
ポリアミド形成成分を含むポリアミド共重合体並びにこ
れらの混合物などがあげられる。ナイロン６はそれ自身
が靱性と剛性のバランスに優れ、剛性が高い割にしなや
かさを備えており最も好適なポリアミド樹脂として用い
ることができる。かかるポリアミドの原料はジアミンと
ジカルボン酸、ラクタム類、または重合可能なω−アミ
ノ酸類、ジアミンとジカルボン酸からなる塩、およびこ
れらの原料のオリゴマーである。ジアミンとしては、下
記一般式（１）The present invention will be described in detail below. The polyamide resin in the present invention has an amide bond (-N in the main chain).
It is a polymer that contains HCO-) and can be melted by heating. Suitable polyamide resins include polytetramethylene adipamide (nylon 46), polycaprolactam (nylon 6), polyhexamethylene adipamide (nylon 6).
6), polyhexamethylene sebacamide (nylon 61
0), polyhexamethylene dodecamide (nylon 61
2), polyundecalactam (nylon 11), polydodecalactam (nylon 12), terephthalic acid and /
Alternatively, a polyamide obtained from isophthalic acid and hexamethylenediamine, a polyamide obtained from adipic acid and metaxylylenediamine, a polyamide obtained from terephthalic acid, adipic acid and hexamethylenediamine, and a dimerized fatty acid as a copolymerization component. And the like, and the polyamide copolymers containing at least two different polyamide forming components and mixtures thereof. Nylon 6 itself has an excellent balance between toughness and rigidity, has high rigidity, but has flexibility, and can be used as the most suitable polyamide resin. The starting materials for such polyamides are diamines and dicarboxylic acids, lactams or polymerizable ω-amino acids, salts of diamines and dicarboxylic acids, and oligomers of these starting materials. As the diamine, the following general formula (1)
【０００８】[0008]
【化１】Ｈ2 Ｎ−Ｘ−ＮＨ2 ………（１） （式中、Ｘは二価の脂肪族基、二価の脂環式基又は二価
の芳香族基であって、これらの基は置換基を有していて
も良い。）Embedded image H 2 N—X—NH 2 (1) (wherein, X is a divalent aliphatic group, a divalent alicyclic group or a divalent aromatic group, The group may have a substituent.)
【０００９】で示される化合物が用いられる。このよう
なジアミンとしては、例えばトリメチレンジアミン、テ
トラメチレンジアミン、ペンタメチレンジアミン、オク
タメチレンジアミン、フェニレンジアミン類、キシリレ
ンジアミン類、２，２，４−又は２，４，４−トリメチ
ルヘキサメチレンジアミン、ビス（４−アミノシクロヘ
キシル）メタン、ビス（４−アミノ−３−メチルシクロ
ヘキシル）メタン、ヘキサメチレンジアミンなどが挙げ
られる。これらのジアミンは一種用いても良いし、二種
以上を組み合わせて用いても良い。また、該ジカルボン
酸としては、下記一般式（２）The compound represented by Examples of such diamines include trimethylenediamine, tetramethylenediamine, pentamethylenediamine, octamethylenediamine, phenylenediamines, xylylenediamines, 2,2,4- or 2,4,4-trimethylhexamethylenediamine. , Bis (4-aminocyclohexyl) methane, bis (4-amino-3-methylcyclohexyl) methane, hexamethylenediamine and the like. These diamines may be used alone or in combination of two or more. Further, as the dicarboxylic acid, the following general formula (2)
【００１０】[0010]
【化２】ＨＯＯＣ−Ｙ−ＣＯＯＨ ………（２） （式中、Ｙは二価の脂肪族基、二価の脂環式基又は二価
の芳香族基であって、これらの基は置換基を有していて
も良い。）で示される化合物が用いられる。HOOC-Y-COOH (2) (wherein Y is a divalent aliphatic group, a divalent alicyclic group or a divalent aromatic group, and these groups are A compound represented by the formula (1) which may have a substituent) is used.
【００１１】このようなジカルボン酸としては、例えば
セバシン酸、オクタデカン二酸、スベリン酸、グルタル
酸、ピメリン酸、アジピン酸などの脂肪族ジカルボン
酸、イソフタル酸、テレフタル酸などの芳香族ジカルボ
ン酸、シクロヘキサン−１，４および１，３−ジカルボ
ン酸などの脂環式ジカルボン酸などがあげられる。これ
らのジカルボン酸は一種用いても良いし、二種以上を組
み合わせて用いても良い。更にこれらのジカルボン酸の
酸塩化物も重合原料として用いることができる。Examples of such dicarboxylic acids include aliphatic dicarboxylic acids such as sebacic acid, octadecanedioic acid, suberic acid, glutaric acid, pimelic acid and adipic acid, aromatic dicarboxylic acids such as isophthalic acid and terephthalic acid, cyclohexane. Examples thereof include alicyclic dicarboxylic acids such as -1,4 and 1,3-dicarboxylic acids. These dicarboxylic acids may be used alone or in combination of two or more. Furthermore, acid chlorides of these dicarboxylic acids can also be used as a polymerization raw material.
【００１２】また、ラクタム類としては、例えばブチル
ラクタム、ピバロラクタム、カプロラクタム、カプリル
ラクタム、エナントラクタム、ウンデカノラクタム、ド
デカノラクタムなどが挙げられる。これらのラクタムは
一種用いても良いし、二種以上を組み合わせて用いても
良い。さらに重合可能なω−アミノ酸類としては、例え
ば６−アミノカプロン酸、７−アミノヘプタン酸、９−
アミノノナン酸、１１−アミノウンデカン酸、１２−ア
ミノドデカン酸などが挙げられる。これらの重合可能な
ω−アミノ酸は一種用いても良いし、二種以上を組み合
わせて用いても良い。The lactams include, for example, butyllactam, pivalolalactam, caprolactam, capryllactam, enanthlactam, undecanolactam, dodecanolactam and the like. These lactams may be used alone or in combination of two or more. Further polymerizable ω-amino acids include, for example, 6-aminocaproic acid, 7-aminoheptanoic acid, 9-amino acid.
Aminononanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and the like can be mentioned. These polymerizable ω-amino acids may be used alone or in combination of two or more.
【００１３】これらの各種のポリアミド樹脂又はポリア
ミド原料は数種組み合わせて用いてもよい。本発明のポ
リアミド樹脂組成物におけるポリアミド樹脂は、その数
平均重合度が７０〜５００の範囲である。数平均重合度
は末端基定量法により測定できる。ここで重合度とは、
分子中の総モノマーユニット数を意味する。重合度がこ
の範囲より低いと組成物の靱性の低下が顕著となり、こ
の範囲より高いと組成物の溶融粘度が高くなりすぎ成形
性が極端に悪化するので好ましくない。なお、本発明の
ポリアミド樹脂組成物におけるポリアミド樹脂の数平均
重合度は、滴定法による末端基定量やゲルパーミエーシ
ョンクロマトグラフィにより測定できる。These various polyamide resins or polyamide raw materials may be used in combination. The polyamide resin in the polyamide resin composition of the present invention has a number average degree of polymerization of 70 to 500. The number average degree of polymerization can be measured by a terminal group quantitative method. Here, the degree of polymerization is
It means the total number of monomer units in the molecule. When the degree of polymerization is lower than this range, the toughness of the composition is remarkably deteriorated, and when the degree of polymerization is higher than this range, the melt viscosity of the composition becomes too high and the moldability is extremely deteriorated. The number average degree of polymerization of the polyamide resin in the polyamide resin composition of the present invention can be measured by quantifying the end groups by a titration method or gel permeation chromatography.
【００１４】本発明のポリアミド樹脂組成物におけるポ
リアミド樹脂は、そのアミノ末端が珪酸塩層とイオン結
合している必要はなく、従って、例えば末端停止剤を添
加しないナイロン６のように本質的にアミノ基濃度〔Ｎ
Ｈ2 〕とカルボキシル基濃度〔ＣＯＯＨ〕が等しい系で
は、層間化合物中の４級アンモニウムイオンの分だけ滴
定法による〔ＮＨ2 〕の値は大きくなる。また、本発明
のポリアミド樹脂組成物は、通常ポリアミド分子鎖末端
が変化したとしても、その性質は大きくは変化しないも
のと言える。The polyamide resin in the polyamide resin composition of the present invention does not need to have its amino terminal ionically bonded to the silicate layer, and therefore, it is essentially an amino group such as nylon 6 without the addition of a terminator. Group concentration [N
In a system in which H 2 ] is equal to the carboxyl group concentration [COOH], the value of [NH 2 ] by the titration method increases by the amount of the quaternary ammonium ion in the intercalation compound. Further, it can be said that the polyamide resin composition of the present invention does not largely change its properties even if the terminal of the polyamide molecular chain changes.
【００１５】本発明における層間化合物としては、層状
珪酸塩をホストとし、４級アンモニウム塩をゲストとす
る層間化合物である。ここで、ホストとは層間化合物の
基本骨格を形成する分子あるいはイオンからなる化合物
を意味し、ゲストとは、ホストとの相互作用によって、
それに組み込まれる分子あるいはイオンからなる化合物
を意味する。陽イオン交換容量が３０ミリ当量／１００
ｇ以上の層状珪酸塩に炭素数１２以上のアルキル基を有
する４級アンモニウムイオンをインターカレーション
（挿入）した層状化合物は、数平均重合度が７０〜５０
０であるポリアミド樹脂と共に溶融混合することによ
り、ポリアミド樹脂組成物中に極めて均一に劈開分散
し、ポリアミド樹脂組成物に対し、無機灰分量として１
〜２０重量％含有されることにより剛性に優れているの
みならず、剛性と延性との良好なバランスを有するポリ
アミド樹脂組成物を与える。The intercalation compound in the present invention is an intercalation compound having a layered silicate as a host and a quaternary ammonium salt as a guest. Here, the host means a compound composed of a molecule or an ion forming the basic skeleton of the intercalation compound, and the guest means by interaction with the host,
A compound consisting of molecules or ions incorporated into it. Cation exchange capacity is 30 meq / 100
A layered compound obtained by intercalating (inserting) a quaternary ammonium ion having an alkyl group having 12 or more carbon atoms into g or more layered silicate has a number average degree of polymerization of 70 to 50.
By melt-mixing with a polyamide resin of 0, it is cleaved and dispersed very uniformly in the polyamide resin composition, and the amount of inorganic ash is 1 as compared to the polyamide resin composition.
By containing 20 to 20% by weight, a polyamide resin composition having not only excellent rigidity but also a good balance between rigidity and ductility is provided.
【００１６】本発明に用いられる層状珪酸塩としては、
Ａｌ，Ｍｇ，Ｌｉ等を含む８面体シート構造を２枚のＳ
ｉＯ4 四面体シート構造がはさんだ形の２：１型が好適
であり、具体的には、モンモリロナイト、ヘクトライ
ト、フッ素ヘクトライト、サポナイト、バイデライト、
スチブンサイト等のスメクタイト系粘土鉱物、Ｌｉ型フ
ッ素テニオライト、Ｎａ型フッ素テニオライト、Ｎａ型
四珪素フッ素雲母、Ｌｉ型四珪素フッ素雲母等の膨潤性
合成雲母、バーミキュライト、フッ素バーミキュライ
ト、ハロイサイト等が挙げられ、天然のものであっても
合成されてものであっても良い。The layered silicate used in the present invention includes:
An octahedral sheet structure containing Al, Mg, Li, etc.
A 2: 1 type in which the tetrahedral sheet structure of iO 4 is sandwiched is preferable, and specifically, montmorillonite, hectorite, fluorohectorite, saponite, beidellite,
Smectite clay minerals such as stevensite, Li-type fluorine teniolite, Na-type fluorine teniolite, swelling synthetic mica such as Na-type tetrasilicon fluoromica, Li-type tetrasilicon fluoromica, vermiculite, fluorovermiculite, halloysite, etc. It may be a synthetic material or a synthetic material.
【００１７】中でも、モンモリロナイト、ヘクトライト
等のスメクタイト系粘土鉱物、Ｌｉ型フッ素テニオライ
ト、Ｎａ型フッ素テニオライト、Ｎａ型四珪素フッ素雲
母等の膨潤性合成雲母が好ましく、特にＬｉ型フッ素テ
ニオライト、Ｎａ型フッ素テニオライト、Ｎａ型四珪素
雲母等の膨潤性フッ素雲母が好ましい。Ｌｉ型フッ素テ
ニオライトは下記式（３）で示される組成、Ｎａ型フッ
素テニオライトは下記式（４）で示される組成、Ｎａ型
四珪素雲母は下記式（５）に示される組成に相当するが
これら式（３），式（４）及び式（５）は理想的な組成
を示したものであり、必らずしも厳密に一致している必
要はない。Among them, swelling synthetic mica such as smectite clay minerals such as montmorillonite and hectorite, Li type fluorine teniolite, Na type fluorine teniolite, Na type tetrasilicon fluorine mica and the like are preferable, and Li type fluorine teniolite and Na type fluorine are particularly preferable. Swelling fluoromica such as teniolite and Na-type tetrasilicon mica are preferred. Li-type fluorine teniolite corresponds to the composition represented by the following formula (3), Na-type fluorine teniolite corresponds to the composition represented by the following formula (4), and Na-type tetrasilicon mica corresponds to the composition represented by the following formula (5). The formulas (3), (4), and (5) show ideal compositions, and do not necessarily have to be exactly the same.
【００１８】[0018]
【化３】 ＬｉＭｇ2 Ｌｉ（Ｓｉ4 Ｏ10）Ｆ2 （３） ＮａＭｇ2 Ｌｉ（Ｓｉ4 Ｏ10）Ｆ2 （４） ＮａＭｇ2.5 （Ｓｉ4 Ｏ10）Ｆ2 （５） 尚、膨潤性フッ素雲母の具体例としては膨潤性合成雲母
（コープケミカル（株）製，商品名ＭＥ１００）が挙げ
られる。Embedded image LiMg 2 Li (Si 4 O 10 ) F 2 (3) NaMg 2 Li (Si 4 O 10 ) F 2 (4) NaMg 2.5 (Si 4 O 10 ) F 2 (5) In addition, swellable fluorine Specific examples of the mica include swellable synthetic mica (trade name: ME100, manufactured by Cope Chemical Co., Ltd.).
【００１９】本発明においては、これらの層状珪酸塩の
陽イオン交換容量（ＣＥＣ）は通常３０ミリ当量／１０
０ｇ以上で、より好ましくは５０ミリ当量／１００ｇ以
上、最も好ましくは７０ミリ当量／１００ｇ以上であ
る。陽イオン交換容量は、メチレンブルーの吸着量測定
により求めることができる。陽イオン交換容量が３０ミ
リ当量／１００ｇ未満では、層状珪酸塩を構成する平面
上の巨大分子層間への４級アンモニウムイオンのインタ
ーカレーション量が不十分となり、ポリアミド樹脂への
層間化合物の分散が悪くなるため、ポリアミド樹脂組成
物の強度や剛性が十分でなく成形表面外観も悪くなる。
又層状珪酸塩の陽イオン交換容量は、壁開性の点より２
００ミリ当量／１００ｇ以下であることが好ましい。In the present invention, the cation exchange capacity (CEC) of these layered silicates is usually 30 meq / 10.
It is 0 g or more, more preferably 50 meq / 100 g or more, and most preferably 70 meq / 100 g or more. The cation exchange capacity can be determined by measuring the adsorption amount of methylene blue. If the cation exchange capacity is less than 30 meq / 100 g, the intercalation amount of the quaternary ammonium ion between the macromolecular layers on the plane forming the layered silicate will be insufficient, and the intercalation compound will be dispersed in the polyamide resin. As a result, the strength and rigidity of the polyamide resin composition are not sufficient, and the appearance of the molded surface is also poor.
Also, the cation exchange capacity of layered silicate is 2 from the viewpoint of wall cleavage.
It is preferably 00 meq / 100 g or less.
【００２０】本発明に用いられる炭素数１２以上のアル
キル基を有する４級アンモニウムイオンは、原料段階で
は通常ハロゲン化物イオンとの塩として取り扱われる。
こうした４級アンモニウムイオンの具体例としては、ト
リメチルドデシルアンモニウム、トリメチルテトラデシ
ルアンモニウム、トリメチルヘキサデシルアンモニウ
ム、トリメチルオクタデシルアンモニウム、トリメチル
エイコサニルアンモニウム、トリメチルオクタデセニル
アンモニウム、トリメチルオクタデカジエニルアンモニ
ウム等のトリメチルアルキルアンモニウム、トリエチル
ドデシルアンモニウム、トリエチルテトラデシルアンモ
ニウム、トリエチルヘキサデシルアンモニウム、トリエ
チルオクタデシルアンモニウム等のトリエチルアルキル
アンモニウム、トリブチルドデシルアンモニウム、トリ
ブチルテトラデシルアンモニウム、The quaternary ammonium ion having an alkyl group having 12 or more carbon atoms used in the present invention is usually treated as a salt with a halide ion in the raw material stage.
Specific examples of such quaternary ammonium ions include trimethyldodecyl ammonium, trimethyl tetradecyl ammonium, trimethyl hexadecyl ammonium, trimethyl octadecyl ammonium, trimethyl eicosanyl ammonium, trimethyl octadecenyl ammonium, trimethyl octadecadienyl ammonium and the like. Trimethylalkylammonium, triethyldodecylammonium, triethyltetradecylammonium, triethylhexadecylammonium, triethylalkylammonium such as triethyloctadecylammonium, tributyldodecylammonium, tributyltetradecylammonium,
【００２１】トリブチルヘキサデシルアンモニウム、ト
リブチルオクタデシルアンモニウム等のトリブチルアル
キルアンモニウム、ジメチルジドデシルアンモニウム、
ジメチルジテトラデシルアンモニウム、ジメチルジヘキ
サデシルアンモニウム、ジメチルジオクタデシルアンモ
ニウム、ジメチルジオクタデセニルアンモニウム、ジメ
チルジオクタデカジエニルアンモニウム等のジメチルジ
アルキルアンモニウム、ジエチルジドデシルアンモニウ
ム、ジエチルジテトラデシルアンモニウム、ジエチルジ
ヘキサデシルアンモニウム、ジエチルジオクタデシルア
ンモニウム等のジエチルジアルキルアンモニウム、ジブ
チルジドデシルアンモニウム、ジブチルジテトラデシル
アンモニウム、ジブチルジヘキサデシルアンモニウム、
ジブチルジオクタデシルアンモニウム等のジブチルジア
ルキルアンモニウム、メチルベンジルジヘキサデシルア
ンモニウム等のメチルベンジルジアルキルアンモニウ
ム、ジベンジルジヘキサデシルアンモニウム等のジベン
ジルアルキルアンモニウム、トリドデシルメチルアンモ
ニウム、トリテトラデシルメチルアンモニウム等のトリ
アルキルメチルアンモニウム、トリドデシルエチルアン
モニウム等のトリアルキルエチルアンモニウム、トリド
デシルブチルアンモニウム等のトリアルキルブチルアン
モニウム等のイオンが挙げられる。中でもトリメチルド
デシルアンモニウム、トリメチルテトラデシルアンモニ
ウム、トリメチルヘキサデシルアンモニウム、トリメチ
ルオクタデシルアンモニウム、トリエチルドデシルアン
モニウム、Tributylalkylammonium such as tributylhexadecylammonium, tributyloctadecylammonium, dimethyldidodecylammonium,
Dimethylditetradecylammonium, dimethyldihexadecylammonium, dimethyldioctadecylammonium, dimethyldioctadecenylammonium, dimethyldioctadecadienylammonium, etc.dimethyldialkylammonium, diethyldidodecylammonium, diethylditetradecylammonium, diethyl Dihexadecylammonium, diethyldialkylammonium such as diethyldioctadecylammonium, dibutyldidodecylammonium, dibutylditetradecylammonium, dibutyldihexadecylammonium,
Dibutyldialkylammonium such as dibutyldioctadecylammonium, methylbenzyldialkylammonium such as methylbenzyldihexadecylammonium, dibenzylalkylammonium such as dibenzyldihexadecylammonium, trialkyl such as tridodecylmethylammonium, tritetradecylmethylammonium Examples thereof include ions such as trialkylethylammonium such as methylammonium and tridodecylethylammonium, and trialkylbutylammonium such as tridodecylbutylammonium. Among them, trimethyldodecyl ammonium, trimethyl tetradecyl ammonium, trimethyl hexadecyl ammonium, trimethyl octadecyl ammonium, triethyl dodecyl ammonium,
【００２２】トリエチルテトラデシルアンモニウム、ト
リエチルヘキサデシルアンモニウム、トリエチルオクタ
デシルアンモニウム等の炭素数１２以上のアルキル基を
１分子中に１つ有する４級アンモニウムのイオン、ジメ
チルジドデシルアンモニウム、ジメチルジテトラデシル
アンモニウム、ジメチルジヘキサデシルアンモニウム、
ジメチルジオクタデシルアンモニウム、ジエチルジドデ
シルアンモニウム、ジエチルジテトラデシルアンモニウ
ム、ジエチルジヘキサデシルアンモニウム、ジエチルジ
オクタデシルアンモニウム等の炭素数１２以上のアルキ
ル基を１分子中に２つ有する４級アンモニウム等のイオ
ンがポリアミド樹脂組成物の靱性保持の点から好まし
く、より好ましくは、トリメチルヘキサデシルアンモニ
ウム、トリメチルオクタデシルアンモニウム等の炭素数
１６以上のアルキル基を１分子中に１つ有する４級アン
モニウム、ジメチルジテトラデシルアンモニウム、ジメ
チルジヘキサデシルアンモニウム、ジメチルジオクタデ
シルアンモニウム等の炭素数１４以上のアルキル基を１
分子中に２つ有する４級アンモニウム等のイオンであ
り、最も好ましくはトリメチルオクタデシルアンモニウ
ムイオン、ジメチルジオクタデシルアンモニウムイオン
である。又、４級アンモニウムイオンとしては、極性溶
媒中での溶解性の点より炭素数１２以上３０以下のアル
キル基を有するものが好ましく、より好ましくは炭素数
１２以上２５以下のアルキル基を有するものである。な
お、これらの４級アンモニウムイオンは、単独でも複数
種類の混合物としても使用できる。４級アンモニウムイ
オンの最長アルキル鎖の炭素数が１２以上であることに
より組成物の靱性が向上する理由は必らずしも十分に明
らかとは言えないが、通常の剪断下溶融混合条件で珪酸
塩層が極めて均一に劈開分散されることの他に、４級ア
ンモニウムイオンがポリアミド成分と珪酸塩層との界面
近傍においてポリアミド鎖の可動性を助長する有効な可
塑剤として機能し、該界面近傍での応力集中破壊を起こ
りにくくしているとも考えられる。Ions of quaternary ammonium having one alkyl group having 12 or more carbon atoms in one molecule such as triethyltetradecylammonium, triethylhexadecylammonium and triethyloctadecylammonium, dimethyldidodecylammonium, dimethylditetradecylammonium, Dimethyldihexadecyl ammonium,
Ions such as quaternary ammonium having two or more alkyl groups having 12 or more carbon atoms in one molecule such as dimethyldioctadecylammonium, diethyldidodecylammonium, diethylditetradecylammonium, diethyldihexadecylammonium, and diethyldioctadecylammonium It is preferable from the viewpoint of maintaining the toughness of the polyamide resin composition, and more preferably quaternary ammonium having one or more alkyl groups having 16 or more carbon atoms in one molecule, such as trimethylhexadecyl ammonium and trimethyl octadecyl ammonium, and dimethylditetradecyl ammonium. , An alkyl group having 14 or more carbon atoms such as dimethyldihexadecyl ammonium, dimethyl dioctadecyl ammonium, etc.
Ions such as quaternary ammonium having two in the molecule, most preferably trimethyloctadecylammonium ion and dimethyldioctadecylammonium ion. The quaternary ammonium ion is preferably one having an alkyl group having 12 to 30 carbon atoms, more preferably an alkyl group having 12 to 25 carbon atoms from the viewpoint of solubility in a polar solvent. is there. These quaternary ammonium ions can be used alone or as a mixture of plural kinds. The reason why the toughness of the composition is improved by having the carbon number of the longest alkyl chain of the quaternary ammonium ion is 12 or more is not always clear enough, but it is not possible to say sufficiently. Besides the fact that the salt layer is cleaved and dispersed very uniformly, the quaternary ammonium ion functions as an effective plasticizer that promotes the mobility of the polyamide chain in the vicinity of the interface between the polyamide component and the silicate layer. It is also thought that stress concentration failure in the is hard to occur.
【００２３】陽イオン交換容量が３０ミリ当量／１００
ｇ以上の層状珪酸塩をホストとし炭素数１２以上のアル
キル基を有する４級アンモニウムイオンをゲストとする
層間化合物は、有機オニウムイオンを負の層格子および
交換可能なカチオンを含有する粘土と反応させる公知の
技術（例えば特公昭６１−５４９２号公報、特開昭６０
−４２４５１号公報等参照）により製造することができ
る。層状珪酸塩の層間への４級アンモニウムイオンの挿
入は、極性溶媒、好ましくは水、メタノール、エタノー
ル、プロパノール、ブタノール等のプロトン性溶媒及び
これら２種以上の混合溶媒中で進行するイオン交換反応
による。層間化合物の製造に好ましい溶媒は、水、メタ
ノール、エタノールであるが４級アンモニウム塩の溶解
度が極端に低くならない限り水が最適である。炭素数１
２以上のアルキル基を有する４級アンモニウムイオン
は、層状珪酸塩の陽イオン交換容量に対し１〜３当量反
応させる。反応の収率（インターカレーション率）は炭
素数１２以上のアルキル基を有する４級アンモニウムイ
オンの溶媒への溶解度や反応温度により若干異なるが、
経済性から好ましくは１．０〜１．５当量の小過剰量を
反応させる。生成する層間化合物中の炭素数１２以上の
アルキル基を有する４級アンモニウムイオンの量は、原
料である層状珪酸塩の陽イオン交換容量に対し０．８〜
２．０当量の範囲であれば特に制限はないが、通常の反
応条件では１．０〜１．３当量となる。この量が０．８
当量よりも少ないと、ポリアミド樹脂への分散性が低下
し、２．０当量より多いと４級アンモニウムイオン由来
の遊離化合物が顕著となり、成形時の熱安定性低下、発
煙、金型汚染、臭気等の原因となる。Cation exchange capacity is 30 meq / 100
An intercalation compound having g or more layered silicate as a host and a quaternary ammonium ion having an alkyl group having 12 or more carbon atoms as a guest reacts an organic onium ion with a clay containing a negative layer lattice and an exchangeable cation Known techniques (for example, Japanese Patent Publication No. 61-5492 and Japanese Patent Laid-Open No. 60)
No. 42451, etc.). Insertion of quaternary ammonium ions between the layers of the layered silicate is carried out by an ion exchange reaction which proceeds in a polar solvent, preferably a protic solvent such as water, methanol, ethanol, propanol, butanol and a mixed solvent of two or more of these. . The preferred solvent for the production of the intercalation compound is water, methanol or ethanol, but water is most suitable as long as the solubility of the quaternary ammonium salt does not become extremely low. Carbon number 1
The quaternary ammonium ion having two or more alkyl groups is reacted in 1 to 3 equivalents with respect to the cation exchange capacity of the layered silicate. The reaction yield (intercalation rate) is slightly different depending on the solubility of the quaternary ammonium ion having an alkyl group having 12 or more carbon atoms in the solvent and the reaction temperature.
From the economical aspect, a small excess amount of 1.0 to 1.5 equivalents is preferably reacted. The amount of the quaternary ammonium ion having an alkyl group having 12 or more carbon atoms in the produced intercalation compound is 0.8 to the cation exchange capacity of the layered silicate as a raw material.
There is no particular limitation as long as it is in the range of 2.0 equivalents, but it is 1.0 to 1.3 equivalents under normal reaction conditions. This amount is 0.8
If the amount is less than the equivalent, the dispersibility in the polyamide resin decreases, and if it exceeds 2.0 equivalent, the free compound derived from quaternary ammonium ion becomes remarkable, and the thermal stability at the time of molding is reduced, smoke generation, mold contamination, and odor. It causes such as.
【００２４】生成した層間化合物は、炭素数１２以上の
アルキル基を有する４級アンモニウムイオンの挿入反応
後、層間以外に残存する余分なイオンを除去するため
に、溶媒中での攪拌洗浄工程と遠心分離や濾過等の分離
工程を繰り返すバッチ洗浄、あるいは連続的に溶媒を流
して洗浄する連続洗浄等の適切な方法による精製を行な
う。精製度は、例えば炭素数１２以上のアルキル基を有
する４級アンモニウムハライドを原料とした場合、硝酸
銀水溶液を洗液に加えて白色のハロゲン化銀の生成が見
られなくなることで確認できる。この精製が不十分な場
合、４級アンモニウムイオン由来の遊離化合物による成
形時の熱安定性低下、発煙、金型汚染、臭気等の原因と
なる。また層間化合物の精製後の水分量は、ポリアミド
成分との混合時の加水分解等の望ましくない副反応を低
減するために、１０ｗｔ％以下、好ましくは５ｗｔ％以
下、最も好ましくは３ｗｔ％以下に制御する。該水分量
が１０ｗｔ％を超えるとポリアミド成分の加水分解等の
副反応による劣化が顕著となり、ポリアミド樹脂組成物
の靱性が大きく低下する。本発明に使用する層間化合物
は、精製後の最大粒径を５００μｍ以下、好ましくは１
００μｍ以下、更に好ましくは５０μｍ以下、最も好ま
しくは１０μｍ以下に粉砕しておくことは剪断効率の異
なる幅広い分散方法に適用するためにも望ましいことで
ある。本発明のポリアミド樹脂組成物においては、該層
間化合物をポリアミド樹脂組成物に対し無機灰分量とし
て１〜２０重量％、好ましくは１〜１０重量％、更に好
ましくは１〜５重量％含むことが望ましい。無機灰分量
は、ポリアミド樹脂組成物の有機成分を６５０℃の電気
炉内で完全に消失せしめた残渣の重量分率から求めるこ
とができる。無機灰分量が１重量％未満の場合は弾性率
の向上が顕著でなく、一方２０重量％を超えると層間化
合物中の４級アンモニウムイオン成分の影響でマトリッ
クスのポリアミド成分の劣化が促進され成形に支障を来
す等の欠点があり好ましくない。なお、層間化合物は各
々単独で用いてもよく併用してもよい。層間化合物の配
合量はポリアミド樹脂１００重量部に対し、１〜５０重
量部、好ましくは１〜３０重量部、より好ましくは１〜
２０重量部である。The resulting intercalation compound is stirred and washed in a solvent and centrifuged in order to remove excess ions remaining other than between the layers after the insertion reaction of the quaternary ammonium ion having an alkyl group having 12 or more carbon atoms. Purification is carried out by an appropriate method such as batch washing in which separation steps such as separation and filtration are repeated, or continuous washing in which a solvent is continuously flowed for washing. The degree of purification can be confirmed, for example, when a quaternary ammonium halide having an alkyl group having 12 or more carbon atoms is used as a raw material, an aqueous silver nitrate solution is added to the washing solution, and white silver halide is not produced. If this purification is insufficient, it may cause a decrease in thermal stability during molding due to a quaternary ammonium ion-derived free compound, smoke generation, mold contamination, odor, and the like. The water content of the intercalation compound after purification is controlled to 10 wt% or less, preferably 5 wt% or less, and most preferably 3 wt% or less in order to reduce undesired side reactions such as hydrolysis during mixing with the polyamide component. To do. When the water content exceeds 10 wt%, deterioration due to side reactions such as hydrolysis of the polyamide component becomes remarkable, and the toughness of the polyamide resin composition is greatly reduced. The intercalation compound used in the present invention has a maximum particle size after purification of 500 μm or less, preferably 1 μm or less.
It is desirable that the particles are pulverized to a particle size of 00 μm or less, more preferably 50 μm or less, and most preferably 10 μm or less in order to apply to a wide range of dispersion methods having different shearing efficiencies. In the polyamide resin composition of the present invention, it is desirable that the interlayer compound is contained in the polyamide resin composition in an amount of 1 to 20% by weight, preferably 1 to 10% by weight, and more preferably 1 to 5% by weight as an inorganic ash content. . The amount of inorganic ash can be determined from the weight fraction of the residue obtained by completely eliminating the organic component of the polyamide resin composition in an electric furnace at 650 ° C. When the amount of inorganic ash is less than 1% by weight, the elastic modulus is not significantly improved. On the other hand, when it exceeds 20% by weight, deterioration of the polyamide component of the matrix is promoted due to the influence of the quaternary ammonium ion component in the intercalation compound, resulting in molding There are drawbacks such as trouble, which is not preferable. The intercalation compounds may be used alone or in combination. The amount of the intercalation compound is 1 to 50 parts by weight, preferably 1 to 30 parts by weight, more preferably 1 to 100 parts by weight, based on 100 parts by weight of the polyamide resin.
20 parts by weight.
【００２５】本発明のポリアミド樹脂組成物は、いわゆ
るスマターバッチとして使用するこることもでき、即ち
本発明のポリアミド樹脂組成物と他の熱可塑性樹脂成分
とを混合して、所望の無機灰分量とすることも可能であ
る。マスターバッチとして本発明のポリアミド樹脂組成
物を利用する場合、マスターバッチの無機灰分量は通常
５〜２０重量％、好ましくは７〜２０重量％、更に好ま
しくは８〜２０重量％である。マスターバッチにおける
無機灰分量が５重量％に満たないとその経済的効果が不
十分となり、２０重量％を超えると混合時の分散不良の
原因とする場合がある。The polyamide resin composition of the present invention can also be used as a so-called smatter batch, that is, the polyamide resin composition of the present invention is mixed with other thermoplastic resin components to obtain a desired inorganic ash content. It is also possible to do so. When the polyamide resin composition of the present invention is used as a masterbatch, the amount of inorganic ash in the masterbatch is usually 5 to 20% by weight, preferably 7 to 20% by weight, more preferably 8 to 20% by weight. If the amount of inorganic ash in the masterbatch is less than 5% by weight, its economic effect becomes insufficient, and if it exceeds 20% by weight, it may cause poor dispersion during mixing.
【００２６】本発明において、層間化合物とポリアミド
樹脂との混合方法には特に制限はないが、例えば、重合
前のポリアミド成分の原料に添加後ポリアミド成分の溶
融重合とともに攪拌混合する方法、該溶融重合途中ない
しは溶融重合後チップ化前に添加し攪拌混合する方法、
あるいはチップ化後のポリアミド成分に添加し押出機等
の混練機にて溶融混合する方法等任意の方法で混合可能
であるが、生産性、簡便性、汎用性から混練機を用いた
方法が好ましい。中でも、剪断効率の高い二軸押出機の
使用が好ましく、該層間化合物に含まれる水分を効率的
に除去できるベント付き二軸押出機の使用が最適であ
る。In the present invention, the method of mixing the intercalation compound and the polyamide resin is not particularly limited, but, for example, a method of adding to the raw material of the polyamide component before polymerization and then stirring and mixing with the melt polymerization of the polyamide component, the melt polymerization A method of adding and stirring and mixing in the middle or after melt polymerization before chip formation,
Alternatively, it can be mixed by any method such as a method of adding to the polyamide component after chip formation and melt-mixing with a kneader such as an extruder, but a method using a kneader is preferable from the viewpoint of productivity, simplicity, and versatility. . Above all, it is preferable to use a twin-screw extruder having high shear efficiency, and it is most preferable to use a twin-screw extruder with a vent capable of efficiently removing water contained in the intercalation compound.
【００２７】また、本発明のポリアミド樹脂組成物に酸
変性ポリオレフィン樹脂を配合することにより、強度、
剛性及び靱性において極めて良好なポリアミド系樹脂組
成物を得ることができる。ポリアミド系樹脂組成物中の
層間化合物は無機灰分量として通常１〜５重量％、靱性
の点で好ましくは１〜４重量％、より好ましくは１〜３
重量％である。ポリアミド樹脂の数平均重合度は７０〜
５００、好ましくは２２０〜５００であるが、更に、靱
性の点でより好ましくは２４０〜５００、成形性の点で
より好ましくは２４０〜４００であり、最も好ましくは
２７〜３８０である。ポリアミド樹脂の数平均重合度が
２２０に満たない場合、靱性が急激に低下する場合があ
る。酸変性ポリオレフィン樹脂は、通常全体の８〜２０
重量％、剛性とのバランスの点で好ましくは８〜１９重
量％、より好ましくは８〜１８重量％であり、更に、靱
性特に耐衝撃性の点からより好ましくは９〜１８重量
％、最も好ましくは９〜１６重量％添加する。Further, by adding an acid-modified polyolefin resin to the polyamide resin composition of the present invention, the strength,
It is possible to obtain a polyamide-based resin composition having extremely good rigidity and toughness. The amount of the intercalation compound in the polyamide resin composition is usually 1 to 5% by weight as an inorganic ash content, preferably 1 to 4% by weight in terms of toughness, more preferably 1 to 3% by weight.
% By weight. The number average degree of polymerization of the polyamide resin is 70 to
It is 500, preferably 220 to 500, more preferably 240 to 500 in terms of toughness, more preferably 240 to 400 in terms of moldability, and most preferably 27 to 380. When the number average degree of polymerization of the polyamide resin is less than 220, the toughness may be rapidly reduced. The acid-modified polyolefin resin is usually 8 to 20% in total.
%, Preferably 8 to 19% by weight, more preferably 8 to 18% by weight from the viewpoint of balance with rigidity, and further preferably 9 to 18% by weight, most preferably 8 to 18% by weight, from the viewpoint of toughness, especially impact resistance. Is added in an amount of 9 to 16% by weight.
【００２８】ここで、酸変性ポリオレフィン樹脂とは、
例えば、ポリエチレン樹脂、ポリプロピレン樹脂、エチ
レン−プロピレン共重合体、エチレン−ブテン共重合体
等のポリオレフィン樹脂に対して、無水マレイン酸、フ
マル酸、アクリル酸、メタクリル酸等の不飽和カルボン
酸を有機過酸化物の存在下溶融混合してグラフトせしめ
たものを言う。Here, the acid-modified polyolefin resin means
For example, unsaturated carboxylic acids such as maleic anhydride, fumaric acid, acrylic acid and methacrylic acid are added to organic resins with polyolefin resins such as polyethylene resins, polypropylene resins, ethylene-propylene copolymers and ethylene-butene copolymers. It is the one that has been melt-mixed and grafted in the presence of an oxide.
【００２９】ポリアミド樹脂、層間化合物及び酸変性ポ
リオレフィン樹脂の混合方法については特に制限はない
が、上述の二軸押出機による溶融混練が好ましく、これ
ら３成分を同時に混練する方法、ポリアミド樹脂と層間
化合物を先に混練し次いで酸変性ポリオレフィン樹脂と
混練する方法、ポリアミド樹脂と酸変性ポリオレフィン
樹脂とを先に混練し次いで層間化合物と混練する方法、
高濃度の該層間化合物をポリアミド樹脂に溶融混練して
得たマスターバッチと高濃度の酸変性ポリオレフィン樹
脂をポリアミド樹脂に溶融混練して得たマスターバッチ
とを所望の組成となるようポリアミド樹脂と配合し溶融
混合する方法等が可能である。層間化合物と酸変性ポリ
オレフィン樹脂とをそれぞれマスターバッチとしポリア
ミド樹脂と所望の組成に配合する方法は、二軸押出機等
による溶融混練を経ず、直接成形機に投入して成形品を
得るいわゆるドライブレンド法として極めて経済的に行
うこともできる。The method of mixing the polyamide resin, the intercalation compound and the acid-modified polyolefin resin is not particularly limited, but the melt kneading by the above-mentioned twin screw extruder is preferable, and the method of simultaneously kneading these three components, the polyamide resin and the intercalation compound. A method of kneading and then kneading with an acid-modified polyolefin resin, a method of kneading a polyamide resin and an acid-modified polyolefin resin first and then kneading with an intercalation compound,
A masterbatch obtained by melt-kneading a high-concentration intercalation compound into a polyamide resin and a masterbatch obtained by melt-kneading a high-concentration acid-modified polyolefin resin into a polyamide resin are blended with a polyamide resin so as to have a desired composition. Then, a method of melt mixing is possible. A method of blending an interlayer compound and an acid-modified polyolefin resin into a masterbatch into a polyamide resin and a desired composition, respectively, is a so-called dry method in which a molded product is obtained by directly introducing the compound into a molding machine without melt-kneading with a twin-screw extruder or the like. The blending method can be performed very economically.
【００３０】本発明のポリアミド樹脂組成物には、本発
明の目的を損なわない限りにおいて必要に応じ常用の各
種添加成分、例えばガラス繊維、炭素繊維等の無機繊
維、ガラスフレーク、ガラスビーズ、雲母、タルク、カ
オリン、ウオラストナイト等の無機粉体、各種可塑剤、
核剤、安定剤、着色剤、難燃剤等を添加できる。更に、
本発明のボリアミド樹脂組成物には、本発明の目的を損
なわない限りにおいて必要に応じ通常のポリアミド樹脂
にブレンドされる熱可塑性樹脂や熱可塑性エラストマ
ー、例えば芳香族ポリエステル樹脂、芳香族ポリカーボ
ネート樹脂、ＡＢＳ樹脂、ポリフェニレンエーテル樹
脂、ポリオキシメチレン樹脂、ポリアリーレンスルフィ
ド樹脂、ポリプロピレン樹脂、ポリエチレン樹脂、エポ
キシ樹脂、フェノキシ樹脂、フェノール樹脂、マレイミ
ド樹脂、スチレン−無水マレイン酸共重合体、エポキシ
基を有する化合物で変性されたポリオレフィン樹脂、ア
イオノマー樹脂、ポリアミドエラストマー、ポリエーテ
ル系エラストマー、ポリエステルエラストマー、カルボ
キシル基又はエポキシ基を有する化合物で変性されたエ
チレン系熱可塑性エラストマー、アクリルゴム、コアー
シェル型アクリルゴム等を加えてもよい。In the polyamide resin composition of the present invention, if necessary, various commonly used additive components such as glass fibers, inorganic fibers such as carbon fibers, glass flakes, glass beads, mica, Inorganic powder such as talc, kaolin, wollastonite, various plasticizers,
Nucleating agents, stabilizers, coloring agents, flame retardants and the like can be added. Furthermore,
The polyamide resin composition of the present invention contains a thermoplastic resin or a thermoplastic elastomer, which is blended with an ordinary polyamide resin as necessary as long as the object of the present invention is not impaired, such as aromatic polyester resin, aromatic polycarbonate resin, ABS. Resin, polyphenylene ether resin, polyoxymethylene resin, polyarylene sulfide resin, polypropylene resin, polyethylene resin, epoxy resin, phenoxy resin, phenol resin, maleimide resin, styrene-maleic anhydride copolymer, modified with a compound having an epoxy group Polyolefin resin, ionomer resin, polyamide elastomer, polyether elastomer, polyester elastomer, ethylene-based thermoplastic elastomer modified with a compound having a carboxyl group or an epoxy group Tomah, acrylic rubber, may be added to core-shell type acrylic rubber.
【００３１】[0031]
【実施例】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越えない限り、以下の実施
例に限定されるものではない。EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to the following examples unless it exceeds the gist thereof.
【００３２】〔評価項目と測定方法〕 〔溶融混練〕東芝機械（株）製の二軸押出機ＴＥＭ３５
Ｂにより、バレル温度設定２８０℃、スクリュ回転数２
５０ｒｐｍの条件で溶融混練しチップ化した。[Evaluation Items and Measuring Method] [Melt-kneading] Twin-screw extruder TEM35 manufactured by Toshiba Machine Co., Ltd.
Depending on B, barrel temperature setting 280 ° C, screw rotation speed 2
Melt kneading was performed under the condition of 50 rpm to form chips.
【００３３】〔射出成形〕日本製鋼所（株）製の射出成
形機Ｊ２８ＳＡにより、バレル温度は２６０℃、但しナ
イロン６６系のみ２８０℃に設定し、金型表面実測温度
９０℃、射出／冷却＝１５／１５秒、スクリュー回転数
１５０ｒｐｍ、射出速度最大の条件で成形してＡＳＴＭ
−Ｄ６３８規格の引張試験片を得た。[Injection molding] With an injection molding machine J28SA manufactured by Japan Steel Works, Ltd., the barrel temperature was set to 260 ° C., but nylon 66 series was set to 280 ° C., the mold surface measured temperature was 90 ° C., injection / cooling = 15/15 seconds, screw rotation speed 150 rpm, injection speed maximum molding conditions ASTM
A tensile test piece of D638 standard was obtained.
【００３４】〔引張試験〕ＡＳＴＭ−Ｄ６３８によっ
た。弾性率Ｍｔ（単位：ｋｇ／ｃｍ2）と破断伸びＥｔ
（単位：％）を測定した。 〔無機灰分量〕引張試験片約１．５ｇを精秤し、６５０
℃の電気炉内で完全に有機物を焼失せしめた残渣の重量
分率（単位：ｗｔ％）から求めた。[Tensile Test] According to ASTM-D638. Elastic modulus Mt (unit: kg / cm 2 ) and breaking elongation Et
(Unit:%) was measured. [Inorganic ash content] About 1.5 g of a tensile test piece is precisely weighed and 650
It was determined from the weight fraction (unit: wt%) of the residue in which the organic matter was completely burned out in an electric furnace at ℃.
【００３５】〔酸素透過速度〕米国ＭＯＣＯＮ社製酸素
透過試験機ＯＸ−ＴＲＡＮ１０／５０Ｈにより２３℃、
相対湿度９０％の条件で測定した。測定には、バレル温
度を２８０℃とし巻き取りロール温度を１２０℃とした
Ｔダイ成形フィルム（２５μｍ厚）を使用し、２５μｍ
厚、１ｍ2 、２４時間当たりの酸素透過量として表し
た。[Oxygen Permeation Rate] An oxygen permeation tester OX-TRAN10 / 50H manufactured by MOCON, USA at 23 ° C.
The measurement was performed under the condition of relative humidity of 90%. For the measurement, a T-die forming film (25 μm thick) having a barrel temperature of 280 ° C. and a winding roll temperature of 120 ° C. was used.
It was expressed as thickness, 1 m 2 , and oxygen permeation amount per 24 hours.
【００３６】〔表面外観観察〕目視評価により射出成形
品の表面の平滑性を比較した。 〔衝撃試験〕ＡＳＴＭ−Ｄ２５６による１／８インチ厚
のノッチつきＩＺＯＤ衝撃試験（ＩＺＯＤと略記、単位
ｋｇ・ｃｍ／ｃｍ）、及びＲｈｅｏｍｅｔｒｉｃ Ｉｎ
ｃ．社製Ｈｉｇｈ Ｒａｔｅ Ｉｍｐａｃｔ Ｔｅｓｔ
ｅｒ ＲＩＴ８０００により、直径１インチの貫通穴の
開いた治具ではさみ、固定した１００ｍｍ四方×２ｍｍ
厚の平板を、先端が球面（曲率半径３／８インチ）の打
撃棒で４．４３ｍ／秒の速度で打ち抜く高速平面衝撃試
験（平面衝撃と略記、単位Ｊ）を行った。 〔荷重たわみ温度〕ＡＳＴＭ−Ｄ６４８によった。荷重
は、４．６ｋｇ／ｃｍ2 、１８．６ｋｇ／ｃｍ2 の２種
とした。 〔使用した層状珪酸塩〕使用した層状珪酸塩の名称、鉱
物名、種類、メチレンブルー吸着法により測定した陽イ
オン交換容量（ＣＥＣと略記）、メーカーを表１に記載
した。[Observation of Surface Appearance] The surface smoothness of injection-molded articles was compared by visual evaluation. [Impact Test] 1/8 inch thick notched IZOD impact test according to ASTM-D256 (abbreviated as IZOD, unit kg · cm / cm), and Rheometric In
c. High Rate Impact Test
er RIT 8000, 100 mm square x 2 mm fixed and pinched by a jig with a 1-inch diameter through hole
A high-speed plane impact test (abbreviated as plane impact, unit J) was performed by punching a thick flat plate with a striking rod having a spherical tip (curvature radius 3/8 inch) at a speed of 4.43 m / sec. [Deflection temperature under load] According to ASTM-D648. The load was two kinds of 4.6 kg / cm 2 and 18.6 kg / cm 2 . [Layered silicate used] Table 1 shows the names, mineral names and types of the layered silicates used, the cation exchange capacity (abbreviated as CEC) measured by the methylene blue adsorption method, and the manufacturers.
【００３７】[0037]
【表１】 表 １ ──────────────────────────────────── 名 称 鉱 物 名 種類 ＣＥＣ1) メーカー ──────────────────────────────────── オスモスＮ モンモリロナイト 天然 １００ 白石工業（株） クニピアＦ モンモリロナイト 天然 １２０ クニミネ工業（株） ＭＥ１００ 膨潤性フッ素雲母 合成 ８０ コープケミカル（株） ダイモナイト 膨潤性フッ素雲母 合成 １４ トピー工業（株） Ａ−６１ 雲 母 天然 イオン交換性なし 山口雲母工業所 （株） ──────────────────────────────────── 1)ミリ当量／１００ｇ[Table 1] Table 1 ──────────────────────────────────── Nominal name Mineral name CEC 1 ) Manufacturer ──────────────────────────────────── Osmos N Montmorillonite Natural 100 Kunipia F, Shiraishi Industry Co., Ltd. Montmorillonite Natural 120 Kunimine Industry Co., Ltd. ME100 Swellable Fluorine Mica Synthetic 80 Corp Chemical Co., Ltd. Daimonite Swellable Fluorine Mica Synthetic 14 Topy Industries Co., Ltd. A-61 Mica Natural Ion Exchangeable Yamaguchi Mica Industry Co., Ltd. ─────────────────────────────────── 1) Milli-equivalent / 100g
【００３８】〔層間化合物の調製法〕層状珪酸塩約１０
０ｇを精秤しこれを室温の水１０リットルに攪拌分散
し、ここに層状珪酸塩のＣＥＣの１．４倍当量のアンモ
ニウムイオンの塩酸塩を添加して６時間攪拌した。精製
した沈降性の固体を濾別し、次いで３０リットルの脱塩
水中で攪拌洗浄後再び濾別した。この洗浄と濾別の操作
を少なくとも３回行い、洗液の硝酸銀試験で塩化物イオ
ンが検出されなくなるのを確認した。得られた固体は３
〜７日の風乾後乳鉢で粉砕し、更に５０℃の温風乾燥を
３〜１０時間行い再度乳鉢で粉砕した。乾燥条件はゲス
トのアンモニウムイオンの種類により変動するが、最大
粒径が１００μｍ程度となる粉砕性の確保と、窒素気流
下１２０℃で１時間保持した場合の熱重量減少で評価し
た残留水分量が２〜３ｗｔ％となることを指標とした。
層間化合物の配合量は、まず層間化合物中の灰分量を、
窒素気流下５００℃で３時間保持した場合の残渣の重量
分率を測定し、この値をもとに組成物中の灰分量（理論
灰分量）が所定の値になるように調整した。[Preparation Method of Intercalation Compound] Layered silicate about 10
0 g was precisely weighed and stirred and dispersed in 10 liters of water at room temperature. An ammonium ion hydrochloride having 1.4 times the equivalent of CEC of the layered silicate was added thereto and stirred for 6 hours. The purified precipitated solid was filtered off, washed with 30 liters of demineralized water with stirring, and then filtered off again. This washing and filtering operation was performed at least three times, and it was confirmed by the silver nitrate test of the washing liquid that chloride ions could not be detected. The solid obtained is 3
After air-drying for 7 days, it was crushed in a mortar and further dried with warm air at 50 ° C. for 3-10 hours, and then crushed again in the mortar. Drying conditions vary depending on the type of guest's ammonium ion, but the residual water content evaluated by securing pulverizability with a maximum particle size of about 100 μm and thermogravimetric reduction when kept at 120 ° C. for 1 hour under a nitrogen stream is shown. The index was set to be 2 to 3 wt%.
The compounding amount of the intercalation compound is first the ash content in the intercalation compound,
The weight fraction of the residue when kept at 500 ° C. for 3 hours under a nitrogen stream was measured, and based on this value, the ash content (theoretical ash content) in the composition was adjusted to a predetermined value.
【００３９】〔実施例１〜８〕ナイロン６（ノバミッド
１０２０Ｊ、三菱化成（株）製、数平均重合度２２０、
ノバミッドは登録商標）のチップと表２に示した層間化
合物とをドライブレンドし溶融混練した。これらの射出
成形品の表面はいずれも平滑で光沢があった。これらの
引張試験結果を表２に示す。Examples 1 to 8 Nylon 6 (Novamid 1020J, manufactured by Mitsubishi Kasei Co., Ltd., number average degree of polymerization: 220,
Novamid was obtained by dry blending chips (registered trademark) and the intercalation compounds shown in Table 2 and melt-kneading. The surfaces of these injection-molded articles were smooth and glossy. The results of these tensile tests are shown in Table 2.
【００４０】〔比較例１〜１５〕実施例１〜８同様の実
験を、表２に示した層間化合物あるいは雲母を用いて行
った。ただし比較例１３においては層間化合物あるいは
雲母を添加しなかった。射出成形品の表面外観は、比較
例１３と比較例１４においては微粒子による微小な凹凸
が観察されたが、比較例１１〜１２及び比較例１５のも
のは実施例１〜８のものと同等であった。これらの引張
試験結果を表２に示す。Comparative Examples 1 to 15 The same experiments as in Examples 1 to 8 were conducted using the intercalation compounds or mica shown in Table 2. However, in Comparative Example 13, no intercalation compound or mica was added. Regarding the surface appearance of the injection-molded products, fine irregularities due to fine particles were observed in Comparative Examples 13 and 14, but those of Comparative Examples 11 to 12 and Comparative Example 15 were equivalent to those of Examples 1 to 8. there were. The results of these tensile tests are shown in Table 2.
【００４１】〔比較例１６〕表２に示す層間化合物を、
ε−カプロラクタム／６−アミノカプロン酸＝９／１
（重量比）の混合物に対し理論無機灰分量が５ｗｔ％と
なるよう混合し、乳鉢で粉砕混合した。次いで、反応器
に仕込み窒素置換後１００℃に昇温融解し攪拌を３０分
行い層間化合物を分散させた。その後２５０℃に昇温し
大気圧で２時間反応後、５０Ｔｏｒｒまで減圧して重合
を完了した。減圧時間は延べ２時間であった。生成した
組成物は剪断速度の低い状態では非常に溶融粘度が高
く、反応器からの通常の抜き出し作業が困難であった。
こうして得た組成物の粉砕物を熱水抽出し水溶性成分を
除去後、真空乾燥（１２０℃、１６時間）して射出成形
に供した。そして、実施例１〜８と同様の評価を行っ
た。射出成形片の表面外観は実施例１〜８のものと同等
であった。引張試験の結果を表２に示す。また、ｍ−ク
レゾール／クロロホルム＝３／７（重量比）の混合溶媒
を展開液とした４０℃のゲルパーミエーションクロマト
グラフィ（カラム：東ソー（株）製ＰＬ−ｇｅｌ１０μ
ｍ ＭＩ×ＥＤ）によれば、ナイロン６成分の数平均重
合度は１９０であった。Comparative Example 16 The intercalation compounds shown in Table 2 were
ε-caprolactam / 6-aminocaproic acid = 9/1
The mixture (weight ratio) was mixed so that the theoretical amount of inorganic ash was 5 wt%, and the mixture was pulverized and mixed in a mortar. Then, the reaction mixture was charged into a reactor and, after purging with nitrogen, the temperature was raised to 100 ° C., melting was carried out, and stirring was carried out for 30 minutes to disperse the intercalation compound. Thereafter, the temperature was raised to 250 ° C., the reaction was carried out at atmospheric pressure for 2 hours, and then the pressure was reduced to 50 Torr to complete the polymerization. The depressurization time was 2 hours in total. The composition thus produced had a very high melt viscosity in a state where the shear rate was low, and it was difficult to carry out the usual operation of extracting from the reactor.
The pulverized product of the composition thus obtained was extracted with hot water to remove the water-soluble components, and then vacuum dried (120 ° C., 16 hours) and subjected to injection molding. And evaluation similar to Examples 1-8 was performed. The surface appearance of the injection-molded pieces was similar to that of Examples 1-8. The results of the tensile test are shown in Table 2. Further, gel permeation chromatography at 40 ° C. using a mixed solvent of m-cresol / chloroform = 3/7 (weight ratio) as a developing solution (column: PL-gel 10 μ manufactured by Tosoh Corporation).
According to (m MI × ED), the number average degree of polymerization of the nylon 6 component was 190.
【００４２】〔実施例９〜１０〕ナイロン６６（Ｚｙｔ
ｅｌ ＦＥ３４２１，Ｄｕ Ｐｏｎｔ社製、数平均重合
度１５０，Ｚｙｔｅｌは登録商標）のチップと表３に示
した層間化合物とをドライブレンドし溶融混練した。こ
れらの射出成形品の表面はいずれも平滑で光沢があっ
た。引張試験の結果を表３に示す。[Examples 9 to 10] Nylon 66 (Zyt
El FE3421, manufactured by Du Pont, number average degree of polymerization: 150, Zytel is a registered trademark) and the intercalation compound shown in Table 3 were dry blended and melt-kneaded. The surfaces of these injection-molded articles were smooth and glossy. The results of the tensile test are shown in Table 3.
【００４３】〔比較例１７〜１８〕実施例９〜１０同様
の実験を、表３に示した層間化合物を用いて行った。た
だし比較例１８においては層間化合物あるいは雲母を添
加しなかった。射出成形品の表面外観は実施例９〜１０
のものと同等であった。[Comparative Examples 17 to 18] The same experiments as in Examples 9 to 10 were conducted using the intercalation compounds shown in Table 3. However, in Comparative Example 18, no intercalation compound or mica was added. The surface appearance of the injection-molded products is shown in Examples 9 to 10.
It was equivalent to that of.
【００４４】〔実施例１１〕ナイロン１２（Ｇｒｉｌａ
ｍｉｄ Ｌ２５，ＥＭＳ ＣＨＥＭＩＥ ＡＧ 社製、
数平均重合度１６０，Ｇｒｉｌａｍｉｄは登録商標）の
チップと表４に示した層間化合物とをドライブレンドし
溶融混練した。射出成形品の表面は平滑で光沢があっ
た。引張試験の結果を表４に示す。Example 11 Nylon 12 (Grilla
mid L25, manufactured by EMS CHEMIE AG,
A chip having a number average degree of polymerization of 160 and Grilamid is a registered trademark) and the intercalation compound shown in Table 4 were dry-blended and melt-kneaded. The surface of the injection molded product was smooth and glossy. Table 4 shows the results of the tensile test.
【００４５】〔比較例１９〕実施例１１と同様の実験を
層間化合物あるいは雲母を加えずに行った。射出成形品
の表面外観は実施例１１のものと同等であった。引張試
験の結果を表４に示す。Comparative Example 19 The same experiment as in Example 11 was conducted without adding an intercalation compound or mica. The surface appearance of the injection-molded product was similar to that of Example 11. Table 4 shows the results of the tensile test.
【００４６】〔実施例１２〜１３〕非晶性ナイロン（ノ
バミッド×２１ Ｓ０４Ｊ、三菱化成（株）製、数平均
重合度８０、ノバミッドは登録商標）のチップと表５に
示した層間化合物とをドライブレンドし溶融混練した。
これらの射出成形品の表面はいずれも平滑で光沢があっ
た。引張試験の結果を表５に示す。[Examples 12 to 13] Chips of amorphous nylon (Novamid x 21 S04J, manufactured by Mitsubishi Kasei Co., Ltd., number average degree of polymerization: 80, Novamid is a registered trademark) and the intercalation compounds shown in Table 5 were used. It was dry-blended and melt-kneaded.
The surfaces of these injection-molded articles were smooth and glossy. The results of the tensile test are shown in Table 5.
【００４７】〔比較例２０〕実施例１２〜１３同様の実
験を層間化合物を加えずに行った。射出成形品の表面外
観は実施例１２〜１３のものと同等であった。引張試験
の結果を表５に示す。[Comparative Example 20] The same experiments as in Examples 12 to 13 were conducted without adding an intercalation compound. The surface appearance of the injection-molded products was similar to that of Examples 12-13. The results of the tensile test are shown in Table 5.
【００４８】〔比較例２１〕実施例１２〜１３で用いた
非晶性ナイロンと同一組成で数平均重合度が６０の非晶
性ナイロンを用い、実施例１３と同様の実験を行った。
射出成形品の表面外観は実施例１３と同等であった。引
張試験の結果を表５に示す。[Comparative Example 21] The same experiment as in Example 13 was conducted using amorphous nylon having the same composition as the amorphous nylon used in Examples 12 to 13 and having a number average degree of polymerization of 60.
The surface appearance of the injection-molded product was the same as in Example 13. The results of the tensile test are shown in Table 5.
【００４９】〔実施例１４〕実施例１〜８において使用
したと同様のナイロン６と表６に示した層間化合物をド
ライブレンドし溶融混練した。得られたポリアミド樹脂
組成物のチップからＴダイ成形フィルムを作り、その酸
素透過性を評価した。Example 14 Nylon 6 similar to that used in Examples 1 to 8 and the intercalation compound shown in Table 6 were dry blended and melt-kneaded. A T-die molding film was produced from the obtained polyamide resin composition chip, and its oxygen permeability was evaluated.
【００５０】〔実施例１５〕実施例１４の組成物のチッ
プと実施例１２〜１３において用いたと同様の非晶性ナ
イロンのチップとを、ナイロン６／非晶性ナイロン＝７
／３（重量比）となるようドライブレンドし溶融混練し
た。得られたポリアミド樹脂組成物のチップからＴダイ
成形フィルムを作り、実施例１４と同様の酸素透過性試
験を行った。Example 15 Chips of the composition of Example 14 and chips of amorphous nylon similar to those used in Examples 12 to 13 were prepared by using nylon 6 / amorphous nylon = 7.
It was dry-blended and melt-kneaded so that the ratio would be / 3 (weight ratio). A T-die molding film was prepared from the obtained polyamide resin composition chip, and the same oxygen permeability test as in Example 14 was conducted.
【００５１】〔比較例２２〕実施例１〜８で使用したと
同様のナイロン６チップからＴダイ成形フィルムを作
り、実施例１４と同様の酸素透過性試験を行った。[Comparative Example 22] A T-die forming film was made from the same nylon 6 chips as used in Examples 1 to 8 and the same oxygen permeability test as in Example 14 was conducted.
【００５２】〔比較例２３〕実施例１２〜１３で用いた
と同様の非晶性ナイロンのチップと実施例１〜８で用い
たと同様のナイロン６のチップとを、ナイロン６／非晶
性ナイロン＝７／３（重量比）となるようドライブレン
ドし溶融混練した。得られたチップからＴダイ成形フィ
ルムを作り、実施例１４と同様の酸素透過性試験を行っ
た。[Comparative Example 23] An amorphous nylon chip similar to that used in Examples 12 to 13 and a nylon 6 chip similar to those used in Examples 1 to 8 were used as nylon 6 / amorphous nylon = The mixture was dry-blended and melt-kneaded so as to be 7/3 (weight ratio). A T-die molding film was prepared from the obtained chips, and the same oxygen permeability test as in Example 14 was conducted.
【００５３】[0053]
【表２】 [Table 2]
【００５４】[0054]
【表３】 [Table 3]
【００５５】[0055]
【表４】 [Table 4]
【００５６】[0056]
【表５】 [Table 5]
【００５７】[0057]
【表６】 [Table 6]
【００５８】〔実施例１６〕数平均重合度２６０のナイ
ロン６チップ７４．６重量％、酸変性エチレン−αオレ
フィン共重合体を約４５重量％含有したタフ化ナイロン
６樹脂（ノバミッドＳＴ１４５、三菱化成（株）製、ベ
ースとなるナイロン６の数平均重合度は１４０、ノバミ
ッドは登録商標）２２．４重量％、及び実施例１で用い
た層間化合物３重量％をドライブレンドし、溶融混練を
行った。但し二軸押出機のスクリュ回転数は１５０ｒｐ
ｍとした。こうして得た樹脂組成物のチップの蟻酸抽出
液を大過剰のメタノール中にゆっくりと滴下し、ナイロ
ン６成分を再沈殿させ、有機溶媒を減圧除去して得たナ
イロン６成分の数平均重合度を比較例１６と同様に測定
したところ２４０であった。Example 16 A tough nylon 6 resin (Novamid ST145, Mitsubishi Kasei) containing 74.6% by weight of nylon 6 chips having a number average degree of polymerization of 260 and about 45% by weight of an acid-modified ethylene-α-olefin copolymer. Nylon 6 used as a base has a number average degree of polymerization of 140, Novamid is a registered trademark of 22.4% by weight, and 3% by weight of the intercalation compound used in Example 1 are dry-blended and melt-kneaded. It was However, the screw rotation speed of the twin-screw extruder is 150 rp
m. The formic acid extract of chips of the resin composition thus obtained was slowly dropped into a large excess of methanol to reprecipitate the nylon 6 component, and the organic solvent was removed under reduced pressure to obtain the number average degree of polymerization of the nylon 6 component. It was 240 when measured in the same manner as in Comparative Example 16.
【００５９】〔実施例１７〕実施例１のナイロン６チッ
プ（数平均重合度２２０）９０重量％と実施例１で用い
た層間化合物１０重量％とをドライブレンドし、溶融混
練を行い、無機灰分量６．１１重量％のチップ（以下マ
スターバッチと称する）を得た。このマスターバッチの
チップ３０重量％、数平均重合度３３０のナイロン６チ
ップ４７．６重量％、及び実施例１６で使用したタフ化
ナイロン６樹脂チップ２２．４重量％をドライブレンド
し、直接射出成形した。但し射出成形機のバレルは２８
０℃に設定し、スクリュ回転数は１００ｒｐｍとした。
実施例１６と同様にして測定した数平均重合℃は、２７
０であった。[Example 17] 90% by weight of nylon 6 chips (number average degree of polymerization: 220) of Example 1 and 10% by weight of the intercalation compound used in Example 1 were dry blended and melt-kneaded to obtain an inorganic ash. Chips having a quantity of 6.11% by weight (hereinafter referred to as masterbatch) were obtained. 30% by weight of chips of this masterbatch, 47.6% by weight of nylon 6 chips having a number average degree of polymerization of 330, and 22.4% by weight of toughened nylon 6 resin chips used in Example 16 were dry-blended and directly injection-molded. did. However, the barrel of the injection molding machine is 28
The temperature was set to 0 ° C. and the screw rotation speed was 100 rpm.
The number average polymerization temperature, measured in the same manner as in Example 16, was 27.
It was 0.
【００６０】〔実施例１８〜１９〕実施例１のナイロン
６チップ（数平均重合度２２０）、実施例１で用いた層
間化合物、及びＡＳＴＭ−Ｄ１２３８に基づく１９０
℃、２．１６ｋｇ／ｃｍ2 荷重のメルトインデックスが
２．０、密度が０．８９である酸変性エチレン−ブテン
共重合体（グラフト酸量は無水マレイン酸として４５０
０ｐｐｍ）を溶融混練した。この時、酸変性エチレン−
ブテン共重合体は１９重量％であり、層間化合物の量は
表７の無機灰分量に示される通りであった。溶融混練条
件は実施例１６と同様にした。Examples 18 to 19 Nylon 6 chips (number average degree of polymerization: 220) of Example 1, the intercalation compound used in Example 1, and 190 based on ASTM-D1238.
An acid-modified ethylene-butene copolymer having a melt index of 2.0 and a density of 0.89 under a load of 2.16 kg / cm 2 ( ° C., a graft acid amount of 450 as maleic anhydride).
0 ppm) was melt-kneaded. At this time, acid-modified ethylene
The butene copolymer was 19% by weight, and the amount of the intercalation compound was as shown in the amount of inorganic ash in Table 7. The melt-kneading conditions were the same as in Example 16.
【００６１】〔実施例２０〕ナイロン６チップとして実
施例１で使用したナイロン６（数平均重合度２２０）を
用いて実施例１６と同様の実験を行った。実施例１６と
同様にして測定した数平均重合度は、２１０であった。Example 20 The same experiment as in Example 16 was carried out using Nylon 6 (number average degree of polymerization: 220) used in Example 1 as a nylon 6 chip. The number average degree of polymerization measured in the same manner as in Example 16 was 210.
【００６２】〔実施例２１〕実施例１７のマスターバッ
チのチップ３０重量％、実施例１で使用したナイロン６
（数平均重合度２２０）のチップ４７．６重量％、及び
実施例１６で使用したフタ化ナイロン６樹脂チップ２
２．４重量％をドライブレンドし、実施例１７同様直接
射出成形した。実施例１６と同様にして測定した数平均
重合度は、２１０であった。[Example 21] 30% by weight of chips of the masterbatch of Example 17, nylon 6 used in Example 1
47.6% by weight of chips having a number average degree of polymerization of 220, and capped nylon 6 resin chips 2 used in Example 16
2.4% by weight was dry blended and directly injection-molded as in Example 17. The number average degree of polymerization measured in the same manner as in Example 16 was 210.
【００６３】〔実施例２２〕実施例１８において、酸変
性エチレン−ブテン共重合体の量を２２重量％に変える
以外は実施例１８と同様に行った。Example 22 The procedure of Example 18 was repeated, except that the amount of the acid-modified ethylene-butene copolymer was changed to 22% by weight.
【００６４】〔実施例２３〕実施例１８において、酸変
性エチレン−ブテン共重合体の量を７重量％に変える以
外は実施例１８と同様に行った。Example 23 The procedure of Example 18 was repeated, except that the amount of the acid-modified ethylene-butene copolymer was changed to 7% by weight.
【００６５】〔実施例２４〕実施例１８において、層間
化合物の量を表７に示すように増やして同様の実験を行
った。Example 24 The same experiment as in Example 18 was carried out by increasing the amount of the intercalation compound as shown in Table 7.
【００６６】〔比較例２４〕実施例１８において、層間
化合物を添加せずに同様の実験を行った。Comparative Example 24 The same experiment as in Example 18 was conducted without adding the intercalation compound.
【００６７】〔比較例２５〕比較例１６の樹脂組成物の
チップ３９．６重量％、数平均重合度が３３０のナイロ
ン６チップ３８重量％、実施例１６で用いたタフ化ナイ
ロン６のチップ２２．４重量％をドライブレンドし、実
施例１７同様に直接射出成形した。実施例１６と同様に
して測定した数平均重合度は、２４０であった。実施例
１６〜２４、比較例２４〜２５、及び実施例２と比較例
１５について、引張試験、衝撃試験、荷重たわみ温度測
定を行った。その結果は、表７に示した。COMPARATIVE EXAMPLE 25 39.6% by weight of the resin composition of Comparative Example 16 and 38% by weight of nylon 6 chip having a number average degree of polymerization of 330, and toughened nylon 6 chip 22 used in Example 16 4% by weight was dry-blended and directly injection-molded in the same manner as in Example 17. The number average degree of polymerization measured in the same manner as in Example 16 was 240. Tensile test, impact test, and deflection temperature under load measurement were performed for Examples 16 to 24, Comparative Examples 24 to 25, and Example 2 and Comparative Example 15. The results are shown in Table 7.
【００６８】[0068]
【表７】 [Table 7]
【００６９】[0069]
【発明の効果】本発明のポリアミド樹脂組成物は、強
度、剛性が高く、かつ延性に優れ、しかも成形品外観が
良好であり、低比重、良好な表面外観、高強度、高剛
性、高靱性、低気体透過性の特徴を生かして、様々な機
械部品、自動車部品、電気電子部品、包装材料等に用い
ることができる。又、本発明のポリアミド樹脂組成物は
ガスバリヤー性にも優れており、包装材料としても有用
である。EFFECTS OF THE INVENTION The polyamide resin composition of the present invention has high strength and rigidity and excellent ductility, and also has a good appearance of molded articles, low specific gravity, good surface appearance, high strength, high rigidity and high toughness. By utilizing the characteristic of low gas permeability, it can be used for various machine parts, automobile parts, electric / electronic parts, packaging materials and the like. Further, the polyamide resin composition of the present invention is also excellent in gas barrier properties and is useful as a packaging material.
【００７０】又、本発明のポリアミド樹脂組成物の製造
方法によれば、強度、剛性が高く、かつ延性に優れ、し
かも成形品の外観が良好なポリアミドを容易に製造する
ことができる。又、本発明のポリアミド系樹脂組成物は
剛性、靱性及び耐熱性において優れ、更に平面衝撃強度
においても極めて優れているという特徴を有する。Further, according to the method for producing a polyamide resin composition of the present invention, it is possible to easily produce a polyamide having high strength and rigidity, excellent ductility, and good appearance of the molded product. Further, the polyamide resin composition of the present invention is characterized in that it is excellent in rigidity, toughness and heat resistance, and is also extremely excellent in plane impact strength.
Claims (8)
０ｇ以上の層状珪酸塩をホストとし炭素数１２以上のア
ルキル基を有する４級アンモニウムイオンをゲストとす
る層間化合物を、無機灰分量として１〜２０重量％含有
し、ポリアミド樹脂の数平均重合度が７０〜５００であ
ることを特徴とするポリアミド樹脂組成物。1. A cation exchange capacity of 30 meq / 10
An interlayer compound containing 0 g or more of a layered silicate as a host and a quaternary ammonium ion having an alkyl group of 12 or more carbon atoms as a guest is contained in an amount of 1 to 20% by weight as an inorganic ash content, and the number average degree of polymerization of a polyamide resin is 70-500, The polyamide resin composition characterized by the above-mentioned.
０ｇ以上の層状珪酸塩をホストとし炭素数１２以上のア
ルキル基を有する４級アンモニウムイオンをゲストとす
る層間化合物を、ポリアミド樹脂１００重量部当り１〜
５０重量部含有し、ポリアミド樹脂の数平均重合度が７
０〜５００であることを特徴とするポリアミド樹脂組成
物。2. The cation exchange capacity is 30 meq / 10.
An intercalation compound having 0 g or more of a layered silicate as a host and a guest of a quaternary ammonium ion having an alkyl group having a carbon number of 12 or more is used in an amount of 1 to 100 parts by weight of a polyamide resin.
Contains 50 parts by weight and has a number average degree of polymerization of polyamide resin of 7
It is 0-500, The polyamide resin composition characterized by the above-mentioned.
ることを特徴とする請求項１または２に記載のポリアミ
ド樹脂組成物。3. The polyamide resin composition according to claim 1 or 2, wherein the layered silicate is swellable fluoromica.
リ当量／１００ｇ以上の層状珪酸塩をホストとし炭素数
１２以上のアルキル基を有する４級アンモニウムイオン
をゲストとする層間化合物と数平均重合度が７０ないし
５００であるポリアミド樹脂とを機械的剪断下溶融混合
し、該層間化合物を無機灰分量として１ないし２０重量
％含有するポリアミド樹脂組成物を製造することを特徴
とするポリアミド樹脂組成物の製造方法。4. An interlayer compound having at least a cation exchange capacity of 30 meq / 100 g or more of a layered silicate as a host and a quaternary ammonium ion having an alkyl group having 12 or more carbon atoms as a guest, and a number average degree of polymerization of the compound. A polyamide resin composition comprising 70 to 500 of polyamide resin melt-mixed under mechanical shearing to produce a polyamide resin composition containing the interlayer compound as an inorganic ash content of 1 to 20% by weight. Method.
リ当量／１００ｇ以上の層状珪酸塩をホストとし炭素数
１２以上のアルキル基を有する４級アンモニウムイオン
をゲストとする層間化合物と数平均重合度が７０ないし
５００であるポリアミド樹脂とを機械的剪断下溶融混合
し、該層間化合物をポリアミド樹脂１００重量部当り１
〜５０重量部含有するポリアミド樹脂組成物を製造する
ことを特徴とするポリアミド樹脂組成物の製造方法。5. An interlayer compound having at least a cation exchange capacity of 30 meq / 100 g or more of a layered silicate as a host and a guest of a quaternary ammonium ion having an alkyl group of 12 or more carbon atoms and a number average degree of polymerization. A polyamide resin of 70 to 500 is melt-mixed under mechanical shearing, and the intercalation compound is mixed in an amount of 1 per 100 parts by weight of the polyamide resin.
A method for producing a polyamide resin composition, which comprises producing a polyamide resin composition containing 50 parts by weight to 50 parts by weight.
リアミド樹脂組成物及び酸変性ポリオレフィン樹脂を含
有することを特徴とするポリアミド系樹脂組成物。6. A polyamide resin composition comprising the polyamide resin composition according to any one of claims 1 to 3 and an acid-modified polyolefin resin.
リアミド樹脂組成物を９２〜８０重量％及び酸変性ポリ
オレフィン樹脂を８〜２０重量％含有するポリアミド系
樹脂組成物であって、該樹脂組成物中の層間化合物の含
有量が無機灰分量として１〜５重量％であることを特徴
とするポリアミド系樹脂組成物。7. A polyamide resin composition containing 92 to 80% by weight of the polyamide resin composition according to any one of claims 1 to 3 and 8 to 20% by weight of an acid-modified polyolefin resin. The polyamide resin composition, wherein the content of the intercalation compound in the composition is 1 to 5% by weight as the amount of inorganic ash.
〜５００であることを特徴とする請求項６又は請求項７
に記載のポリアミド樹脂系組成物。8. The number average degree of polymerization of the polyamide resin is 220.
~ 500 is the claim 6 or claim 7 characterized in that
The polyamide resin composition according to item 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23174894A JPH0812881A (en) | 1993-09-30 | 1994-09-27 | Polyamide resin composition and method for producing the same |
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24519993 | 1993-09-30 | ||
| JP5-245199 | 1994-04-26 | ||
| JP8850894 | 1994-04-26 | ||
| JP6-88508 | 1994-04-26 | ||
| JP23174894A JPH0812881A (en) | 1993-09-30 | 1994-09-27 | Polyamide resin composition and method for producing the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0812881A true JPH0812881A (en) | 1996-01-16 |
Family
ID=27305833
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23174894A Pending JPH0812881A (en) | 1993-09-30 | 1994-09-27 | Polyamide resin composition and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0812881A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5879589A (en) * | 1996-01-31 | 1999-03-09 | Kao Corporation | Process for antistatic treatment of resin and antistatic resin composition |
| WO1999048973A1 (en) * | 1998-03-20 | 1999-09-30 | Ube Industries, Ltd. | Resin composition reinforced with polyamide fibers and process for producing the same |
| JP2006131831A (en) * | 2004-11-09 | 2006-05-25 | Unitika Ltd | Polyamide resin composition |
| CN100374491C (en) * | 2000-09-14 | 2008-03-12 | 通用电气公司 | Polymer-organoclay composite compositions, method for making and article therefrom |
| JP2009542836A (en) * | 2006-07-07 | 2009-12-03 | アプライド・ナノテック・ホールディングス・インコーポレーテッド | Nanocomposite and method for producing the same |
-
1994
- 1994-09-27 JP JP23174894A patent/JPH0812881A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5879589A (en) * | 1996-01-31 | 1999-03-09 | Kao Corporation | Process for antistatic treatment of resin and antistatic resin composition |
| WO1999048973A1 (en) * | 1998-03-20 | 1999-09-30 | Ube Industries, Ltd. | Resin composition reinforced with polyamide fibers and process for producing the same |
| CN100374491C (en) * | 2000-09-14 | 2008-03-12 | 通用电气公司 | Polymer-organoclay composite compositions, method for making and article therefrom |
| JP2006131831A (en) * | 2004-11-09 | 2006-05-25 | Unitika Ltd | Polyamide resin composition |
| JP2009542836A (en) * | 2006-07-07 | 2009-12-03 | アプライド・ナノテック・ホールディングス・インコーポレーテッド | Nanocomposite and method for producing the same |
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