JPH0220588A - Antistatic agent for thermoplastic resin, production thereof and resin composition having permanent antistatic property - Google Patents
Antistatic agent for thermoplastic resin, production thereof and resin composition having permanent antistatic propertyInfo
- Publication number
- JPH0220588A JPH0220588A JP16965288A JP16965288A JPH0220588A JP H0220588 A JPH0220588 A JP H0220588A JP 16965288 A JP16965288 A JP 16965288A JP 16965288 A JP16965288 A JP 16965288A JP H0220588 A JPH0220588 A JP H0220588A
- Authority
- JP
- Japan
- Prior art keywords
- antistatic agent
- copolymer
- weight
- antistatic
- group
- 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
- 239000002216 antistatic agent Substances 0.000 title claims abstract description 55
- 229920005992 thermoplastic resin Polymers 0.000 title claims abstract description 31
- 239000011342 resin composition Substances 0.000 title claims description 17
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 229920001577 copolymer Polymers 0.000 claims abstract description 47
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 22
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 21
- -1 methacryloyl groups Chemical group 0.000 claims abstract description 21
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 18
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims abstract description 15
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229920000233 poly(alkylene oxides) Polymers 0.000 claims abstract description 13
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 9
- 239000000178 monomer Substances 0.000 claims abstract description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims abstract description 7
- 125000003277 amino group Chemical group 0.000 claims description 12
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 4
- 230000000694 effects Effects 0.000 abstract description 31
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 34
- 230000000052 comparative effect Effects 0.000 description 15
- 238000000034 method Methods 0.000 description 14
- 229920000638 styrene acrylonitrile Polymers 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 239000003153 chemical reaction reagent Substances 0.000 description 9
- 238000007334 copolymerization reaction Methods 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-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
- 239000004793 Polystyrene Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- IUVCFHHAEHNCFT-INIZCTEOSA-N 2-[(1s)-1-[4-amino-3-(3-fluoro-4-propan-2-yloxyphenyl)pyrazolo[3,4-d]pyrimidin-1-yl]ethyl]-6-fluoro-3-(3-fluorophenyl)chromen-4-one Chemical compound C1=C(F)C(OC(C)C)=CC=C1C(C1=C(N)N=CN=C11)=NN1[C@@H](C)C1=C(C=2C=C(F)C=CC=2)C(=O)C2=CC(F)=CC=C2O1 IUVCFHHAEHNCFT-INIZCTEOSA-N 0.000 description 2
- ARSRBNBHOADGJU-UHFFFAOYSA-N 7,12-dimethyltetraphene Chemical compound C1=CC2=CC=CC=C2C2=C1C(C)=C(C=CC=C1)C1=C2C ARSRBNBHOADGJU-UHFFFAOYSA-N 0.000 description 2
- VFZRZRDOXPRTSC-UHFFFAOYSA-N DMBA Natural products COC1=CC(OC)=CC(C=O)=C1 VFZRZRDOXPRTSC-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 229940038597 peroxide anti-acne preparations for topical use Drugs 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000012744 reinforcing agent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 125000001989 1,3-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([H])C([*:2])=C1[H] 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- UIQGEWJEWJMQSL-UHFFFAOYSA-N 2,2,4,4-tetramethylpentan-3-one Chemical compound CC(C)(C)C(=O)C(C)(C)C UIQGEWJEWJMQSL-UHFFFAOYSA-N 0.000 description 1
- KXYAVSFOJVUIHT-UHFFFAOYSA-N 2-vinylnaphthalene Chemical compound C1=CC=CC2=CC(C=C)=CC=C21 KXYAVSFOJVUIHT-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-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
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- 102220504829 BTB/POZ domain-containing protein 1_D14A_mutation Human genes 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 241001446467 Mama Species 0.000 description 1
- 229920009204 Methacrylate-butadiene-styrene Polymers 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920002319 Poly(methyl acrylate) Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229960003328 benzoyl peroxide Drugs 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- ZGQOVGXPFYKMRS-UHFFFAOYSA-M benzyl-dimethyl-[3-(2-methylprop-2-enoyloxy)propyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCCC[N+](C)(C)CC1=CC=CC=C1 ZGQOVGXPFYKMRS-UHFFFAOYSA-M 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002981 blocking agent Substances 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
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000007257 malfunction Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 229940102396 methyl bromide Drugs 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007717 redox polymerization reaction Methods 0.000 description 1
- 102200017208 rs1555451582 Human genes 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Graft Or Block Polymers (AREA)
Abstract
Description
【発明の詳細な説明】
[産業上の利用分野]
この発明は、帯電防止剤に関し、より詳細には、基体の
熱可塑性樹脂に配合され、熱可塑性樹脂成形品の帯電防
止性を向上させる帯電防止剤、およびその製造方法、帯
′電防止剤が配合された永久制電性樹脂組成物に関する
。[Detailed Description of the Invention] [Industrial Application Field] This invention relates to an antistatic agent, and more specifically, an antistatic agent that is blended into a thermoplastic resin as a base material and improves the antistatic properties of a thermoplastic resin molded product. This invention relates to an antistatic agent, a method for producing the same, and a permanent antistatic resin composition containing the antistatic agent.
[従来の技術]
熱可塑性樹脂は、−船釣に成形性および電気絶縁性に優
れているので、電気製品、事務機器などの筐体や部品な
どの種々の成形品の製造に用いられている。しかしなが
ら、熱可塑性樹脂成形品は、容易に帯電し易く、そのた
めに、成形品表面にゴミやホコリが付着して製品外観を
損なわせるばかりか、成形品が電気製品や電子機器の筐
体や部品である場合には、電気部品の絶縁不良、回路の
短絡、電子部品の劣化、誤動作などを起こす原因になる
。[Prior Art] Thermoplastic resins have excellent moldability and electrical insulation properties, so they are used to manufacture various molded products such as housings and parts for electrical products and office equipment. . However, thermoplastic resin molded products are easily charged with electricity, and as a result, not only does dirt and dust adhere to the surface of the molded product, damaging the appearance of the product, but the molded product can also be used as a housing or component of electrical products or electronic devices. If this happens, it may cause poor insulation of electrical parts, short circuits, deterioration of electronic parts, malfunctions, etc.
これらの熱可塑性樹脂の帯電性に対して、従来から、帯
電防止剤を成形品表面に塗布する方法、および帯電防止
剤を成形用熱可塑性樹脂に練り込む方法が実施されてき
た。Conventionally, methods of applying an antistatic agent to the surface of a molded article and methods of kneading an antistatic agent into a thermoplastic resin for molding have been carried out to address the electrostatic properties of these thermoplastic resins.
[発明が解決しようとする課題]
帯電防止剤を成形品表面に塗布する方法では、経時変化
、または洗浄などによって帯電防止剤の塗膜が剥離して
帯電防止効果が経時的に失われ、また成形工程とは別に
帯電防止剤塗布工程を追加する必要があり、成形品の製
造コストを上げ、生産性を低下させる。[Problems to be Solved by the Invention] In the method of applying an antistatic agent to the surface of a molded product, the coating film of the antistatic agent peels off due to changes over time or washing, and the antistatic effect is lost over time. It is necessary to add an antistatic agent coating process in addition to the molding process, which increases the manufacturing cost of the molded product and reduces productivity.
塗布する前記方法に対して、帯電防止剤を熱可塑性樹脂
に練り込む方法では、永久制電性樹脂組成物が得られ、
帯電防止剤膜の剥離による経時的劣化を防止し、工程数
を低減させて生産性を向上させるが、経時的に練り込ん
だ帯電防止剤がブリード・アウトして成形品表面を汚し
、また帯電防止効果の持続性を低下させる。In contrast to the above method of coating, a method of kneading an antistatic agent into a thermoplastic resin yields a permanently antistatic resin composition.
This prevents deterioration over time due to peeling of the antistatic agent film, reduces the number of steps, and improves productivity. Decreases the durability of the preventive effect.
上記の従来技術に加えて、イオン性残基を有するビニル
系モノマーを、熱可塑性樹脂を構成する重合性七ツマ−
と共重合させて、共重合体中にイオン構造単位を導入す
ることによって、熱可塑性樹脂に帯電防止性を付与する
ことが知られている。In addition to the above-mentioned conventional technology, vinyl monomers having ionic residues can be used as polymerizable seven polymers constituting thermoplastic resins.
It is known that antistatic properties can be imparted to thermoplastic resins by copolymerizing them with ionic structural units and introducing ionic structural units into the copolymer.
しかしながら、共重合体成分として導入されたイオン構
造単位が、分子の大きさのオーダーで樹脂内部に均一に
分散されるので、この共重合体を含む熱可塑性樹脂より
得られる成形品表面の帯電防止効果は小さく、十分な帯
電防止効果を発揮させるためには、上記共重合体を大量
配合せねばならず、その結果、上記共重合体を含む熱可
塑性樹脂の性能を低下する恐れがある。However, since the ionic structural units introduced as copolymer components are uniformly dispersed inside the resin in the order of molecular size, the surface of molded products obtained from thermoplastic resins containing this copolymer is prevented from becoming static. The effect is small, and in order to exhibit a sufficient antistatic effect, a large amount of the above-mentioned copolymer must be blended, and as a result, the performance of the thermoplastic resin containing the above-mentioned copolymer may be deteriorated.
この発明は上述の背景に基づきなされたものであり、そ
の目的とするところは、基体の熱可塑性樹脂に練り込ん
でも、ブリード・アウトせずに帯電防止効果が経時的に
失わず、分散性、相溶性に優れた帯電防止剤、およびそ
の製造方法、並びに、その帯電防止剤が配合された永久
制電性樹脂組成物を提供することである。This invention was made based on the above-mentioned background, and its purpose is to prevent bleed-out and prevent loss of antistatic effect over time even when kneaded into a base thermoplastic resin, and to maintain dispersibility and The object of the present invention is to provide an antistatic agent with excellent compatibility, a method for producing the same, and a permanently antistatic resin composition containing the antistatic agent.
[課題を解決するための手段]
本発明者らは、上述の課題を解決すべく種々の試験研究
を行った結果、帯電防止剤として、アンモニウム塩を含
有する特定の組成のクシ型共重合体を用いれば、熱可塑
性樹脂に練り込んでもブリード・アウトせずに帯電防止
効果が経時的に失われず、分散性、相溶性に優れている
との知見を得た。この知見に基づき更に開発を進めた結
果、アンモニウム塩含有クシ型共重合体の製造に際して
は、原料のアンモニウム塩含有モノマーと分枝構造(ク
シ)を発現させる高分子モノマーとの双方に良溶媒が無
く、重合系が不均一で、かつ溶剤回収が困難な混合溶媒
等を用いざるを得なかったが、−旦アミン基含有クシ型
共重合体を調製し、次いでこのアミン基をアンモニウム
塩にアンモニウム化すれば、有効に目的生成物が得られ
ることが判明し、この発明を完成するに至った。[Means for Solving the Problems] As a result of conducting various tests and studies to solve the above-mentioned problems, the present inventors have developed a comb-shaped copolymer with a specific composition containing an ammonium salt as an antistatic agent. It has been found that when used, the antistatic effect does not bleed out and the antistatic effect is not lost over time even when kneaded into a thermoplastic resin, and the dispersibility and compatibility are excellent. As a result of further development based on this knowledge, we found that when producing an ammonium salt-containing comb-shaped copolymer, a good solvent is required for both the raw material ammonium salt-containing monomer and the polymer monomer that develops the branched structure (comb). However, first, an amine group-containing comb-shaped copolymer was prepared, and then the amine group was converted into an ammonium salt. It was found that the desired product could be effectively obtained by converting the above-described method into a compound, leading to the completion of this invention.
すなわち、この発明の熱可塑性樹脂用帯電防止剤は、下
記コモノマーより構成されたクシ型共重合体からなる。That is, the antistatic agent for thermoplastic resins of the present invention is composed of a comb-shaped copolymer composed of the following comonomers.
(a) 分子末端にアクリロイル基またはメタクリロ
イル基を有する末端重合性ポリアルキレンオキシド、好
ましくは、繰返し単位エチレンオキサイドまたは/およ
び繰返し単位プロピレンオキサイドとの末端重合性共重
合体
(b) アンモニウム塩含有のアクリレートまたはメ
タクリレート
(c) 分子末端にアクリロイル基、メタクリロイル
基またはビニル芳香族基を有するアクリロニトリルとス
チレンとの末端重合性共重合体必要に応じて、コモノマ
ー(a)〜(c)と共重合可能なビニル系モノマー(d
)を用いることができる。(a) A terminally polymerizable polyalkylene oxide having an acryloyl group or a methacryloyl group at the molecular end, preferably a terminally polymerizable copolymer with a repeating unit of ethylene oxide or/and a repeating unit of propylene oxide (b) Ammonium salt-containing acrylate or methacrylate (c) A terminally polymerizable copolymer of acrylonitrile and styrene having an acryloyl group, methacryloyl group, or vinyl aromatic group at the molecular end. If necessary, a vinyl copolymerizable with comonomers (a) to (c). system monomer (d
) can be used.
この発明の製造方法は、前記帯電防止剤を製造する方法
であって、
(a) 分子末端にアクリロイル基またはメタクリロ
イル基を有する末端重合性ポリアルキレンオキシド10
〜80ffi量部と、
(b′) アミノ基含有のアクリレートまたはメタクリ
レート0.5ff1m部以上と、(c) 分子末端に
アクリロイル基、メタクリロイル基またはビニル芳香族
基を有するアクリロニトリルとスチレンとの末端重合性
共重合体10〜90重量部(ただし、七ツマ−(a)〜
(c)は合計100重量部とする。)と、
(d) 必要に応じて、前記コモノマー(a)〜(c
)と共重合可能なビニル系七ツマー100重二部以下と
、
を共重合させてクシ型共重合体を生成する重合工程Aお
よび、
得られたクシ型共重合体のアミノ基をアンモニウム塩に
するアンモニウム化工程Bとを含むことを特徴とするも
のである。The production method of the present invention is a method for producing the antistatic agent, comprising: (a) a terminal polymerizable polyalkylene oxide 10 having an acryloyl group or a methacryloyl group at the molecular terminal;
~80ffi parts, (b') 0.5ff1m part or more of amino group-containing acrylate or methacrylate, and (c) terminal polymerizability of styrene and acrylonitrile having an acryloyl group, methacryloyl group, or vinyl aromatic group at the molecular end. 10 to 90 parts by weight of copolymer (however, 7 months (a) to
The total amount of (c) is 100 parts by weight. ), and (d) if necessary, the comonomers (a) to (c
) and 100 parts or less of vinyl heptamer copolymerizable with 100 parts or less of vinyl heptamer to produce a comb-shaped copolymer. Polymerization step A of producing a comb-shaped copolymer; This method is characterized in that it includes an ammonium forming step B.
この発明による帯電防止剤が配合された好ましい永久制
電性樹脂組成物は、前記で特定された帯電防止剤1〜2
0重量部と、この帯電防止剤と相溶性のある熱可塑性樹
脂99〜80ffiffi部とからなることを特徴とす
るものである。A preferred permanent antistatic resin composition containing the antistatic agent according to the present invention is the antistatic agent 1 to 2 specified above.
0 parts by weight, and 99 to 80 parts of a thermoplastic resin compatible with the antistatic agent.
以下、この発明をより詳細に説明する。This invention will be explained in more detail below.
帯電防止剤の製造方法
この発明の帯電防止剤の製造方法の重合工程Aにおいて
、コモノマー(a)と(b′)と(c)とを、若しくは
、コモノマー(a)と(b′)と(c)と(d)とを、
共重合させてクシ型共重合体を生成する。Method for producing an antistatic agent In the polymerization step A of the method for producing an antistatic agent of the present invention, comonomers (a), (b'), and (c), or comonomers (a), (b'), and ( c) and (d),
Copolymerization produces a comb-shaped copolymer.
この発明で用いられるコモノマー(a)は、分子末端に
アクリロイル基またはメタクリロイル基を有する末端重
合性ポリアルキレンオキシドである。より具体的には、
例えば、下記構造式(I)で表される末端重合性ポリマ
ーがあげらる。The comonomer (a) used in this invention is a terminally polymerizable polyalkylene oxide having an acryloyl group or a methacryloyl group at the molecular end. More specifically,
For example, a terminal polymerizable polymer represented by the following structural formula (I) can be mentioned.
(式中、R1、R2は水素、またはメチル基、R3は水
素または炭素数1〜6、好ましくは1〜4のアルキル基
などの炭化水素基、nは2〜500の整数である)
アルキレンオキシドの結合単位nは、2〜500の範囲
で選ばれる。nが大きいほど帯電防止剤としての効果が
顕著であるが、共重合反応性は小さくなる。(In the formula, R1 and R2 are hydrogen or a methyl group, R3 is hydrogen or a hydrocarbon group such as an alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, and n is an integer of 2 to 500.) Alkylene oxide The bonding unit n is selected in the range of 2 to 500. The larger n is, the more pronounced the effect as an antistatic agent is, but the copolymerization reactivity becomes smaller.
好ましいコモノマー(a)としては、繰返し単位エチレ
ンオキサイドまたは/および繰返し単位プロピレンオキ
サイドの共重合体である末端重合性ポリアルキレンオキ
シドがあげられる。Preferred comonomers (a) include terminally polymerizable polyalkylene oxides which are copolymers of repeating units of ethylene oxide and/or repeating units of propylene oxide.
共重合に際して用いられるコモノマー(a)の使用量は
、10〜80重量部である。10重量部未満では帯電防
止効果などの制電効果を賦与できず、帯電防止効果が得
られなくなる。80重量部を超えるとコモノマー(c)
の使用量が相対的に減少して得られた共重合体のよる制
電効果が低下し、帯電防止効果が得られなくなる。The amount of comonomer (a) used in the copolymerization is 10 to 80 parts by weight. If it is less than 10 parts by weight, antistatic effects such as antistatic effects cannot be imparted, and the antistatic effect cannot be obtained. If it exceeds 80 parts by weight, the comonomer (c)
When the amount of the copolymer used is relatively reduced, the antistatic effect of the obtained copolymer decreases, and the antistatic effect is no longer obtained.
この発明で用いられるコモノマー(b′)は、アミノ基
含有のアクリレートまたはメタクリレートである。より
具体的には、例えば、下記構造式(II)で表されるア
クリレートまたはメタクリレートの誘導体があげられる
。The comonomer (b') used in this invention is an acrylate or methacrylate containing an amino group. More specifically, examples include acrylate or methacrylate derivatives represented by the following structural formula (II).
R40
(式中、Rは水素、またはメチル基、R5は炭素数1〜
6、好ましくは1〜4のアルキレン基などの2価の炭化
水素基、R6、R7は水素またはメチル基、エチル基等
のアルキル基、またはフェニル基、ベンジル基等のアル
アルキル基を表す)共重合に際して用いられるコモノマ
ー(b′)の使用量は、0.5重量部、好ましくは1重
量部以上である。1重量部未満では十分な制電効果を賦
与できず、0.5重量部未満ではその傾向が顕著になり
、帯電防止効果が得られなくなる。R40 (wherein, R is hydrogen or a methyl group, R5 has 1 to 1 carbon atoms)
6, preferably a divalent hydrocarbon group such as 1 to 4 alkylene groups, R6 and R7 represent hydrogen or an alkyl group such as a methyl group or an ethyl group, or an aralkyl group such as a phenyl group or a benzyl group) The amount of comonomer (b') used in the polymerization is 0.5 part by weight, preferably 1 part by weight or more. If it is less than 1 part by weight, a sufficient antistatic effect cannot be imparted, and if it is less than 0.5 part by weight, this tendency becomes noticeable and an antistatic effect cannot be obtained.
この発明で用いられるコモノマー(c)は、分子の片末
端にアクリロイル基、メタクリロイル基またはビニル芳
香族基等の重合性官能基を有するアクリロニトリルとス
チレンとの末端重合性共重合体である。コモノマー(c
)の数平均分子量は、200〜2万が好ましく、200
未満であると相溶性の向上の効果が少なく、2万を超え
ると共重合反応性が小さくなるので好ましくない。コモ
ノマー(c)における分子末端のビニル芳香族基とは、
重合性ビニル基を有する芳香族基であり、例えばビニル
−p−フェニレン基、イソプロペニルm−フェニレン基
などがあげられる。The comonomer (c) used in this invention is an end-polymerizable copolymer of acrylonitrile and styrene, which has a polymerizable functional group such as an acryloyl group, a methacryloyl group, or a vinyl aromatic group at one end of the molecule. Comonomer (c
The number average molecular weight of ) is preferably 200 to 20,000, and 200 to 20,000.
If it is less than 20,000, the effect of improving compatibility will be small, and if it exceeds 20,000, copolymerization reactivity will decrease, which is not preferable. The vinyl aromatic group at the end of the molecule in comonomer (c) is
It is an aromatic group having a polymerizable vinyl group, such as vinyl-p-phenylene group and isopropenyl m-phenylene group.
共重合に際して用いられるコモノマー(e)の使用量は
、10〜90重量部、好ましくは20〜80重量部であ
る。20重量部未満では帯電防止剤と基体である熱可塑
性樹脂との相溶性が低下するため制電効果の持続性に劣
り、10重量部未満ではその傾向が顕著になり、80重
量部を超えると相溶性は良好であるが制電効果が低下し
、90重量部を超えるとその傾向がさらに顕著になるか
らである。The amount of comonomer (e) used in the copolymerization is 10 to 90 parts by weight, preferably 20 to 80 parts by weight. If it is less than 20 parts by weight, the compatibility between the antistatic agent and the base thermoplastic resin will be reduced, resulting in poor antistatic effect sustainability; if it is less than 10 parts by weight, this tendency will be noticeable, and if it exceeds 80 parts by weight, the antistatic effect will be poor. This is because although the compatibility is good, the antistatic effect decreases, and this tendency becomes even more pronounced when the amount exceeds 90 parts by weight.
コモノマー(a)、(b′)、(c)の合計使用量は1
00重量部とする。The total amount of comonomers (a), (b'), and (c) used is 1
00 parts by weight.
この発明で必要に応じて用いられるコモノマー(d)は
、コモノマー(a)〜(c)と前記コモノマーと共重合
可能なビニル系モノマーである。The comonomer (d) used as necessary in the present invention is a vinyl monomer copolymerizable with the comonomers (a) to (c) and the comonomers described above.
このようなビニル系モノマーとしては、例えば、アクリ
ル酸またはメタクリル酸の炭素数1〜10個のアルキル
エステル、アクリロニトリル、スチレン、α−メチルス
チレン、o−lm−またはp−ビニルトルエン若しくは
これらの混合物、核ハロゲン化スチレン、α−若しくは
β−ビニルナフタリンなどがあげらる。これらは、1種
または2種以、上の混合物であってもよい。このなかで
も、アクリル酸またはメタクリル酸のアルキルエステル
、特にメチルメタクリレートが好適である=共重合工程
Aにおける共重合方法として、溶液重合法が最も適して
いる。Examples of such vinyl monomers include alkyl esters of acrylic acid or methacrylic acid having 1 to 10 carbon atoms, acrylonitrile, styrene, α-methylstyrene, o-lm- or p-vinyltoluene, or mixtures thereof; Examples include nuclear halogenated styrene, α- or β-vinylnaphthalene, and the like. These may be used alone or in combination of two or more. Among these, alkyl esters of acrylic acid or methacrylic acid, particularly methyl methacrylate, are preferred; as a copolymerization method in copolymerization step A, solution polymerization is most suitable.
共重合工程Aにおける共重合に際して、通常のラジカル
重合開始剤、また、必要に応じて、分子ffi調整のた
めに連鎖移動剤を用いることができる。During copolymerization in copolymerization step A, a normal radical polymerization initiator and, if necessary, a chain transfer agent can be used to adjust the molecular ffi.
溶液重合法によって共重合を行う場合、重合開始剤とし
て、アゾビスイソブチロニトリルなどのアゾ化合物、ベ
ンゾパーオキサイドなどの過酸化物を用いることができ
る。When copolymerizing by a solution polymerization method, an azo compound such as azobisisobutyronitrile or a peroxide such as benzoperoxide can be used as a polymerization initiator.
溶液重合法において使用される溶媒としては、各コモノ
マーを溶解することができるものが好ましく、その具体
的な例としては、アセトン、メチルエチルケトン、ジエ
チルケトン、t−ブチルケトン、テトラヒドロフラン、
ジメチルホルムアミド、ベンゼン、トルエン、メタノー
ル、エタノールなどがあげられる。ここで用いる溶媒の
選択は、生成されたアミノ基含有共重合体をアンモニウ
ム塩に変換する工程での試薬の種類に応じて行うことが
好ましく、アンモニウム化試薬(例えば、酸性物質)に
対して易溶性または可溶性の溶媒を選択する。例えば、
酸性物質としては、塩酸を用いる場合、アセトン、テト
ラヒドロフラン、エタノール、メタノールなどが望まし
い。The solvent used in the solution polymerization method is preferably one that can dissolve each comonomer, and specific examples include acetone, methyl ethyl ketone, diethyl ketone, t-butyl ketone, tetrahydrofuran,
Examples include dimethylformamide, benzene, toluene, methanol, and ethanol. The solvent used here is preferably selected depending on the type of reagent used in the step of converting the produced amino group-containing copolymer into an ammonium salt, and is easily resistant to ammonium-forming reagents (e.g., acidic substances). Choose a solvent that is soluble or soluble. for example,
As the acidic substance, when using hydrochloric acid, acetone, tetrahydrofuran, ethanol, methanol, etc. are preferable.
この発明の帯電防止剤の製造方法の工程Bにおいては、
上記工程Aで得られたアミノ基含有クシ型共重合体を、
アンモニウム化試薬および要すればアンモニウム化触媒
等の助剤を加えてアンモニウム塩含有クシ型共重合体に
変換し、次いで、不要になった溶媒などを除去する。In step B of the method for producing an antistatic agent of this invention,
The amino group-containing comb-shaped copolymer obtained in the above step A,
An ammonium-forming reagent and, if necessary, an auxiliary agent such as an ammonium-forming catalyst are added to convert it into an ammonium salt-containing comb-shaped copolymer, and then unnecessary solvents and the like are removed.
アンモニウム化試薬としては、アミノ基を対応するアン
モニウム塩に変換する試薬であり、例えば、塩酸、臭化
水素酸、硫酸、亜硫酸、リン酸、ホウ酸、硫酸1ナトリ
ウム塩、リン酸1ナトリウム塩、ギ酸、酢酸、プロピオ
ン酸、シュウ酸などのカルボン酸、p−トルエンスルホ
ン酸、アルキルホスホン酸などの酸性物質、エチルクロ
ライド、臭化メチルなどのアルキルハロゲン化物、また
はベンジルクロライドなどのアルアルキルハロゲン化物
などがある。これらは、1種または211以上の混合物
であってもよい。The ammonium-forming reagent is a reagent that converts an amino group into the corresponding ammonium salt, such as hydrochloric acid, hydrobromic acid, sulfuric acid, sulfite, phosphoric acid, boric acid, monosodium sulfate, monosodium phosphate, Carboxylic acids such as formic acid, acetic acid, propionic acid, and oxalic acid, acidic substances such as p-toluenesulfonic acid and alkylphosphonic acid, alkyl halides such as ethyl chloride and methyl bromide, or aralkyl halides such as benzyl chloride, etc. There is. These may be one type or a mixture of 211 or more.
使用するアンモニウム化試薬の量は、アミノ基に対して
30〜100%のモル数に対応する範囲が望ましい。The amount of ammoniumation reagent used is preferably in a range corresponding to 30 to 100% of the number of moles based on the amino group.
この発明のアンモニウム塩含有クシ型共重合体からなる
帯電防止剤の製造方法としては、上記に説明した例に限
定されず、種々の方法により製造することができる。The method for producing the antistatic agent comprising the ammonium salt-containing comb copolymer of the present invention is not limited to the example described above, and can be produced by various methods.
例えば、溶液重合において、混合溶媒を用いて重合する
ことができ、また、溶液重合の他に、懸濁重合法、乳化
重合法のいずれかの方法を利用することができる。懸濁
重合法では、溶液重合と同様のアゾ化合物や過酸化物な
どの重合開始剤を用いることができ、乳化重合法では、
過硫酸カリウムなどの水溶性過酸化物の他、レドックス
系重合開始剤も使用することができる。For example, in solution polymerization, a mixed solvent can be used for polymerization, and in addition to solution polymerization, either a suspension polymerization method or an emulsion polymerization method can be used. In suspension polymerization, the same polymerization initiators as azo compounds and peroxides can be used in solution polymerization, and in emulsion polymerization,
In addition to water-soluble peroxides such as potassium persulfate, redox polymerization initiators can also be used.
帯電防止剤
この発明の帯電防止剤は、アンモニウム塩を含有するク
シ型共重合体であり、
(a) 分子末端にアクリロイル基またはメタクリロ
イル基を有する末端重合性ポリアルキレンオキシド、好
ましくは繰返し単位エチレンオキサイドまたは/および
繰返し単位プロピレンオキサイドの末端重合性共重合体
と、
(b) アンモニウム塩含有のアクリレートまたはメ
タクリレートと、
(c) 分子末端にアクリロイル基、メタクリロイル
基またはビニル芳香族基を有するアクリロニトリルとス
チレンとの末端重合性共重合体と、(d) 必要に応
じて用いられる、コモノマー(a)〜(c)と共重合可
能なビニル第七ツマ−とより構成されるクシ型共重合体
である。Antistatic agent The antistatic agent of the present invention is a comb-shaped copolymer containing an ammonium salt, (a) a terminally polymerizable polyalkylene oxide having an acryloyl group or a methacryloyl group at the molecular end, preferably a repeating unit of ethylene oxide; or/and a terminally polymerizable copolymer of propylene oxide repeating unit; (b) acrylate or methacrylate containing an ammonium salt; (c) acrylonitrile and styrene having an acryloyl group, methacryloyl group, or vinyl aromatic group at the molecular end; and (d) a vinyl seventh polymer copolymerizable with the comonomers (a) to (c), which is used as necessary.
クシ型共重合体の分子量などは、用途、加工方法などに
応じて適宜選択することができる。The molecular weight of the comb-shaped copolymer can be appropriately selected depending on the use, processing method, etc.
永久制電性樹脂組成物
この発明による永久制電性樹脂組成物は、上記に詳説し
たこの発明の帯電防止剤0.5〜30重量部、好ましべ
は1〜20重量部と、帯電防止剤と相溶性のある熱可塑
性樹脂99.5〜70重量部、好ましくは99〜80重
量部とからなる。Permanent Antistatic Resin Composition The permanent antistatic resin composition according to the present invention contains 0.5 to 30 parts by weight, preferably 1 to 20 parts by weight, of the antistatic agent of the present invention detailed above, and an antistatic agent. It consists of 99.5 to 70 parts by weight, preferably 99 to 80 parts by weight of a thermoplastic resin that is compatible with the agent.
これは、1重量部未満では永久制電性樹脂組成物の制電
性が乏しく、0.5重量部未満ではその傾向が著しく、
20重量部を超えると製造コストが上がり、経済的では
なくなると同時に、熱可塑性樹脂組成物の物性が変化し
、目的の物性が得られなくなるからである。This means that if it is less than 1 part by weight, the antistatic properties of the permanent antistatic resin composition will be poor, and if it is less than 0.5 part by weight, this tendency will be marked.
This is because if the amount exceeds 20 parts by weight, the manufacturing cost increases and becomes uneconomical, and at the same time, the physical properties of the thermoplastic resin composition change, making it impossible to obtain the desired physical properties.
この発明による永久制電性樹脂組成物に用いることがで
きる熱可塑性樹脂は、帯電防止剤と相溶性のあるもので
あり、例えば、ポリスチレン、ゴム強化ポリスチレン、
ポリスチレン/ポリフェニレンエーテルのポリマーアロ
イ、スチレン−アクリロニトリル共重合体、ABS樹脂
、MBS樹脂、AES樹脂、ポリメチルメタクリレート
、ポリアクリル酸メチル、ポリ酢酸ビニル、ポリフェニ
レンオキサイド、ポリカーボネート、ポリアミドなどが
あげられるが、この発明においてこれらは2種以上の混
合物であってもよい。The thermoplastic resin that can be used in the permanent antistatic resin composition according to the present invention is one that is compatible with the antistatic agent, and includes, for example, polystyrene, rubber-reinforced polystyrene,
Polymer alloys of polystyrene/polyphenylene ether, styrene-acrylonitrile copolymer, ABS resin, MBS resin, AES resin, polymethyl methacrylate, polymethyl acrylate, polyvinyl acetate, polyphenylene oxide, polycarbonate, polyamide, etc. In the invention, a mixture of two or more of these may be used.
相溶性および分散性などを考慮して、スチレン−アクリ
ロニトリル共重合体、ABS樹脂などの熱可塑性樹脂を
配合するときは、帯電防止剤であるクシ型共重合体中の
スチレン−アクリロニトリル末端重合性共重合体のスチ
レン−アクリロニトリル組成と、基体である熱可塑性樹
脂中のスチレン−アクリロニトリル共重合体などの組成
とを合セルナどの工夫を行い、制電性を持続させること
が好ましい。When blending thermoplastic resins such as styrene-acrylonitrile copolymers and ABS resins in consideration of compatibility and dispersibility, it is important to consider It is preferable to maintain antistatic properties by combining the styrene-acrylonitrile composition of the polymer with the composition of the styrene-acrylonitrile copolymer or the like in the thermoplastic resin base.
この発明の永久制電性樹脂組成物には、上記の成分以外
に、可塑剤、滑剤、酸化防止剤、充填剤、強化剤、補強
剤、改質剤、難燃剤、着色剤、熱安定剤、発泡剤、軟化
剤、粘着防止剤、表面処理剤などの添加剤を配合するこ
とができる。In addition to the above-mentioned components, the permanent antistatic resin composition of the present invention includes a plasticizer, a lubricant, an antioxidant, a filler, a reinforcing agent, a reinforcing agent, a modifier, a flame retardant, a colorant, and a heat stabilizer. , foaming agents, softeners, anti-blocking agents, surface treatment agents, and other additives may be added.
この発明の永久制電性樹脂組成物に、上述の成分や添加
剤を配合するには、タンブラ−、ミキサ、ニーダ−1押
出し機などの通常の装置を用いることができる。In order to blend the above-mentioned components and additives into the permanent antistatic resin composition of the present invention, conventional equipment such as a tumbler, mixer, kneader 1 extruder, etc. can be used.
[作 用]
この発明において、末端重合性ポリアルキレンオキシド
、アンモニウム基金を(メタ)アクリレートとAS(ア
クリロニトリルとスチレン)末端重合性共重合体とから
得られるアンモニウム塩含有クシ型共重合体は、側鎖部
分がポリアルキレンオキシドに対応する分枝鎖と、AS
共重合体に対応する分枝鎖と、これらの分枝鎖と相乗効
果をもつアンモニウム塩含有の電気伝導性鎖とから主に
構成されている。[Function] In this invention, an ammonium salt-containing comb-shaped copolymer obtained from a terminal polymerizable polyalkylene oxide, an ammonium base, a (meth)acrylate, and an AS (acrylonitrile and styrene) terminal polymerizable copolymer is A branched chain whose chain portion corresponds to polyalkylene oxide, and AS
It is mainly composed of branched chains corresponding to the copolymer and electrically conductive chains containing ammonium salts that have a synergistic effect with these branched chains.
理論的に必ずしも明らかではないが、分子内のアンモニ
ウム塩は、イオン性をクシ型共重合体に賦与し、ポリア
ルキレンオキシドに対応する分枝鎖がイオン伝導に寄与
して、クシ型共重合体を電気伝導性あるポリマーにする
。このクシ型共重合体が配合された熱可塑性樹脂組成物
の成形品では、イオン性アンモニウム塩鎖およびイオン
伝導性ポリアルキレンオキシド鎖が成形体表面に移行若
しくは配向し、成形体表面に濃縮させる。この様に表面
に濃縮されたイオン伝導性(電気伝導性)により、その
表面に帯電した電荷を外に逃がして帯電を抑制・防止す
る。Although it is not necessarily theoretically clear, the ammonium salt in the molecule imparts ionicity to the comb copolymer, and the branched chain corresponding to the polyalkylene oxide contributes to ionic conduction, resulting in the formation of a comb copolymer. into an electrically conductive polymer. In a molded article of a thermoplastic resin composition containing this comb-shaped copolymer, the ionic ammonium salt chain and the ion-conductive polyalkylene oxide chain migrate or orient to the surface of the molded article, and are concentrated on the surface of the molded article. The ionic conductivity (electrical conductivity) concentrated on the surface allows the charges on the surface to escape to the outside, thereby suppressing and preventing electrification.
[発明の効果コ
上記の構成および作用を有するこの発明は、以下の効果
を有する。[Effects of the Invention] This invention having the above-described structure and operation has the following effects.
(イ) 請求項1、請求項2または請求項3による組成
をもつ帯電防止効果では、基体の成形用熱可塑性樹脂と
ブレンドして成形に供され、得られた成形品の表面抵抗
を10〜1010Ω程度の低いレベルにすることができ
る。従って、成形品に帯電防止効果を発揮させることが
できる。(b) The antistatic effect having the composition according to claim 1, claim 2, or claim 3 is obtained by blending with the thermoplastic resin for molding of the base body and providing it for molding, and the surface resistance of the obtained molded product is 10 to 10. It can be made to a low level of about 1010Ω. Therefore, the molded product can exhibit an antistatic effect.
(ロ)請求項4による帯電防止剤の製造方法では、アン
モニウム塩含有クシ型共重合体を直接に製造せず、−旦
アミン基含有クシ型共重合体を調製し、次いでこのアミ
ン基をアンモニウム塩にアンモニウム化するので、クシ
型共重合体の原料コモノマー成分の双方を溶解する溶媒
を選択することができ、重合系を不均一にしかつ困難な
溶剤回収を行う必要がない。(b) In the method for producing an antistatic agent according to claim 4, an ammonium salt-containing comb copolymer is not directly produced, but an amine group-containing comb copolymer is first prepared, and then this amine group is replaced with an ammonium salt. Since ammonium is converted into a salt, it is possible to select a solvent that dissolves both of the raw material comonomer components of the comb-shaped copolymer, and there is no need to make the polymerization system heterogeneous or to perform difficult solvent recovery.
(ハ)請求項5による成形用樹脂組成物では、AS末端
重合性共重合体に対応する分枝鎖が、基体となる成形用
熱可塑性樹脂との相溶性および分散性を高め、熱可塑性
樹脂の分子鎖と絡み合うので、配合された帯電防止剤が
成形品からグレード・アウトしたり、成形品から剥離す
ることがなく、帯電防止効果などの制電性を持続する能
力を大巾に向上させることができる。(c) In the molding resin composition according to claim 5, the branched chain corresponding to the AS-terminated polymerizable copolymer increases the compatibility and dispersibility with the molding thermoplastic resin serving as the base, and the thermoplastic resin Because the antistatic agent is entangled with the molecular chains of the antistatic agent, it does not grade out or peel off from the molded product, greatly improving the ability to maintain antistatic properties such as antistatic effects. be able to.
[実施例コ
以下、この発明を実施例および比較例にもとづいて具体
的に説明するが、この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] This invention will be specifically explained below based on Examples and Comparative Examples, but the present invention will not exceed its gist.
The present invention is not limited to the following examples.
実施例A−1
(1)帯電防止剤の製造
撹拌機を備えた容Ja500mlのフラスコに、テトラ
ヒドロフランを3001に入れ、次いで撹拌下、片末端
にメタクリロイル基を有するアクリロニトリルとスチレ
ンとの末端重合性共重合体(以下SANmlと略す、ア
クリロニトリル含ff123重量%、数平均分子量55
00)30gと、片末端にアクリロイル基を有するポリ
エチレンオキサイド(以下、PE0m1と略す、構造式
(I)のR3−エチル、nn−3)61と、ジメチルア
ミノエチルアクリレート(以下DMAと略す)9gと、
を添加・溶解させた。Example A-1 (1) Preparation of antistatic agent Tetrahydrofuran was added to 3001 in a Ja 500 ml flask equipped with a stirrer, and then, under stirring, an end-polymerizable copolymer of acrylonitrile having a methacryloyl group at one end and styrene was added. Polymer (hereinafter abbreviated as SANml, containing acrylonitrile ff 123% by weight, number average molecular weight 55
00) 30 g, polyethylene oxide having an acryloyl group at one end (hereinafter abbreviated as PE0m1, R3-ethyl of structural formula (I), nn-3) 61, and 9 g of dimethylaminoethyl acrylate (hereinafter abbreviated as DMA). ,
was added and dissolved.
フラスコ内を窒素で置換し、重合開始剤アゾビスイソブ
チロニトリル0,1gを更に添加し、70℃で重合を6
時間行った。重合終了後に、36重量%の塩酸を5.7
5g(ジメチルアミノエチルアクリレートに対して90
モル%)を撹拌下添加し、30分後に溶液をテフロン製
容器に移し、溶媒を減圧除去して重合物を得た。The inside of the flask was replaced with nitrogen, 0.1 g of azobisisobutyronitrile as a polymerization initiator was further added, and the polymerization was continued at 70°C for 60 minutes.
Time went. After the polymerization was completed, 5.7% of 36% by weight hydrochloric acid was added.
5g (90% for dimethylaminoethyl acrylate)
mol %) was added under stirring, and 30 minutes later, the solution was transferred to a Teflon container, and the solvent was removed under reduced pressure to obtain a polymer.
(11)帯電防止効果の評価
前記の重合物5gと、アクリロニトリルとスチレンとの
共重合体(以下SANと略す、アクリロニトリル含量2
9. 5ffi量%、数平均分子量11万)45gとを
ブラベンダーブラストグラフ、で200℃、5分間混練
し、更に粉砕した後、シリンダ−温度235℃、金型温
度40℃の射出成形機で75+omX 130mmX
25m+wの平板サンプルを成形した。(11) Evaluation of antistatic effect 5 g of the above polymer and a copolymer of acrylonitrile and styrene (hereinafter abbreviated as SAN, acrylonitrile content 2
9. 5ffi weight%, number average molecular weight 110,000) was kneaded with a Brabender blastograph at 200°C for 5 minutes, and after further pulverization, an injection molding machine with a cylinder temperature of 235°C and a mold temperature of 40°C was used to form a 75+ om x 130 mm x
A flat sample of 25 m+w was molded.
得られたサンプルについて、下記の測定法および測定条
件で表面抵抗を測定した。The surface resistance of the obtained sample was measured using the following measurement method and measurement conditions.
表面抵抗測定法
75關X130+amX25m■の平板サンプルを用い
て、表面抵抗測定器(Rcslstlvity Ce1
l)旧ghResistance Meter、ヒユー
レットφパツカード社製)で測定する方法。Surface Resistance Measuring Method Using a flat plate sample of 75 m x 130 m x 25 m
l) A method of measuring with the old ghResistance Meter (manufactured by Huyuret φPatsu Card Co., Ltd.).
この測定値(表面抵抗(Ω))が小さいほど帯電防止効
果は良好であると評価される。It is evaluated that the smaller this measured value (surface resistance (Ω)) is, the better the antistatic effect is.
7I−1定条件
(1) サンプルを23℃、相対湿度50%の恒温恒湿
器内で24時間保持した後、測定(未洗浄測定)
(2) サンプルを洗剤(ママローヤル、ライオン(株
)製)水溶液を含浸したガーゼで十分洗浄し、次いで蒸
溜水で十分に濯いでから表面から水を除去し、23℃相
対湿度50%の恒温恒湿器内で24時間保持するサイク
ルを10回繰返した後、測定した(洗浄−乾燥サイクル
、10回後に測定)
ΔP1定の結果を第1表に示す。7I-1 Conditions (1) Measure the sample after keeping it in a constant temperature and humidity chamber at 23°C and 50% relative humidity for 24 hours (unwashed measurement) (2) Wash the sample with detergent (Mama Royal, Lion Co., Ltd.) Wash thoroughly with gauze impregnated with an aqueous solution (manufactured by Mikuni), then thoroughly rinse with distilled water, remove water from the surface, and hold in a constant temperature and humidity chamber at 23°C and 50% relative humidity for 24 hours. Repeat the cycle 10 times. Table 1 shows the results of ΔP1 constant (measured after 10 washing-drying cycles).
実施例A−2〜A−23
実施例A−1に記載の例において、コモノマーの種類お
よび重量比、アンモニウム化試薬、帯電防止剤/基体樹
脂との重量比を第1表に示すように変更した他は同例に
おけるとと同様の手順で帯電防止剤を製造し、得られた
帯電防止剤について、同例におけると同様にして帯電防
止効果を評価した。Examples A-2 to A-23 In the example described in Example A-1, the type and weight ratio of the comonomer, the ammonium forming reagent, and the weight ratio of antistatic agent/base resin were changed as shown in Table 1. Other than that, an antistatic agent was produced in the same manner as in the same example, and the antistatic effect of the obtained antistatic agent was evaluated in the same manner as in the same example.
結果を第1表に示す。The results are shown in Table 1.
比較例1〜7
実m例A−1に記載の例において、コモノマーの種類お
よび重量比、アンモニウム化試薬の種類、帯電防止剤/
基体樹脂との重量比を第1表に示すように変更した他は
、同例におけると同様の手順で帯電防止剤を製造した。Comparative Examples 1 to 7 In the example described in Example A-1, the type and weight ratio of the comonomer, the type of ammonium-forming reagent, the antistatic agent/
An antistatic agent was produced in the same manner as in the same example except that the weight ratio with the base resin was changed as shown in Table 1.
得られた帯電防止剤について、同例におけると同様にし
て帯電防止効果を評価した。The antistatic effect of the obtained antistatic agent was evaluated in the same manner as in the same example.
結果を第1表に示す。The results are shown in Table 1.
第1
例
実施例A1
実施例A2
実施例A3
実施例A4
比較例A1
比較例A2
実施例A5
実施例A6
実施例A7
実施例A8
実施例A9
実施例ALO
比較例A3
比較例A3
比較例A5
帯電防止剤製造コモノマー等の種類および重量比コモノ
マー(a)コモノマー(bo)コモノマー(c)コモノ
マー(d)PEOml 61 DMA 9
5ANIIl 30PE伽2 61 DMA
9 5ANIIl 30PE〜3 61
DMA 9 SAllJml 30PEOI
3 61 DMA 9 5ANII 30
DMA 9 5ANn+1 300A 6
1 DMA 9 5ANsl 30PEO
1261DMA I 5ANI11 30P
EOm2 61 D14A 9 SANm
l 30PE伽2 57 DMA15
SANml 28PEOm2 78 DMA
2 5ANIIl 20PEOm2 69
D)4A 9 5ANal 22PEOm2
11 DMA 9 SANml 80
PE珈2 81 DMA 9 5ANa+1
10PEOn+2 1 D)tA Q
5ANa+1 90PR)+112 67 −
5ANi1 33アンモニウム化試薬
塩酸 2.07
塩酸 2.07
塩酸 2.07
塩酸 2.07
塩酸 2.07
塩酸 2.07
塩酸 0.23
塩酸 2.07
塩酸 3.44
塩酸 0.46
塩酸 2.07
塩酸 2.07
塩酸 2.07
塩酸 2.07
樹脂組成物
帯電防止剤/基体樹脂
10/90 (SAN)
10/90 (SAN)
10/90 (SAN)
10/90 (SAN)
10/90 (SAN)
10/90 (SAN)
10/90 (ABS)
10/90 (ABS)
10/90 (ABS)
10/90 (ABS)
10/90 (ABS)
10/90 (ABS)
10/90 (SAN)
10/90 (SAN)
10/90 (SAN)
表面抵抗(Ω)
未洗浄 10回洗浄
lX1O129xlO”
7X10116×1011
6X10117xlO”
6X10114X10”
5X10135X1014
7X10115×1014
5×10127×1012
3×10112×1011
6×1093×1010
5X10124X1.012
2X10■14X1011
4X10125×1012
4xlO” 3X10”’
2×10142×1014
1刈0131X1013
実施例B−1〜B−17
実施例A−1に記載の例において、重合溶媒としてテト
ラヒドロフランとエタノールとの混合溶媒(混合比15
0:20)を用い、更に、第2表に示されるコモノマー
111m比、帯電防止剤/基体樹脂との重量比で実施す
る他は同例と同様に帯電防止剤を製造し、帯電防止効果
を評価した。1st Example Example A1 Example A2 Example A3 Example A4 Comparative Example A1 Comparative Example A2 Example A5 Example A6 Example A7 Example A8 Example A9 Example ALO Comparative Example A3 Comparative Example A3 Comparative Example A5 Antistatic Type and weight ratio of comonomers, etc. for agent production Comonomers (a) Comonomer (bo) Comonomer (c) Comonomer (d) PEOml 61 DMA 9
5ANIIl 30PEK2 61 DMA
9 5ANIIl 30PE~3 61
DMA 9 SAllJml 30PEOI
3 61 DMA 9 5ANII 30
DMA 9 5ANn+1 300A 6
1 DMA 9 5ANsl 30PEO
1261DMA I 5ANI11 30P
EOm2 61 D14A 9 SANm
l 30PE 2 57 DMA15
SANml 28PEOm2 78 DMA
2 5ANIIl 20PEOm2 69
D) 4A 9 5ANal 22PEOm2
11 DMA 9 SANml 80
PE 2 81 DMA 9 5ANa+1
10PEOn+2 1 D)tA Q
5ANa+1 90PR)+112 67 −
5ANi1 33 Ammoniumation reagent Hydrochloric acid 2.07 Hydrochloric acid 2.07 Hydrochloric acid 2.07 Hydrochloric acid 2.07 Hydrochloric acid 2.07 Hydrochloric acid 2.07 Hydrochloric acid 0.23 Hydrochloric acid 2.07 Hydrochloric acid 3.44 Hydrochloric acid 0.46 Hydrochloric acid 2.07 Hydrochloric acid 2.07 Hydrochloric acid 2.07 Hydrochloric acid 2.07 Resin composition antistatic agent/base resin 10/90 (SAN) 10/90 (SAN) 10/90 (SAN) 10/90 (SAN) 10/90 (SAN) 10/90 (SAN) 10/90 (ABS) 10/90 (ABS) 10/90 (ABS) 10/90 (ABS) 10/90 (ABS) 10/90 (ABS) 10/90 (SAN) 10/ 90 (SAN) 10/90 (SAN) Surface resistance (Ω) Uncleaned 10 times washed lX1O129xlO" 7X10116x1011 6X10117xlO"6X10114X10" 5X10135X1014 7X10115x1014 5x10127x1012 3 ×10112×1011 6×1093×1010 5X10124X1. 012 2X10■14X1011 4X10125×1012 4xlO” 3X10”’ 2×10142×1014 1 0131X1013 Examples B-1 to B-17 In the example described in Example A-1, a mixed solvent of tetrahydrofuran and ethanol was used as the polymerization solvent. (Mixing ratio 15
Further, an antistatic agent was produced in the same manner as in the same example except that the comonomer 111m ratio and the weight ratio of antistatic agent/base resin shown in Table 2 were used to obtain an antistatic effect. evaluated.
結果を第2表に示す。The results are shown in Table 2.
比較例B−1〜B−6
実施例A−1に記載の例において、重合溶媒としてテト
ラヒドロフランとエタノールとの混合溶媒(混合比15
0:20)を用い、更に、第2表に示されるコモノマー
重量比、帯電防止剤/基体樹脂との重量比の条件で行う
他は同例と同様に帯電防止効果を製造し、帯電防止効果
を評価した。Comparative Examples B-1 to B-6 In the example described in Example A-1, a mixed solvent of tetrahydrofuran and ethanol (mixing ratio 15
Further, the antistatic effect was produced in the same manner as in the same example except that the comonomer weight ratio and the antistatic agent/base resin weight ratio shown in Table 2 were used. was evaluated.
結果を第2表に示す。The results are shown in Table 2.
例
実施例B1
実施例B2
実施例B3
実施例B4
比較例B1
比較例B2
実施例B5
実施例B6
実施例B7
実施例B8
実施例B9
実施例BIO
比較例B3
比較例B4
比較例B5
実施例Bll
実施例B12
実施例B13
実施例B14
実施例BL5
実施例BIG
比較例B6
実施例B17
第2表
帯電防止剤製造コモノマー等の種類および重量比コモノ
マー(a)コモノマー(b)コモノマー(c)コモノマ
ー(d)PIEOml 61 TMA 9
SANml 30P[EOm2 61 T
MA 9 SANml 30PEOm3 6
1 TMA 9 SANml 30PE
Om3 61 TMA 9 SANml
30− TKA 9
SANml 300A 61 T
MA 9 SANml 30PEO1i2
66 TMA I SANml 33
PIEOm2 61 TKA 9 SAN
ml 30PEOm2 57 TMA15
SANml 28PrEOm2 78 T)
4A 2 SANml 20PEOm2 6
9 TMA 9 SANml 22PEO
m2 11 TMA 9 SANml
80PEOm2 81 TMA
9 SANml 1010PE0
1 TMA 9 SAN+++1
90PEOm2 67 − SANml
3BPEOm5 61 T14A 9
SANm2 30PPOm 61 TMA
9 SAtJml 30PAOm 6
1 TMA 9 SANml
30PEOm2 61 DMBA
9 SANml 30P[EO
m2 61 T)tA 9 SANml
30PEOm2 61 TMA
9 5ANIIll 30PEOm2 6
1 TMA 9 SAN+nl 30
MMA 40樹脂組成物
DMBA
;メタクリロイルオキシプロピルジメチルベンジルアン
モニウムクロライド上記の結果から明かな様に、
この発明の組成範
囲かが選択された帯電防止剤を含む熱可塑性樹脂成形品
は、
比較例の樹脂成形品に比べて帯電防止
効果に優れ、
また優れた持続性、
すなわち優れた
制電性を有することがわかる。Examples Example B1 Example B2 Example B3 Example B4 Comparative Example B1 Comparative Example B2 Example B5 Example B6 Example B7 Example B8 Example B9 Example BIO Comparative Example B3 Comparative Example B4 Comparative Example B5 Example Bll Implementation Example B12 Example B13 Example B14 Example BL5 Example BIG Comparative Example B6 Example B17 Second table Antistatic agent production Types and weight ratios of comonomers etc. Comonomer (a) Comonomer (b) Comonomer (c) Comonomer (d) PIEOml 61 TMA 9
SANml 30P [EOm2 61T
MA 9 SANml 30PEOm3 6
1 TMA 9 SANml 30PE
Om3 61 TMA 9 SANml
30- TKA 9
SANml 300A 61T
MA 9 SANml 30PEO1i2
66 TMA I SANml 33
PIEOm2 61 TKA 9 SAN
ml 30PEOm2 57 TMA15
SANml 28PrEOm2 78T)
4A 2 SANml 20PEOm2 6
9 TMA 9 SANml 22PEO
m2 11 TMA 9 SANml
80PEOm2 81 TMA
9 SANml 1010PE0
1 TMA 9 SAN+++1
90PEOm2 67-SANml
3BPEOm5 61 T14A 9
SANm2 30PPOm 61 TMA
9 SAtJml 30PAOm 6
1 TMA 9 SANml
30PEOm2 61 DMBA
9 SANml 30P[EO
m2 61 T)tA 9 SANml
30PEOm2 61 TMA
9 5ANIIll 30PEOm2 6
1 TMA 9 SAN+nl 30
MMA 40 resin composition DMBA; methacryloyloxypropyldimethylbenzyl ammonium chloride As is clear from the above results, thermoplastic resin molded articles containing an antistatic agent selected from the composition range of this invention were compared to the resin molded products of the comparative example. It can be seen that the antistatic effect is superior to that of other products, and it also has excellent sustainability, that is, excellent antistatic properties.
Claims (1)
型共重合体からなる熱可塑性樹脂用帯電防止剤。 (a)分子末端にアクリロイル基またはメタクリロイル
基を有する末端重合性ポリアルキレンオキシド (b)アンモニウム塩含有のアクリレートまたはメタク
リレート (c)分子末端にアクリロイル基、メタクリロイル基ま
たはビニル芳香族基を有するアクリロニトリルとスチレ
ンとの末端重合性共重合体2、クシ型共重合体が、コモ
ノマー(a)〜(c)と前記コモノマーと共重合可能な
ビニル系モノマー(d)とからなる請求項1記載の帯電
防止剤。 3、末端重合性ポリアルキレンオキシドが、繰返し単位
エチレンオキサイドまたは/および繰返し単位プロピレ
ンオキサイドの共重合体である請求項1または請求項2
記載の帯電防止剤。 4、(a)分子末端にアクリロイル基また はメタクリロイル基を有する末端重合性ポリアルキレン
オキシド10〜80重量部と、 (b)アミノ基含有のアクリレートまたは メタクリレート0.5重量部以上と、 (c)分子末端にアクリロイル基、メタクリロイル基ま
たはビニル芳香族基を有するアクリロニトリルとスチレ
ンとの末端重合性共重合体10〜90重量部(ただし、
コモノマー(a)〜(c)は合計100重量部とする。 )と、 (d)必要に応じて、前記コモノマー(a)〜(c)と
共重合可能なビニル系モノマー100重量部以下と、 を共重合させてクシ型共重合体を生成し、 該クシ型共重合体のアミノ基をアンモニウム塩にするこ
とを特徴とする帯電防止剤の製造方法。 5、請求項1、請求項2または請求項3のいずれか1項
に記載の帯電防止剤1〜20重量部と、この帯電防止剤
と相溶性のある熱可塑性樹脂99〜80重量部とからな
ることを特徴とする永久制電性樹脂組成物。[Scope of Claims] 1. An antistatic agent for thermoplastic resins comprising a comb-shaped copolymer composed of the following comonomers (a) to (c). (a) Terminal polymerizable polyalkylene oxide having an acryloyl group or methacryloyl group at the molecular end (b) Acrylate or methacrylate containing an ammonium salt (c) Acrylonitrile and styrene having an acryloyl group, methacryloyl group, or vinyl aromatic group at the molecular end The antistatic agent according to claim 1, wherein the terminal polymerizable copolymer 2 and the comb-shaped copolymer are composed of comonomers (a) to (c) and a vinyl monomer (d) copolymerizable with the comonomers. . 3. Claim 1 or Claim 2, wherein the terminally polymerizable polyalkylene oxide is a copolymer of a repeating unit of ethylene oxide and/or a repeating unit of propylene oxide.
Antistatic agent as described. 4. (a) 10 to 80 parts by weight of a terminally polymerizable polyalkylene oxide having an acryloyl or methacryloyl group at the end of the molecule, (b) 0.5 parts by weight or more of an acrylate or methacrylate containing an amino group, and (c) the molecule 10 to 90 parts by weight of a terminally polymerizable copolymer of acrylonitrile and styrene having an acryloyl group, methacryloyl group, or vinyl aromatic group at the end (however,
The total amount of comonomers (a) to (c) is 100 parts by weight. ), and (d) if necessary, 100 parts by weight or less of a vinyl monomer copolymerizable with the comonomers (a) to (c), to produce a comb-shaped copolymer; A method for producing an antistatic agent, which comprises converting an amino group of a type copolymer into an ammonium salt. 5. From 1 to 20 parts by weight of the antistatic agent according to any one of claims 1, 2, or 3, and 99 to 80 parts by weight of a thermoplastic resin that is compatible with this antistatic agent. A permanent antistatic resin composition characterized by:
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP16965288A JPH0220588A (en) | 1988-07-07 | 1988-07-07 | Antistatic agent for thermoplastic resin, production thereof and resin composition having permanent antistatic property |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP16965288A JPH0220588A (en) | 1988-07-07 | 1988-07-07 | Antistatic agent for thermoplastic resin, production thereof and resin composition having permanent antistatic property |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH0220588A true JPH0220588A (en) | 1990-01-24 |
Family
ID=15890440
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP16965288A Pending JPH0220588A (en) | 1988-07-07 | 1988-07-07 | Antistatic agent for thermoplastic resin, production thereof and resin composition having permanent antistatic property |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0220588A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008115234A (en) * | 2006-11-02 | 2008-05-22 | Toyo Ink Mfg Co Ltd | Photocuring antistatic agent and its manufacturing method |
JP2010241991A (en) * | 2009-04-08 | 2010-10-28 | Toray Fine Chemicals Co Ltd | Acrylonitrile copolymer composition and method for producing acrylonitrile copolymer |
-
1988
- 1988-07-07 JP JP16965288A patent/JPH0220588A/en active Pending
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008115234A (en) * | 2006-11-02 | 2008-05-22 | Toyo Ink Mfg Co Ltd | Photocuring antistatic agent and its manufacturing method |
JP2010241991A (en) * | 2009-04-08 | 2010-10-28 | Toray Fine Chemicals Co Ltd | Acrylonitrile copolymer composition and method for producing acrylonitrile copolymer |
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