JPS63110245A - Polyacetal resin composition - Google Patents
Polyacetal resin compositionInfo
- Publication number
- JPS63110245A JPS63110245A JP25622586A JP25622586A JPS63110245A JP S63110245 A JPS63110245 A JP S63110245A JP 25622586 A JP25622586 A JP 25622586A JP 25622586 A JP25622586 A JP 25622586A JP S63110245 A JPS63110245 A JP S63110245A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- parts
- poly
- polymer
- polyacetal resin
- 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
- 229930182556 Polyacetal Natural products 0.000 title claims abstract description 22
- 229920006324 polyoxymethylene Polymers 0.000 title claims abstract description 22
- 239000011342 resin composition Substances 0.000 title claims abstract description 10
- -1 epsilon-caprolactam) Chemical compound 0.000 claims abstract description 55
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 47
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims abstract description 21
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000011347 resin Substances 0.000 claims abstract description 20
- 229920005989 resin Polymers 0.000 claims abstract description 20
- 229920006146 polyetheresteramide block copolymer Polymers 0.000 claims abstract description 19
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000003951 lactams Chemical class 0.000 claims abstract description 6
- 150000003839 salts Chemical class 0.000 claims abstract description 6
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000004985 diamines Chemical class 0.000 claims abstract description 5
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 11
- 229920000570 polyether Polymers 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 150000002148 esters Chemical class 0.000 claims description 7
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 abstract description 16
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 abstract description 11
- 229920001577 copolymer Polymers 0.000 abstract description 7
- 230000005611 electricity Effects 0.000 abstract description 4
- 230000003068 static effect Effects 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 description 34
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 22
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 14
- 239000000203 mixture Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 238000002844 melting Methods 0.000 description 13
- 230000008018 melting Effects 0.000 description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 238000002425 crystallisation Methods 0.000 description 11
- 230000008025 crystallization Effects 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 11
- PBLZLIFKVPJDCO-UHFFFAOYSA-N 12-aminododecanoic acid Chemical compound NCCCCCCCCCCCC(O)=O PBLZLIFKVPJDCO-UHFFFAOYSA-N 0.000 description 10
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000001361 adipic acid Substances 0.000 description 7
- 235000011037 adipic acid Nutrition 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 5
- 239000004952 Polyamide Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000004898 kneading Methods 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 229920002647 polyamide Polymers 0.000 description 5
- 229920002523 polyethylene Glycol 1000 Polymers 0.000 description 5
- 239000012429 reaction media Substances 0.000 description 5
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 4
- 229920002292 Nylon 6 Polymers 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000002216 antistatic agent Substances 0.000 description 4
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 4
- 238000007334 copolymerization reaction 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
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 125000005704 oxymethylene group Chemical group [H]C([H])([*:2])O[*:1] 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- GRWFGVWFFZKLTI-IUCAKERBSA-N (-)-α-pinene Chemical compound CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-N 0.000 description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 2
- GUOSQNAUYHMCRU-UHFFFAOYSA-N 11-Aminoundecanoic acid Chemical compound NCCCCCCCCCCC(O)=O GUOSQNAUYHMCRU-UHFFFAOYSA-N 0.000 description 2
- FJDLQLIRZFKEKJ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanamide Chemical compound CC(C)(C)C1=CC(CCC(N)=O)=CC(C(C)(C)C)=C1O FJDLQLIRZFKEKJ-UHFFFAOYSA-N 0.000 description 2
- UFFRSDWQMJYQNE-UHFFFAOYSA-N 6-azaniumylhexylazanium;hexanedioate Chemical compound [NH3+]CCCCCC[NH3+].[O-]C(=O)CCCCC([O-])=O UFFRSDWQMJYQNE-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910015900 BF3 Inorganic materials 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 239000005639 Lauric acid Substances 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- YWJUZWOHLHBWQY-UHFFFAOYSA-N decanedioic acid;hexane-1,6-diamine Chemical compound NCCCCCCN.OC(=O)CCCCCCCCC(O)=O YWJUZWOHLHBWQY-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000010292 electrical insulation Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- SGBXIDHAUUXLOV-UHFFFAOYSA-N 1-sulfocyclohexa-3,5-diene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC=CC(S(O)(=O)=O)(C(O)=O)C1 SGBXIDHAUUXLOV-UHFFFAOYSA-N 0.000 description 1
- BHUXUQTZNTVSHP-UHFFFAOYSA-N 2-[(4-hydroxyphenyl)methyl]-3,3-dimethylbutanamide Chemical compound CC(C)(C)C(C(N)=O)CC1=CC=C(O)C=C1 BHUXUQTZNTVSHP-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 1
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 description 1
- KMEQXYJELYYJGF-UHFFFAOYSA-N 7-aminooctanoic acid Chemical compound CC(N)CCCCCC(O)=O KMEQXYJELYYJGF-UHFFFAOYSA-N 0.000 description 1
- UQXNEWQGGVUVQA-UHFFFAOYSA-N 8-aminooctanoic acid Chemical compound NCCCCCCCC(O)=O UQXNEWQGGVUVQA-UHFFFAOYSA-N 0.000 description 1
- VWPQCOZMXULHDM-UHFFFAOYSA-N 9-aminononanoic acid Chemical compound NCCCCCCCCC(O)=O VWPQCOZMXULHDM-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 230000000397 acetylating effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- MVNCAPSFBDBCGF-UHFFFAOYSA-N alpha-pinene Natural products CC1=CCC23C1CC2C3(C)C MVNCAPSFBDBCGF-UHFFFAOYSA-N 0.000 description 1
- 229960002684 aminocaproic acid Drugs 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- GRWFGVWFFZKLTI-UHFFFAOYSA-N rac-alpha-Pinene Natural products CC1=CCC2C(C)(C)C1C2 GRWFGVWFFZKLTI-UHFFFAOYSA-N 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 229940116351 sebacate Drugs 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は永久帯電防止性を有し、かつ耐衝撃性に優れた
制電性ポリアセタール樹脂に関する。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to an antistatic polyacetal resin that has permanent antistatic properties and excellent impact resistance.
〈従来の技術〉
ポリアセタール樹脂はバランスの整った機械的物性を有
するエンジニアリング・プラスチックとして知られ、機
械機構部分など広範な分野において使用されている。ま
た、ポリアセタール樹脂は、電気絶縁性にも優れている
が、良好な電気絶縁性ゆえに、静電気が発生し易く、静
電気による障害を受は易い電気用品や各種防塵用部品に
は使用できないという問題点を有している。<Prior Art> Polyacetal resin is known as an engineering plastic having well-balanced mechanical properties, and is used in a wide range of fields such as mechanical parts. In addition, polyacetal resin has excellent electrical insulation properties, but because of its good electrical insulation properties, it easily generates static electricity and cannot be used for electrical appliances and various dustproof parts that are susceptible to damage caused by static electricity. have.
従来、ポリアセタール樹脂に帯電防止性を付与するべく
種々の帯電防止剤を混練する方法が検討されている。例
えば比較的低分子量の帯電防止剤としては、Ｎ、Ｎ−ビ
ス（アルコキシ）アミン（特公昭４６−１８５７号公報
）、グリセリンのモノ脂肪酸と硼酸とのエステル（特開
昭５０−１５１９５２号公報）等が知られている。また
高分子量の帯電防止剤としては、ポリエーテルエステル
アミド（特開昭５９−１９１７５２号公報）等が知られ
ている。Conventionally, methods of kneading various antistatic agents have been studied in order to impart antistatic properties to polyacetal resins. For example, relatively low molecular weight antistatic agents include N,N-bis(alkoxy)amine (Japanese Patent Publication No. 46-1857), ester of glycerin monofatty acid and boric acid (Japanese Patent Publication No. 50-151952) etc. are known. Further, as a high molecular weight antistatic agent, polyether ester amide (Japanese Unexamined Patent Publication No. 191752/1983) is known.
〈発明が解決しようどする問題点〉
しかしながら、上記特公昭４６−１８５７号公報及び特
開昭５０−１５１９５２号公報の低分子量の帯電防止剤
は、ブリード現象を引起こして製品の品質を損なったり
、時間の経過と共に帯電防止性が低下するなどの問題点
を有している。<Problems to be solved by the invention> However, the low molecular weight antistatic agents disclosed in Japanese Patent Publication No. 46-1857 and Japanese Patent Application Laid-open No. 50-151952 cause a bleeding phenomenon and impair product quality. However, there are problems such as a decrease in antistatic properties over time.
また、特開昭５９−１９１７５２号公報に記載されてい
るナイロン１２及びポリ（テトラメチレンオキシド）か
らなるポリニーデルエステルアミドブロック共重合体は
、ポリ（テトラメチレンオキシド）鎖の吸水性が低いた
めに帯電防止性能がなお十分でなく、機械的特性も満足
できるものではなかった。In addition, the polyneedle ester amide block copolymer made of nylon 12 and poly(tetramethylene oxide) described in JP-A-59-191752 has low water absorption of poly(tetramethylene oxide) chains. However, the antistatic performance was still insufficient, and the mechanical properties were also not satisfactory.
これはポリ（エチレンオキシド）鎖以外の他のポリ（ア
ルキレンオキシド）鎖、例えばポリ（ポリプロピレンオ
キシド）鎖等を使用しても同様である。This is true even if a poly(alkylene oxide) chain other than the poly(ethylene oxide) chain, such as a poly(polypropylene oxide) chain, is used.
本発明は、永久帯電防止性を有し、かつ機械的特性に優
れたポリアセタール樹脂組成物を提供することを目的と
する。An object of the present invention is to provide a polyacetal resin composition that has permanent antistatic properties and excellent mechanical properties.
く問題点を解決するための手段〉
本発明者らは、上記問題点を解決すべく鋭意検討した結
果、ポリアセタール樹脂に対して、そのポリエーテル成
分がポリ（エチレンオキシド）グリコール残基であり、
かつ、特定の共重合組成を有するポリエーテルエステル
アミドを添加混練することにより、上記目的が達成され
ることを見出し、本発明に到達した。Means for Solving the Problems> As a result of intensive studies to solve the above problems, the present inventors found that the polyether component of the polyacetal resin is a poly(ethylene oxide) glycol residue,
Furthermore, the inventors have discovered that the above object can be achieved by adding and kneading a polyether ester amide having a specific copolymerization composition, and have arrived at the present invention.
即ち本発明は、Ａ、ポリアセクール樹脂５０〜９９重量
％とＢ、 （ａ）炭素数６以上のアミノカルボン酸また
はラクタムもしくは炭素数６以上のジアミンとジカルボ
ン酸の塩、（ｂ）数平均分子１２００〜１０，０００の
ポリ（エチレンオキシド）グリコール及び（ｃ）炭素数
４〜２０のジカルボン酸から誘導され、ポリエーテルエ
ステルブロック単位が１０・〜９０重量％であるポリエ
ーテルエステルアミド１〜５０重量％とからなるポリア
セタール樹脂組成物である。That is, the present invention comprises A, 50 to 99% by weight of polyacecool resin and B, (a) a salt of an aminocarboxylic acid or lactam having 6 or more carbon atoms or a diamine and dicarboxylic acid having 6 or more carbon atoms, (b) a number average molecular weight of 1200 ~10,000 poly(ethylene oxide) glycol and (c) a dicarboxylic acid having 4 to 20 carbon atoms and 1 to 50% by weight of a polyetherester amide having 10.~90% by weight of polyetherester block units. It is a polyacetal resin composition consisting of.
本発明で使用されるＡ、ポリアセタール樹脂とはオキシ
メチレン単独重合体及び主としてオキシメチレン単位か
らなり、主鎖中に２〜８個の隣接する炭素原子を有する
オキシアルキレン単位を１５重量％以下含有するオキシ
メチレン共重合体を意味する。A, polyacetal resin used in the present invention is composed of an oxymethylene homopolymer and mainly oxymethylene units, and contains 15% by weight or less of oxyalkylene units having 2 to 8 adjacent carbon atoms in the main chain. Means an oxymethylene copolymer.
オキシ、メチレン単独重合体は、例えば実質的に無水の
ホルムアルデヒドを有機アミンのような塩・基性重合触
媒を含有する有機溶媒中に導入して重合した後、無水酢
酸により末端をアセチル化して製造する。Oxy, methylene homopolymers are produced by, for example, introducing substantially anhydrous formaldehyde into an organic solvent containing a salt/base polymerization catalyst such as an organic amine, polymerizing it, and then acetylating the terminals with acetic anhydride. do.
また、オキシメチレン共重合体は、例えば実質的に無水
のトリオキサンおよびエチレンオキシドや１．３−ジオ
キソランのような共重合成分をシクロヘキサンのような
有機溶媒中に溶解あるいは懸濁した後、三フッ化ホウ素
・ジエチルエーテラートのようなルイス酸触媒を添加し
て重合し、不安定末端を塩基性化合物により分解除去し
て製造する。あるいは溶媒を全く使用せずに、セルフク
リーニング型撹拌機の中ヘトリオキサン、共重合成分及
び触媒を導入して塊状重合した後、さらに塩基性物質を
添加して不安定末端を分解除去して製造する。Oxymethylene copolymers can also be prepared by dissolving or suspending substantially anhydrous trioxane and copolymer components such as ethylene oxide or 1,3-dioxolane in an organic solvent such as cyclohexane, and then adding boron trifluoride to the oxymethylene copolymer.・Produced by polymerizing by adding a Lewis acid catalyst such as diethyl etherate, and decomposing and removing unstable terminals with a basic compound. Alternatively, without using any solvent, hetrioxane, a copolymerization component, and a catalyst are introduced into a self-cleaning stirrer to perform bulk polymerization, and then a basic substance is added to decompose and remove unstable ends. do.
本発明で使用する８、ポリエーテルエステルアミドとは
ポリアミドブロック単位とポリエーテルエステルブロッ
ク単位とからなるブロック共重合体である。 本発明に
おける炭素数６以上のアミノカルボ〉′酸またはラクタ
ムもしくは炭素数６以上のジアミンとジカルボン酸の塩
（ａ）としては、６−アミノヘキサン酸、７−アミノオ
クタン酸、８−アミノオクタン酸、９−アミノノナン酸
、１０−アミ、ノブカン酸、１１−アミノウンデカン酸
、１２−アミノドデカン酸あるいはこれらのラクタムお
よびヘキサメチレンジアミン−アジピン酸塩、ヘキサメ
チレンジアミン−セバシン酸塩、ヘキサメチレンジアミ
ン−イソフタル酸塩などのジアミン−ジカルボン酸塩が
あるが、特にε−カプロラクタム、１１−アミノウンデ
カン酸、１２−アミノドデカン酸、ヘキサメチレンジア
ミン−アジピン酸塩が好ましい。さらに好ましくはε−
カプロラクタム、１２−アミノドデカン酸である。8. Polyether ester amide used in the present invention is a block copolymer consisting of polyamide block units and polyether ester block units. In the present invention, the aminocarboxylic acid or lactam having 6 or more carbon atoms or the salt of diamine and dicarboxylic acid having 6 or more carbon atoms (a) includes 6-aminohexanoic acid, 7-aminooctanoic acid, 8-aminooctanoic acid, 9-aminononanoic acid, 10-amino, nobucanic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid or their lactams and hexamethylenediamine-adipate, hexamethylenediamine-sebacate, hexamethylenediamine-isophthalic acid Among diamine dicarboxylic acid salts such as salts, ε-caprolactam, 11-aminoundecanoic acid, 12-aminododecanoic acid, and hexamethylenediamine adipate are particularly preferred. More preferably ε−
caprolactam and 12-aminododecanoic acid.
数平均分子量２００〜１０，０００のポリ（エチレンオ
キシド）グリコール（ｂ）は、ポリエーテルエステル単
位の形成成分として使用されるが、中でも数平均分子量
３００〜６，０００が好ましく、５００〜５，０００が
特に好ましい。Poly(ethylene oxide) glycol (b) having a number average molecular weight of 200 to 10,000 is used as a forming component of the polyether ester unit, and among them, a number average molecular weight of 300 to 6,000 is preferable, and a number average molecular weight of 500 to 5,000 is preferable. Particularly preferred.
炭素数４〜２０のジカルボン酸（ｃ）としては、テレフ
タル酸、イソフタル酸、フタル酸、ナフタレ、シー２．
フージカルボン酸、ジフェニル−４，４゛−ジカルボン
酸、３−スルホイソフタル酸のような芳香族ジカルボン
酸、１，４−シクロヘキサンジカルボン酸、１．２−シ
クロヘキサンジカルボン酸、ジシクロへキシル−４，４
′−ジカルボン酸のような脂環式ジカルボン酸およびシ
ュウ酸、コハク酸、アジピン酸、セバシン酸、“ドデカ
ンニ酸のような脂肪族ジカルボン酸が挙げられるが、特
にテレフタル酸、イソフタル酸、アジピン酸、セバシン
酸、ドデカンニ酸が好ましい。Examples of the dicarboxylic acid (c) having 4 to 20 carbon atoms include terephthalic acid, isophthalic acid, phthalic acid, naphthalene, and C2.
Aromatic dicarboxylic acids such as fudicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, 3-sulfoisophthalic acid, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, dicyclohexyl-4,4
'-dicarboxylic acids and aliphatic dicarboxylic acids such as oxalic acid, succinic acid, adipic acid, sebacic acid, dodecanoic acid, but especially terephthalic acid, isophthalic acid, adipic acid, Sebacic acid and dodecanniic acid are preferred.
ポリアミドブロック単位とポリエーテルエステルブロッ
ク単位との組成比は、ポリエーテルエステルブロック単
位が１０〜９０重量％、好ましくは２０〜８０重量％、
さらに好ましくは３０〜７０重量％である。ポリエーテ
ルエステルブロック単位が１０重量％より少ないとポリ
アセタール樹脂との相溶性が悪くなり、また帯電防止効
果も低下する。一方、ポリエーテルエステルブロック単
位が９０重量％を越えると、ポリエーテルエステルアミ
ドの高重合度化が困難になると共に組成物の機械的強度
が低下するめで好ましくない。The composition ratio of polyamide block units and polyether ester block units is 10 to 90% by weight, preferably 20 to 80% by weight,
More preferably, it is 30 to 70% by weight. If the polyether ester block unit is less than 10% by weight, the compatibility with the polyacetal resin will be poor and the antistatic effect will also be reduced. On the other hand, if the polyether ester block unit exceeds 90% by weight, it is not preferable because it becomes difficult to increase the degree of polymerization of the polyether ester amide and the mechanical strength of the composition decreases.
ポリエーテルエステルアミドの重合方法は特に限定され
ず公知の方法を利用することができる。The method for polymerizing polyether ester amide is not particularly limited, and any known method can be used.
例えば、アミノカルボン酸またはラクタムもしくはジア
ミンとジカルボン酸の塩（ａ）とジカルボン酸（ｃ）と
を反応させて両末端がカルボキシル基のポリアミドプレ
ポリマを作り、これにポリ（エチレンオキシド）グリコ
ール（ｂ）を真空下に反応させる方法、あるいは上記（
ａ）、（ｂ）、（ｃ）を同時に反応槽に仕込み、水の存
在下または不存在下に高温で加熱反応させることにより
カルボキシル基末端のポリアミドプレポリマを作り、そ
の後に常圧または減圧下で重合を進める方法が知られて
いる。For example, a polyamide prepolymer having carboxyl groups at both ends is prepared by reacting an aminocarboxylic acid, a lactam, or a diamine with a dicarboxylic acid salt (a) and a dicarboxylic acid (c), and this is coated with poly(ethylene oxide) glycol (b). A method of reacting under vacuum, or the above (
A), (b), and (c) are simultaneously charged into a reaction tank, and a carboxyl group-terminated polyamide prepolymer is produced by heating and reacting at high temperature in the presence or absence of water, and then under normal pressure or reduced pressure. A method of proceeding with polymerization is known.
また、上記（ａ）、 （ｂ）、 （ｃ）を同時に反応槽
に仕込み、溶融重合した後、高真空下で一挙に重合を進
める方法もあり、むしろこの方法がポリマの着色も少な
く好ましい。Alternatively, there is also a method in which the above (a), (b), and (c) are simultaneously charged into a reaction tank, melt-polymerized, and then polymerized all at once under high vacuum, and this method is preferable since it causes less coloring of the polymer.
本発明においてポリエーテルエステルアミドの配合量は
１〜５０重量％、好ましくは１〜３０重量％、さらに好
ましくは２〜２５重景％重量る。ポリエーテルエステル
アミドが５０重量％を越えると、ポリアセタール樹脂の
特性、特に機械的強度が著しく損なわれるので好ましく
ない。In the present invention, the amount of polyether ester amide blended is 1 to 50% by weight, preferably 1 to 30% by weight, and more preferably 2 to 25% by weight. If the amount of polyether ester amide exceeds 50% by weight, the properties of the polyacetal resin, especially the mechanical strength, will be significantly impaired, which is not preferable.
本発明の樹脂組成物は溶融混練することが好ましく、溶
融混練には公知の方法を用いることができる。例えばバ
ンバリーミキサ−、ゴムロール機、−軸もしくは二軸押
出機などを用い、１２０〜２８０℃の温度で溶融混練し
て樹脂組成物とすることができる。The resin composition of the present invention is preferably melt-kneaded, and known methods can be used for melt-kneading. For example, the resin composition can be prepared by melt-kneading at a temperature of 120 to 280° C. using a Banbury mixer, a rubber roll machine, a screw-screw or twin-screw extruder, or the like.
また、本発明の樹脂組成物には、公知の酸化防止剤、熱
分解防止剤、加水分解防止剤、着色剤（顔料、染料）、
カーボンブラック等の導電剤、難燃剤、ガラス繊維や炭
素繊維等の補強剤、シリカ、クレー、炭酸カルシウム等
の充填剤、滑剤、核剤、離型剤、可塑剤、接着助剤、粘
着剤等を任意に含有せしめることができる。The resin composition of the present invention also includes known antioxidants, thermal decomposition inhibitors, hydrolysis inhibitors, colorants (pigments, dyes),
Conductive agents such as carbon black, flame retardants, reinforcing agents such as glass fiber and carbon fiber, fillers such as silica, clay, calcium carbonate, lubricants, nucleating agents, mold release agents, plasticizers, adhesion aids, adhesives, etc. can be optionally included.
〈実施例〉 以下、実施例によって本発明を説明する。<Example> The present invention will be explained below with reference to Examples.
なお、実施例および比較例中に示される成形品の機械物
性、相対粘度ηｒ 、加熱分解率Ｋｘ、ポリマ融点Ｔｍ
、結晶化温度Ｔｃ、表面固有抵抗ρＳ、体積固有抵抗ρ
Ｖは次のようにして測定した。In addition, the mechanical properties, relative viscosity ηr, thermal decomposition rate Kx, and polymer melting point Tm of the molded products shown in Examples and Comparative Examples
, crystallization temperature Tc, surface resistivity ρS, volume resistivity ρ
V was measured as follows.
成形＝５オンスの射出能力を有する射出成形機を用いて
、シリンダ温度２００℃、金型温度６０℃および成形サ
イクル５０秒に設定して、ＡＳＴＨ１号ダンベル試験片
とアイゾツト衝撃試験片および３ｍｍ厚の角板を射出成
形した。Using an injection molding machine with an injection capacity of 5 ounces, the cylinder temperature was set at 200°C, the mold temperature was 60°C, and the molding cycle was 50 seconds. The square plate was injection molded.
機械物性：上記射出成形で１１％られなＡＳＴＨ１号ダ
ンベル試験片を用い、ＡＳＴＨＤ−６３８法に準じて引
張強度を測定した。またアイゾツト試験片を用い、ＡＳ
ＴＨＤ−２５６法に準じて衝撃強度を測定した。Mechanical properties: Tensile strength was measured according to the ASTHD-638 method using an ASTH No. 1 dumbbell test piece that had been molded by 11%. In addition, using an Izot test piece, AS
Impact strength was measured according to the THD-256 method.
電気特性：上記射出成形で得られた８０ｍｍ Ｘ ８０
ｍｍ Ｘ３ｍｍ厚の角板を用いて表面固有抵抗及び体積
固有抵抗を測定した。Electrical properties: 80mm x 80 obtained by injection molding above
Surface resistivity and volume resistivity were measured using a square plate of mm x 3mm thick.
相対粘度ηｒ（ｐＣｐ、６０℃）＝２％のα−ピネンを
含有するｐ−クロルフェノール１００ ｍｌ中に、０．
５ｇのポリマを溶解し、６０℃の温度で測定した。In 100 ml of p-chlorophenol containing α-pinene with relative viscosity ηr (pCp, 60°C) = 2%, 0.
5 g of polymer was dissolved and measured at a temperature of 60°C.
相対粘度ηｒ（ＯＣｐ、２５°Ｃ）：ｏ−クロルフェノ
ール１００ ｍｌ中に０．５１（のポリマを溶解し、２
５°Ｃの温度で測定した。 。Relative viscosity ηr (OCp, 25 °C): Dissolve 0.51 (of the polymer in 100 ml of o-chlorophenol,
Measurements were made at a temperature of 5°C. .
加熱分解率Ｋｘ：Ｋｘは、ｘ℃で６０分間放置した時の
分解率を意味し、熱天びん装置を使用して、約１０■の
サンプルを、空気雰囲気下、ｘ℃で放置し、下記式で求
めた。Thermal decomposition rate Kx: Kx means the decomposition rate when left at x°C for 60 minutes. Using a thermobalance device, approximately 10 cm of sample was left at x°C in an air atmosphere, and the following equation was calculated: I asked for it.
Ｋｘ＝ （ＷＯ−Ｗｌ ） ｘ１００／ＷＯ％ここで、
ＷＯは加熱前のサンプル重量、Ｗｌは加熱後のサンプル
重量を意味する。Kx= (WO-Wl) x100/WO% where,
WO means the sample weight before heating, and Wl means the sample weight after heating.
なお、熱天びん装置は、デュポン（Ｄｕ Ｐｏｎｔ）社
の熱分析機１０９０／１０９１を使用しな。Note that the thermal analyzer 1090/1091 manufactured by Du Pont was used as the thermal balance device.
ポリマ融点（Ｔｍ）、結晶化度（Ｔｃ）：差動走査熱量
計を使用して、窒素雰囲気下、１０℃／分の昇温速度で
昇温し、ポリマ融点（Ｔｍ）を測定後、１０℃／分で降
温し、結晶化温度を測定した。Polymer melting point (Tm), crystallinity (Tc): Using a differential scanning calorimeter, the temperature was raised at a rate of 10°C/min in a nitrogen atmosphere, and the polymer melting point (Tm) was measured. The temperature was lowered at a rate of °C/min, and the crystallization temperature was measured.
参考例１ポリアセタール樹脂（Ａ）の製造Ａ−１オキシ
メチレンホモポリマの製造パラホルムアルデヒドを熱分
解して得たホルムアルデヒドを反応媒体として０℃のト
ルエンを含有する連続式の２毛反応容器に導入した。重
合開始剤として、トルエンに溶解したテトラ（ｎ−ブチ
ル）アンモニウムイオダイドとラウリン酸の等モル混合
物を供給した。全ての反応成分は連続的にポンプで供給
し、重合体状の分散生成物を滞留時間が１０分であるよ
うな速度で取出した。ホルムアルデヒドは約８ｇ／′分
の速度で反応器に通じ、重合開始剤は、テトラ（ｎ−ブ
チル）イオダイドの濃度が反応媒体１ｇあたり１．８７
■、ラウリン酸濃度が反応媒体１１あたり０．９９■で
あるような割合で供給した。反応媒体は６５°Ｃに保ち
、良く撹拌した。反応媒体１ｐあたり４００ ｇ／ｈの
割合で重合体が生成した。得られた重合体を濾過して取
出し、アセトン洗浄およびメタノール洗浄して乾燥した
。Reference Example 1 Production of polyacetal resin (A) A-1 Production of oxymethylene homopolymer Formaldehyde obtained by thermally decomposing paraformaldehyde was introduced into a continuous two-hair reaction vessel containing toluene at 0°C as a reaction medium. . As a polymerization initiator, an equimolar mixture of tetra(n-butyl)ammonium iodide and lauric acid dissolved in toluene was supplied. All reaction components were pumped in continuously and the polymeric dispersion product was removed at such a rate that the residence time was 10 minutes. Formaldehyde was passed through the reactor at a rate of approximately 8 g/min and the polymerization initiator was supplied at a concentration of tetra(n-butyl) iodide of 1.87 g/g of reaction medium.
(2) Lauric acid was supplied at a rate such that the concentration was 0.992/11 reaction medium. The reaction medium was kept at 65°C and stirred well. Polymer was produced at a rate of 400 g/h per p of reaction medium. The obtained polymer was taken out by filtration, washed with acetone and methanol, and dried.
この組型合体５００ｇ、無水酢酸４０００ ｇ、酢酸ナ
トリウム１．６ｇの混合物を１３９℃で１時間還流した
。冷却後、重合体を濾過し、アセトン洗浄および水洗し
た後乾燥した。このポリマの融点は１７９°Ｃ１結晶化
度は１５０℃、ｙ７ ｒ （ｐＣｐ、 ６０°Ｃ）＝１
．９０、Ｋ２２２ ＝７３．２％であった。A mixture of 500 g of this combination, 4000 g of acetic anhydride, and 1.6 g of sodium acetate was refluxed at 139° C. for 1 hour. After cooling, the polymer was filtered, washed with acetone and water, and then dried. The melting point of this polymer is 179°C, the crystallinity is 150°C, y7 r (pCp, 60°C) = 1
．． 90, K222 = 73.2%.
Ａ−２オキシメチレンコポリマの製造
トリオキサン９００ｇ、エチレンオキシド８．８ｇを４
５０ｇのシクロヘキサンに溶解し、０．３ ｇの三フッ
化ホウ素・ジエチルエーテラートを含有する６０ｍ１の
ベンゼンを添加し、６０°Ｃで撹拌した。三フッ化ホウ
素・ジエチルエーテラートを添加後、約１分間で反応液
は白濁し、重合体が析出してきた。３０分後、■・リエ
チルアミンの１０％ベンゼン溶液１０ｍ１を添加して重
合反応を停止した後、析出している重合体を濾過して集
め、アセトン洗浄次いで水洗した。この重合体を、メタ
ノール／水／アンモニア＝ ５９．５／４０１０．５重
量比の加水分解溶液１０９中に投入し、オートクレーブ
中１６０℃で１０分間加熱撹拌しな。冷却後、重合体を
濾過して集め、水洗次いでアセトン洗浄し、乾燥した。A-2 Production of oxymethylene copolymer 900 g of trioxane and 8.8 g of ethylene oxide were
60 ml of benzene containing 0.3 g of boron trifluoride diethyl etherate dissolved in 50 g of cyclohexane was added and stirred at 60°C. After adding boron trifluoride/diethyl etherate, the reaction solution became cloudy in about 1 minute and a polymer began to precipitate. After 30 minutes, 10 ml of a 10% solution of ethylamine in benzene was added to stop the polymerization reaction, and the precipitated polymer was collected by filtration, washed with acetone and then with water. This polymer was put into a hydrolysis solution 109 having a methanol/water/ammonia weight ratio of 59.5/4010.5, and heated and stirred at 160° C. for 10 minutes in an autoclave. After cooling, the polymer was collected by filtration, washed with water and then acetone, and dried.
このポリマの融点は１６７℃、結晶化温度は１４７℃、
ηｒ＝（四ｐ、 ６０’Ｃ）＝１ 、９１、Ｋ２２２＝
４６．８％であった。The melting point of this polymer is 167°C, the crystallization temperature is 147°C,
ηr=(4p, 60'C)=1, 91, K222=
It was 46.8%.
Ａ−３オキシメチレンコポリマの製造
２枚のΣ型撹拌翼を有する３に−ダにトリオキサン３０
００ ｇ、１，３−ジオキソラン５０ｍ１、三フッ化ホ
ウ素・ジエチルエーテラート０．３ ｇを含有するベン
ゼン３０ｍ１を加え、６５°ＣＣ１４０ｐｐで撹拌した
。A-3 Production of oxymethylene copolymer Trioxane 30 with two Σ-type stirring blades
00 g, 50 ml of 1,3-dioxolane, and 30 ml of benzene containing 0.3 g of boron trifluoride diethyl etherate were added, and the mixture was stirred at 65°C and 140 pp.
約１分後に反応が始まり、内温が上昇した。約９５℃ま
で上昇したがそのまま１０分間撹拌した。反応混合物は
粉砕されて白色粉末となった。The reaction started after about 1 minute, and the internal temperature rose. The temperature rose to about 95°C, but the mixture was stirred for 10 minutes. The reaction mixture was ground into a white powder.
この反応混合物に５．４ｇのビス（１，２，２，６，６
−ベンタメチルー４−ピペリジニル）セバケート（チバ
、ガイギー（ｃｈ ｉ ｂａ−Ｇｅ １（ＪＶ）社製“
サノール（Ｓａｎｏｌ）”：ＬＳ７６５）を含有するベ
ンゼン５０ｍ１を添加し、３５℃で１５分間撹拌しな。To this reaction mixture was added 5.4 g of bis(1,2,2,6,6
-bentamethyl-4-piperidinyl) sebacate (manufactured by Ciba, Geigy (JV))
Add 50 ml of benzene containing Sanol (LS765) and stir for 15 minutes at 35°C.
さらに３．０ｇの水酸化カルシウム、１５．０ｇのペン
タエリスリチル−テトラキス［３−（３，５−ジーｔｅ
ｒｔ−ブチルー４−ヒドロキシフェニル）プロピオネー
ト１（チバ・ガイギー社製゛イルガノックス（Ｉｒｇａ
ｎｏｘ）”１０１０）を添加し、２１０°Ｃに昇温しで
、そのまま２０分間溶溶融金した。さらに０、３０ ｇ
のジシアンジアミドを添加し、２１０℃で１０分間溶融
混練してポリマを製造した。In addition, 3.0 g of calcium hydroxide, 15.0 g of pentaerythrityl-tetrakis [3-(3,5-tetrakis)
rt-butyl-4-hydroxyphenyl) propionate 1 (Irganox (Irga) manufactured by Ciba Geigy)
1010) was added, the temperature was raised to 210°C, and the mixture was melted for 20 minutes.Additionally, 0.30 g
of dicyandiamide was added and melt-kneaded at 210° C. for 10 minutes to produce a polymer.
このポリマの融点は１６７°Ｃ１結晶化温度１４７°Ｃ
１ηｒ（［）ｃｐ、６０°Ｃ）＝１．９２、Ｋ ２２２
＝１ 、７％であった。The melting point of this polymer is 167°C1 the crystallization temperature is 147°C
1ηr([)cp, 60°C)=1.92, K 222
= 1, 7%.
参考例２ポリニーデルエステルアミド（Ｂ）の製造［３
−１ポリカプロラクタム／ポリ（エチレンオキシド）グ
リコール（数平均分子量１０００） （Ｎ−６／ＰＥＧ
１０００）＝５０１５０の製造
カプロラクタム５００部、数平均分子量１０００のポリ
（エチレンオキシド）グリコール４５０部、及びアジピ
ン酸６６部をＮ、Ｎ’−へキサメチレンビス（３，５−
シーｔｅｒｔ−ブチル−４−ヒドロキシ−ヒドロシンナ
マミド）（チバ・ガイギー社製゛イルガノックス゛１０
９８）５．０部と共にヘリカルリボン撹拌翼を備えた重
合装置に仕込み、窒素雰囲気下、２６０℃で１時間加熱
撹拌して均質透明溶液とした後、三酸化アンチモン触媒
１．０部を添加した。減圧を開始して、１時間で１ｍｍ
ＨＧ以下とした後、３．０時間反応させた。得られた粘
稠な溶融ポリマをガツト状に水中へ吐出すると結晶化し
て固化した。このポリマの融点は１８３℃、結晶化温度
１４１℃、ηｒ＝（ｃ）Ｃｐ。Reference Example 2 Production of polyneedle ester amide (B) [3
-1 polycaprolactam/poly(ethylene oxide) glycol (number average molecular weight 1000) (N-6/PEG
1000) = 50150 500 parts of caprolactam, 450 parts of poly(ethylene oxide) glycol having a number average molecular weight of 1000, and 66 parts of adipic acid were mixed with N,N'-hexamethylenebis(3,5-
Tert-butyl-4-hydroxy-hydrocinnamamide) (Irganox 10 manufactured by Ciba Geigy)
98) 5.0 parts were charged into a polymerization apparatus equipped with a helical ribbon stirring blade, heated and stirred at 260°C for 1 hour in a nitrogen atmosphere to obtain a homogeneous transparent solution, and then 1.0 parts of antimony trioxide catalyst was added. . 1mm in 1 hour after starting decompression
After setting the temperature to HG or less, the reaction was carried out for 3.0 hours. When the obtained viscous molten polymer was discharged into water in a gut shape, it crystallized and solidified. The melting point of this polymer is 183°C, the crystallization temperature is 141°C, and ηr=(c)Cp.
２５°Ｃ）＝１．９８であった。25°C) = 1.98.
Ｂ−２Ｎ−６／ＰＥＧ１０００＝５／９５力プロラクタ
ム９５０部、数平均分子量１０００のポリ（エチレンオ
キシド）グリコール４４，３部、及びアジピン酸６．５
部、Ｎ、Ｎ−へキサメチレンビス（３，５−ジーｔｅｒ
ｔ−ブチルー４−ヒドロキシ−ヒドロシンナマミド）（
チバ・ガイギー社製“パイルガノックス” １０９８）
５．０部及び三酸化アンチモン１６０部からＢ−１と同
様にしてポリマを重合した。B-2N-6/PEG1000=5/95 950 parts of prolactam, 44.3 parts of poly(ethylene oxide) glycol having a number average molecular weight of 1000, and 6.5 parts of adipic acid.
part, N, N-hexamethylene bis(3,5-ter
t-butyl-4-hydroxy-hydrocinnamamide) (
Ciba Geigy “Pile Ganox” 1098)
A polymer was polymerized from 5.0 parts and 160 parts of antimony trioxide in the same manner as B-1.
このポリマの融点は２０３℃、結晶化温度１６３℃、ｒ
） ｒ＝（ＯＣｐ、２５℃）＝１．９０であった。The melting point of this polymer is 203°C, the crystallization temperature is 163°C, r
) r=(OCp, 25°C)=1.90.
Ｂ−３８−Ｇ／ＰＥＧ１０００＝５／９５の製造カプロ
ラクタム５０部、数平均分子量１０００のポリ（エチレ
ンオキシド）グリコール８４２部、アジピン酸１２３部
、Ｎ、Ｎ−ヘキサメチレンビス（３，５−ジーｔｅｒｔ
−ブチルー４−ヒドロキシ−ヒドロシンナマミド）（チ
バ・ガイギー社製゛′イルガノックス“’ １０９８）
５．０部及び三酸化アンチモン１．０部から８−１と同
様にしてポリマの重合を試みたが、重合度が上がらず半
液状のポリマであった。Production of B-38-G/PEG1000=5/95 50 parts of caprolactam, 842 parts of poly(ethylene oxide) glycol with a number average molecular weight of 1000, 123 parts of adipic acid, N,N-hexamethylene bis(3,5-di-tert)
-Butyl-4-hydroxy-hydrocinnamamide) (manufactured by Ciba-Geigy 'Irganox' 1098)
Polymerization of the polymer was attempted in the same manner as in 8-1 using 5.0 parts of antimony trioxide and 1.0 parts of antimony trioxide, but the polymerization degree did not increase and the polymer was semi-liquid.
Ｂ−４ポリカプロラクタム／ポリ（エチレンオキシド）
グリコール（数平均分子量４０００） （Ｎ−６／ＰＥ
Ｇ４０００）＝５０１５０の製造
カプロラクタム５００部、数平均分子量４０００のポリ
（エチレンオキシド）グリコール４８４部、アジピン酸
１８部、Ｎ、Ｎ−へキサメチレンビス（３，５−シイｅ
ｒｔ−ブチルー４−ヒドロキシ−ヒドロシンナマミド）
（チバ・ガイギー社製・パイルガノックス゛’ １０９
８）５．０部及び三酸化アンチモン１．０部からＢ−１
と同様にしてポリマを重合した。得られたポリマの融点
は２０６°Ｃ１結晶化温度１６４℃、ｒ） ｒ （ＯＣ
ｐ、 ２５℃）＝１．８７であった。B-4 Polycaprolactam/Poly(ethylene oxide)
Glycol (number average molecular weight 4000) (N-6/PE
Production of G4000) = 50150 500 parts of caprolactam, 484 parts of poly(ethylene oxide) glycol with a number average molecular weight of 4000, 18 parts of adipic acid, N,N-hexamethylene bis(3,5-cye)
rt-butyl-4-hydroxy-hydrocinnamamide)
(Manufactured by Ciba Geigy, Pile Ganox '109
8) 5.0 parts and 1.0 parts of antimony trioxide to B-1
The polymer was polymerized in the same manner as described above. The melting point of the obtained polymer is 206°C1 crystallization temperature 164°C, r) r (OC
p, 25°C) = 1.87.
Ｂ−５ポリカプロラクタム／′ポリ（エチレンオキシド
）グリコール（数平均分子量８０００） （Ｎ−６／Ｐ
ＥＧ３０００）＝５０１５０の製造
カプロラクタム５００部、数平均分子量８０００のポリ
（エチレンオキシド）グリコール４９２部、アジピン酸
９．０部、Ｎ、Ｎ−ヘキサメチレンビス（３，５−ジー
ｔｅｒｔ−ブチルー４−ヒドロキシ−ヒドロシンナマミ
ド）（チバ・ガイギー社製“′イルガノックス°“１０
９８）５．０部及び三酸化アンチモン１．０部から８−
１と同様にしてポリマの重合を試みたが、相分離が激し
く、重合できなかった。B-5 polycaprolactam/'poly(ethylene oxide) glycol (number average molecular weight 8000) (N-6/P
Production of EG3000)=50150 500 parts of caprolactam, 492 parts of poly(ethylene oxide) glycol having a number average molecular weight of 8000, 9.0 parts of adipic acid, N,N-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy- hydrocinnamamide) (manufactured by Ciba Geigy “Irganox°”10
98) 5.0 parts and 1.0 parts of antimony trioxide to 8-
Polymerization of the polymer was attempted in the same manner as in 1, but phase separation was severe and polymerization was not possible.
Ｂ−６ポリドデカンアミド、／ポリ（エチレンオキシド
）グリコール（数平均分子１１０００） （Ｎ−１２／
ＰＥＧＩＯ００）＝５０１５０の製造
１２−アミノドデカン酸５５０部、数平均分子量１００
０のポリ（エチレンオキシド）グリコール４３６部、テ
レフタル酸７２部、Ｎ、Ｎ−へキサメチレンビス（３，
５−ジーｔｅｒｔ−ブヂルー４−ヒドロキシ−ヒドロシ
ンナマミド）（チバ・ガイギー社製“′、イルガノック
ス°’ １０９８）５．０部及び三酸化アンチモン１．
０部からＢ−１と同様にしてポリマを重合した。B-6 polydodecanamide, / poly(ethylene oxide) glycol (number average molecule 11000) (N-12/
Production of PEGIO00)=50150 12-aminododecanoic acid 550 parts, number average molecular weight 100
0 poly(ethylene oxide) glycol, 72 parts of terephthalic acid, N,N-hexamethylene bis(3,
5.0 parts of 5-tert-budyl-4-hydroxy-hydrocinnamamide (manufactured by Ciba Geigy, Irganox °' 1098) and 1.0 parts of antimony trioxide.
A polymer was polymerized from 0 parts in the same manner as in B-1.
得られたポリマの融点は１６３℃、結晶化速度１１７℃
、ｙ７ ｒ （ＯＣＩ）、 ２５℃）＝１．８５であっ
た。The melting point of the obtained polymer was 163°C, and the crystallization rate was 117°C.
, y7r (OCI), 25°C) = 1.85.
Ｂ−７ポリへキサメチレンセベカミド／ポリ（エチレン
オキシド）グリコール（数平均分子１１０００）（Ｎ−
６，１０／ＰＥＧ１０００）＝５０１５０の製造ヘキサ
メチレンジアミン−セバシン酸塩５６４部、数平均分子
１１０００のポリ（エチレンオキシド）グリコール４４
３部、−インフタル酸７４部、Ｎ、Ｎ−へキサメチレン
ビス（３，５−ジーｔｅｒｔ−ブチルー４−ヒドロキシ
−ヒドロシンナマミド）（チバ・ガイギー社製“°イル
ガノックス“’ １０９８）５．０部及び三酸化アンチ
モン１．０部から８−１と同様にしてポリマを重合した
。得られたポリマの融点は１５８°Ｃ，結晶化温度１１
１℃、ｒ） ｒ （ＯＣＩ）、 ２５℃）＝１．８６で
あった。B-7 Polyhexamethylene sebecamide/poly(ethylene oxide) glycol (number average molecule 11000) (N-
Preparation of 6,10/PEG1000) = 50150 564 parts of hexamethylene diamine sebacate, poly(ethylene oxide) glycol 44 with number average molecular weight 11000
3 parts, -inphthalic acid 74 parts, N,N-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamamide) (manufactured by Ciba Geigy "°Irganox"' 1098) 5 A polymer was polymerized in the same manner as in 8-1 from .0 part of antimony trioxide and 1.0 part of antimony trioxide. The melting point of the obtained polymer was 158°C, and the crystallization temperature was 11
1°C, r) r (OCI), 25°C) = 1.86.
８−８ポリカプロラクタム／ポリ（テトラメチレンオキ
シド）グリコール（数平均分子量１０００）（Ｎ−６／
。8-8 polycaprolactam/poly(tetramethylene oxide) glycol (number average molecular weight 1000) (N-6/
.
ＰＴＭＧＩ Ｃｏｏ）＝５０１５０の製造カプロラクタ
ム５００部、数平均分子ｚｉｏｏｏのポリ（テトラメチ
レンオキシド）グリコール４４２部、テレフタル酸７３
部、Ｎ、Ｎ−ヘキサメチレンビス（３，５−ジーｔｅｒ
・℃−ブチルー４−ヒドロキシーヒドロシンナマミド）
（チバ・ガイギー社製“イルガノックス” １０９８）
５．０部及び三酸化アンチモン１．０部から８−１と同
様にしてポリマを製造した。このポリマの融点は１８６
℃、結晶化温度１２９℃、ｒ） ｒ （ｏｃｐ、 ２５
℃）＝ｉ、９４であった。Production of PTMGI Coo) = 50150 500 parts of caprolactam, 442 parts of poly(tetramethylene oxide) glycol with number average molecular weight ziooo, 73 parts of terephthalic acid
part, N, N-hexamethylene bis(3,5-ter
・℃-butyl-4-hydroxy-hydrocinnamamide)
(“Irganox” 1098 manufactured by Ciba Geigy)
A polymer was produced in the same manner as in 8-1 from 5.0 parts and 1.0 parts of antimony trioxide. The melting point of this polymer is 186
°C, crystallization temperature 129 °C, r) r (ocp, 25
°C) = i, 94.
Ｂ−９ポリドデカンアミド／ポリ（テトラメチレンオキ
シド）グリコール（数平均分子ｚ１４ｏｏ） （Ｎ−１
２／ＰＴ）ＩＧ１４００）＝４０／６０の製造１２−ア
ミノドデカン酸４３７部、数平均分子量１４００ｃｒ）
月でり（テトラメチレ・ン′オキシド）グリコール５４
９部、テレフタル酸６５部、Ｎ、Ｎ’−へキサメチレン
ビス（３，５−ジーｔｅｒｔ−ブチルー４−ビトロキシ
−ヒドロシンナマミド）（チバ・ガイギー社製“′イル
ガノックス” １０９ｇ）５．０部及び三酸化アンチモ
ン１．０部から８−１と同様にしてポリマを製造した。B-9 polydodecanamide/poly(tetramethylene oxide) glycol (number average molecule z14oo) (N-1
2/PT) IG1400) = 40/60 production 12-aminododecanoic acid 437 parts, number average molecular weight 1400 cr)
Tsukideri (tetramethylene oxide) glycol 54
9 parts of terephthalic acid, 65 parts of N,N'-hexamethylenebis(3,5-di-tert-butyl-4-bitroxy-hydrocinnamamide) (109 g of "Irganox" manufactured by Ciba Geigy)5. A polymer was produced in the same manner as in 8-1 from 0 part and 1.0 part of antimony trioxide.
このポリマの融点は１５８℃、結晶化温度１１３℃、η
ｒ（ｏｃｐ、２５℃）＝１．８９であった。The melting point of this polymer is 158°C, the crystallization temperature is 113°C, and η
r(ocp, 25°C) = 1.89.
実施例１〜９、比較例１〜５
参考例１で製造したポリアセクール樹脂（Ａ−１〜３）
に対して、参考例２で製造したポリエーテルエステルア
ミド（Ｂ−１）を表１に示した割合で配合し、二軸３０
ｍｍφ押出機を使用して、シリンダ温度１８５℃で溶融
混練した。得られた組成物の成形品の物性を表１に示す
。また、比較例１，２．５として、参考例１で製造した
ポリアセタール樹脂（Ａ−１〜３）の物性を表１に示し
た。Examples 1 to 9, Comparative Examples 1 to 5 Polyacecool resins produced in Reference Example 1 (A-1 to 3)
The polyether ester amide (B-1) produced in Reference Example 2 was blended in the ratio shown in Table 1, and the biaxial 30
The mixture was melt-kneaded using a mmφ extruder at a cylinder temperature of 185°C. Table 1 shows the physical properties of the molded article of the obtained composition. Moreover, as Comparative Examples 1 and 2.5, the physical properties of the polyacetal resins (A-1 to A-3) manufactured in Reference Example 1 are shown in Table 1.
表１より明らかに、ポリエーテルエステルアミド（Ｂ−
１：Ｎ−６／ＰＥＧ１０００＝５０１５０）を混練する
ことにより、アイゾツト衝撃値が増大して耐衝撃性が向
上していることがわかる。また、体積固有抵抗及び表面
固有抵抗が低下し、制電性が向上していることもわかる
。これらの効果は、ポリエーテルエステルアミドの配合
量の増加と共に増大する。しかしながら、比較例３のよ
うに配合量が１重量％未満では、その効果が得られない
。また、比較例４のように５０重量％を越えると、引張
強度など機械的物性の低下が著し、く、ポリアセタール
樹脂の特性が損なわれてしまうので好ましくない。It is clear from Table 1 that polyether ester amide (B-
It can be seen that by kneading 1:N-6/PEG1000=50150), the Izot impact value increases and the impact resistance improves. It can also be seen that the volume resistivity and surface resistivity are reduced, and the antistatic property is improved. These effects increase as the amount of polyether ester amide increases. However, if the amount is less than 1% by weight as in Comparative Example 3, this effect cannot be obtained. Moreover, if it exceeds 50% by weight as in Comparative Example 4, mechanical properties such as tensile strength will be significantly reduced, and the properties of the polyacetal resin will be impaired, which is not preferable.
実施例１０〜”１２、比較例６〜１１
参考例２で製造したポリエーテルエステルアミド（Ｂ−
１〜４）を表２に示した割合でポリアセタール樹脂（Ａ
−１〜３）に配合し、二軸３０ｍｍφ押出機を使用して
シリンダ温度１８５℃で溶融混練した。得られた組成物
の成形品の物性を表２に示す。なお、参考のために前記
実施例２．５．’８及び比較例１゜２．５も併記する。Examples 10 to 12, Comparative Examples 6 to 11 Polyether ester amide (B-
1 to 4) in the proportions shown in Table 2, polyacetal resin (A
-1 to 3) and melt-kneaded using a twin-screw 30 mmφ extruder at a cylinder temperature of 185°C. Table 2 shows the physical properties of the molded article of the obtained composition. For reference, the above-mentioned Examples 2.5. '8 and Comparative Example 1°2.5 are also listed.
比較例６．８．１０よりポリエーテル部分の共重合量が
５重量％のポリエーテルエステルアミドでは耐衝撃性、
訓電性共に向上しないことがわかる。From Comparative Example 6.8.10, polyether ester amide with a copolymerization amount of the polyether portion of 5% by weight had impact resistance,
It can be seen that neither the training performance nor the training performance improves.
また、比較例７，９．１１よりポリエーテル部分の共重
合量が９５重量％のポリエーテルエステルアミドでは、
制電性は向上するものの、引張強度などの機械的物性の
低下が著しいことがわかる。In addition, from Comparative Example 7, 9.11, in polyether ester amide with a copolymerization amount of the polyether portion of 95% by weight,
It can be seen that although the antistatic properties are improved, the mechanical properties such as tensile strength are significantly reduced.
実施例２．５．８と１０．１１．１２の比較から、ポリ
エーテル部分の分子量を変更しても組成物の物性に及ぼ
ず効果は変わらないことがわがる実施例１３〜１８
参考例２で製造したポリエーテルエステルアミド（Ｂ−
６〜７）を表３に示した割合でポリアセタール樹脂（Ａ
−１〜３）に配合し、二軸３０ｍｍφ押出機を使用して
シリンダ温度１８５℃で溶融混練した。得られた組成物
の成形品の特性を表３に示す。なお、参考のために前記
比較例１，２．５も併記する。Comparison of Examples 2.5.8 and 10.11.12 shows that even if the molecular weight of the polyether moiety is changed, the physical properties of the composition are not affected and the effect remains unchanged. Examples 13 to 18 Reference Example 2 Polyether ester amide (B-
6 to 7) in the proportions shown in Table 3, polyacetal resin (A
-1 to 3) and melt-kneaded using a twin-screw 30 mmφ extruder at a cylinder temperature of 185°C. Table 3 shows the properties of the molded article of the obtained composition. For reference, Comparative Examples 1 and 2.5 are also listed.
表３より明らかにポリアミドブロック単位としてポリド
デカンアミドあるいはポリへキサメチレンセバカミドを
使用しても耐衝撃性及び制電性向上に大きな効果のある
ことがわかる。Table 3 clearly shows that even when polydodecanamide or polyhexamethylene sebamide is used as the polyamide block unit, it is highly effective in improving impact resistance and antistatic properties.
比較例１２〜１７
比較例として、参考例２で製造したポリエーテルエステ
ルアミド（Ｂ−８〜９）を表４に示した割合でポリアセ
タール樹脂（Ａ−１〜３）に配合し、二軸３０ｍｍφ押
出機を使用してシリンダ温度１８５℃で溶融混練した。Comparative Examples 12 to 17 As comparative examples, the polyether ester amides (B-8 to 9) produced in Reference Example 2 were blended with polyacetal resins (A-1 to A-3) in the proportions shown in Table 4, and a biaxial 30 mmφ The mixture was melt-kneaded using an extruder at a cylinder temperature of 185°C.
得られた成形品の物性を表４に示す。なお、参考のため
に前記比較例ｔ、２．５も併記する。Table 4 shows the physical properties of the molded product obtained. In addition, the said comparative example t, 2.5 is also written for reference.
表４より明らかにポリエーテルニスデルアミドとしてＢ
−８（Ｎ−１３／ＰＴ）ＩＧｌｏｏｏ）やＢ−９（Ｎ−
１２／Ｐｒ）ｌＧ１４００）を配合することにより、引
張強度や耐衝撃性など機械的物性が著しく損なわれるこ
とがわかる。これはポリくテトラメチレンオキシド）鎖
がポリ（エチレンオキシド）鎖に比べてポリアセタール
樹脂との相溶性が低いということに起因していると考え
られる。また、制電性もあまり向上していない。これは
ポリ（テトラメチレンオキシド）鎖がポリ（エチレンオ
キシド）鎖に比べて吸水性が低いとい・うことに起因し
ていると考えられる。From Table 4, it is clear that B as polyether nisdelamide
-8 (N-13/PT) IGlooo) and B-9 (N-
12/Pr)lG1400), mechanical properties such as tensile strength and impact resistance are significantly impaired. This is thought to be due to the fact that poly(tetramethylene oxide) chains have lower compatibility with polyacetal resins than poly(ethylene oxide) chains. Moreover, the antistatic property has not improved much. This is thought to be due to the fact that poly(tetramethylene oxide) chains have lower water absorption than poly(ethylene oxide) chains.
〈発明の効果〉
本発明の樹脂組成物は、制電性及び耐衝撃性に優れるた
め、静電気の発生を嫌う電気部品や防塵用部品など広範
な用途に使用することができる。<Effects of the Invention> Since the resin composition of the present invention has excellent antistatic properties and impact resistance, it can be used in a wide range of applications such as electrical parts and dustproof parts where generation of static electricity is averse.
Claims (1)
炭素数６以上のアミノカルボン酸またはラクタムもしく
は炭素数６以上のジアミンとジカルボン酸の塩、（ｂ）
数平均分子量２００〜１０，０００のポリ（エチレンオ
キシド）グリコール及び（ｃ）炭素数４〜２０のジカル
ボン酸から誘導され、ポリエーテルエステルブロック単
位が１０〜９０重量％であるポリエーテルエステルアミ
ド１〜５０重量％とからなるポリアセタール樹脂組成物
。A, 50-99% by weight of polyacetal resin and B, (a)
Aminocarboxylic acid or lactam having 6 or more carbon atoms or salt of diamine and dicarboxylic acid having 6 or more carbon atoms, (b)
Polyether ester amide 1 to 50 derived from poly(ethylene oxide) glycol having a number average molecular weight of 200 to 10,000 and (c) dicarboxylic acid having 4 to 20 carbon atoms, and containing 10 to 90% by weight of polyether ester block units. A polyacetal resin composition consisting of % by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25622586A JPS63110245A (en) | 1986-10-28 | 1986-10-28 | Polyacetal resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25622586A JPS63110245A (en) | 1986-10-28 | 1986-10-28 | Polyacetal resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63110245A true JPS63110245A (en) | 1988-05-14 |
Family
ID=17289671
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25622586A Pending JPS63110245A (en) | 1986-10-28 | 1986-10-28 | Polyacetal resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63110245A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1989012660A1 (en) * | 1988-06-22 | 1989-12-28 | Toray Industries, Inc. | Polyacetal resin composition |
| WO2020250895A1 (en) * | 2019-06-10 | 2020-12-17 | 旭化成株式会社 | Polyacetal resin composition |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59191752A (en) * | 1983-04-15 | 1984-10-30 | Mitsubishi Gas Chem Co Inc | Acetal resin composition |
| JPS61183345A (en) * | 1985-02-12 | 1986-08-16 | Toray Ind Inc | Resin composition |
-
1986
- 1986-10-28 JP JP25622586A patent/JPS63110245A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59191752A (en) * | 1983-04-15 | 1984-10-30 | Mitsubishi Gas Chem Co Inc | Acetal resin composition |
| JPS61183345A (en) * | 1985-02-12 | 1986-08-16 | Toray Ind Inc | Resin composition |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1989012660A1 (en) * | 1988-06-22 | 1989-12-28 | Toray Industries, Inc. | Polyacetal resin composition |
| WO2020250895A1 (en) * | 2019-06-10 | 2020-12-17 | 旭化成株式会社 | Polyacetal resin composition |
| JPWO2020250895A1 (en) * | 2019-06-10 | 2021-11-25 | 旭化成株式会社 | Polyacetal resin composition |
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