JPS63284264A - Easily lubricative thermoplastic resin composition - Google Patents
Easily lubricative thermoplastic resin compositionInfo
- Publication number
- JPS63284264A JPS63284264A JP8628188A JP8628188A JPS63284264A JP S63284264 A JPS63284264 A JP S63284264A JP 8628188 A JP8628188 A JP 8628188A JP 8628188 A JP8628188 A JP 8628188A JP S63284264 A JPS63284264 A JP S63284264A
- Authority
- JP
- Japan
- Prior art keywords
- thermoplastic resin
- weight
- film
- lubricant
- 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.)
- Granted
Links
- 229920005992 thermoplastic resin Polymers 0.000 title claims abstract description 104
- 239000011342 resin composition Substances 0.000 title claims abstract description 13
- 229920001577 copolymer Polymers 0.000 claims abstract description 27
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 24
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 21
- 239000000178 monomer Substances 0.000 claims abstract description 18
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 13
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 3
- 238000000465 moulding Methods 0.000 abstract description 7
- 238000002156 mixing Methods 0.000 abstract description 6
- 150000002148 esters Chemical class 0.000 abstract description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 abstract 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 abstract 1
- 239000000314 lubricant Substances 0.000 description 98
- 229920005989 resin Polymers 0.000 description 67
- 239000011347 resin Substances 0.000 description 67
- 230000000052 comparative effect Effects 0.000 description 30
- 238000000034 method Methods 0.000 description 27
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 20
- -1 vinyl resins, acrylic Chemical compound 0.000 description 20
- 239000007788 liquid Substances 0.000 description 17
- 238000012360 testing method Methods 0.000 description 17
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 15
- 230000000903 blocking effect Effects 0.000 description 15
- 238000005266 casting Methods 0.000 description 15
- 239000007787 solid Substances 0.000 description 15
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 14
- 238000004806 packaging method and process Methods 0.000 description 13
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
- 238000012545 processing Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 239000004925 Acrylic resin Substances 0.000 description 10
- 229920000178 Acrylic resin Polymers 0.000 description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 10
- 235000014113 dietary fatty acids Nutrition 0.000 description 10
- 239000000194 fatty acid Substances 0.000 description 10
- 229930195729 fatty acid Natural products 0.000 description 10
- 150000004665 fatty acids Chemical class 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 235000019441 ethanol Nutrition 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 238000007334 copolymerization reaction Methods 0.000 description 8
- 239000004014 plasticizer Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 7
- 239000004677 Nylon Substances 0.000 description 7
- 239000004698 Polyethylene Substances 0.000 description 7
- 229920001778 nylon Polymers 0.000 description 7
- 229920000573 polyethylene Polymers 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 6
- 229920006122 polyamide resin Polymers 0.000 description 6
- 230000003068 static effect Effects 0.000 description 6
- 229920002554 vinyl polymer Polymers 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 5
- 125000005907 alkyl ester group Chemical group 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 230000007774 longterm Effects 0.000 description 5
- 230000001050 lubricating effect Effects 0.000 description 5
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 5
- 229920001707 polybutylene terephthalate Polymers 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 description 4
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 4
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 4
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 4
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 229920002292 Nylon 6 Polymers 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 239000011354 acetal resin Substances 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 239000012461 cellulose resin Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012785 packaging film Substances 0.000 description 3
- 229920006280 packaging film Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229920006324 polyoxymethylene Polymers 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000012748 slip agent Substances 0.000 description 3
- 239000000344 soap Substances 0.000 description 3
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 239000001993 wax Substances 0.000 description 3
- WROUWQQRXUBECT-UHFFFAOYSA-N 2-ethylacrylic acid Chemical compound CCC(=C)C(O)=O WROUWQQRXUBECT-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 239000005909 Kieselgur Substances 0.000 description 2
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 229920000299 Nylon 12 Polymers 0.000 description 2
- 229920002302 Nylon 6,6 Polymers 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 239000002981 blocking agent Substances 0.000 description 2
- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229960000541 cetyl alcohol Drugs 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000010410 dusting Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- ZNAOFAIBVOMLPV-UHFFFAOYSA-N hexadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCOC(=O)C(C)=C ZNAOFAIBVOMLPV-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 229940043348 myristyl alcohol Drugs 0.000 description 2
- XGFDHKJUZCCPKQ-UHFFFAOYSA-N nonadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCO XGFDHKJUZCCPKQ-UHFFFAOYSA-N 0.000 description 2
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 2
- REIUXOLGHVXAEO-UHFFFAOYSA-N pentadecan-1-ol Chemical compound CCCCCCCCCCCCCCCO REIUXOLGHVXAEO-UHFFFAOYSA-N 0.000 description 2
- 239000000088 plastic resin Substances 0.000 description 2
- 239000004431 polycarbonate resin Substances 0.000 description 2
- 229920005668 polycarbonate resin Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 229940012831 stearyl alcohol Drugs 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- KJIOQYGWTQBHNH-UHFFFAOYSA-N undecanol Chemical compound CCCCCCCCCCCO KJIOQYGWTQBHNH-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 230000037303 wrinkles Effects 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 239000004605 External Lubricant Substances 0.000 description 1
- 239000004610 Internal Lubricant Substances 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229920000571 Nylon 11 Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229920001074 Tenite Polymers 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 229920003233 aromatic nylon Polymers 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- MIMDHDXOBDPUQW-UHFFFAOYSA-N dioctyl decanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC MIMDHDXOBDPUQW-UHFFFAOYSA-N 0.000 description 1
- XWVQUJDBOICHGH-UHFFFAOYSA-N dioctyl nonanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCC(=O)OCCCCCCCC XWVQUJDBOICHGH-UHFFFAOYSA-N 0.000 description 1
- HGQSXVKHVMGQRG-UHFFFAOYSA-N dioctyltin Chemical compound CCCCCCCC[Sn]CCCCCCCC HGQSXVKHVMGQRG-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- PZDUWXKXFAIFOR-UHFFFAOYSA-N hexadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCOC(=O)C=C PZDUWXKXFAIFOR-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000012690 ionic polymerization Methods 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 229940049920 malate Drugs 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N malic acid Chemical compound OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- ZMHZSHHZIKJFIR-UHFFFAOYSA-N octyltin Chemical compound CCCCCCCC[Sn] ZMHZSHHZIKJFIR-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 229940037312 stearamide Drugs 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- ATZHWSYYKQKSSY-UHFFFAOYSA-N tetradecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCOC(=O)C(C)=C ATZHWSYYKQKSSY-UHFFFAOYSA-N 0.000 description 1
- XZHNPVKXBNDGJD-UHFFFAOYSA-N tetradecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCOC(=O)C=C XZHNPVKXBNDGJD-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- KEROTHRUZYBWCY-UHFFFAOYSA-N tridecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCOC(=O)C(C)=C KEROTHRUZYBWCY-UHFFFAOYSA-N 0.000 description 1
- XOALFFJGWSCQEO-UHFFFAOYSA-N tridecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCOC(=O)C=C XOALFFJGWSCQEO-UHFFFAOYSA-N 0.000 description 1
- 229940057402 undecyl alcohol Drugs 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】 本発明は易滑性可塑性樹脂組成物に関するものである。[Detailed description of the invention] The present invention relates to a slippery plastic resin composition.
詳しくは、アクリル酸、メタクリル酸、炭素原子数が１
で２個のアルキル基をもつアクリル酸エステル、炭素原
子数が１〜２個のアルキル基をもつメタクリル酸エステ
ル、の群より選ばれた一または二以上の単量体と、炭素
原子数が１１〜２０個のアルキル基をもつアクリル酸エ
ステル、炭素原子数が１１〜２０個のアルキル基をもつ
α置換アクリル酸エステル、の群より選ばれた一または
二以上の単量体を、特定の割合で共重合させた特定範囲
の平均分子量を有する熱可塑性樹脂滑剤の特定量が熱可
塑性樹脂に含まれた易滑性熱可塑性樹脂組成物に関する
ものである。In detail, acrylic acid, methacrylic acid, carbon atom number is 1
one or more monomers selected from the group of acrylic esters having two alkyl groups, and methacrylic esters having an alkyl group having 1 to 2 carbon atoms; - One or more monomers selected from the group of acrylic esters having 20 alkyl groups, α-substituted acrylic esters having an alkyl group having 11 to 20 carbon atoms, in a specific proportion. The present invention relates to an easily slippery thermoplastic resin composition in which a thermoplastic resin contains a specific amount of a thermoplastic resin lubricant having an average molecular weight within a specific range, copolymerized with the following.
従来より、ビニル樹脂、アクリル樹脂、ポリアミド樹脂
、繊維素誘導体樹脂等の熱可塑性樹脂を、例えばフィル
ム等の成形品に成形する場合、該成形品に優れた透明性
と外部滑性を同時に付与するには滑剤上の問題があった
。Conventionally, when molding thermoplastic resins such as vinyl resins, acrylic resins, polyamide resins, and cellulose derivative resins into molded products such as films, it has been necessary to simultaneously impart excellent transparency and external lubricity to the molded product. had lubricant problems.
従来より、これらの熱可塑性樹脂成形品に外部滑性を付
与する方法として、高級脂肪酸および該脂肪酸のアミド
誘導体類、脂肪族高級アルカリ土類金属石ケン類、低分
子量のポリエチレンを主成分とするポリエチレンワック
ス類等の滑剤を添加する方法、スリップ剤またはアンチ
ブロッキング剤としてシリカ、クレー、珪藻土、タルク
、澱粉等の添加または成形品に後散布する方法等が一般
に用いられている。Traditionally, as a method of imparting external lubricity to these thermoplastic resin molded articles, methods have been used that mainly contain higher fatty acids and amide derivatives of the fatty acids, aliphatic higher alkaline earth metal soaps, and low molecular weight polyethylene. Generally used are a method of adding a lubricant such as polyethylene wax, a method of adding silica, clay, diatomaceous earth, talc, starch, etc. as a slip agent or anti-blocking agent, or a method of post-spraying the molded product.
しかし、高級脂肪酸および該脂肪酸のアミド誘導体類、
脂肪族高級アルカリ土類金属石ケン類、ポリエチレンワ
ックス類等を熱可塑性樹脂に添加する場合、該滑剤が熱
可塑性樹脂の相溶性限界以下の添加量では、該滑剤の殆
んどが成形品の中に透明な状態で相溶されるので、成形
品の表面上に該滑剤の表面層が形成されるに至らず、従
うて外部滑性効果が発揮されないが、相溶性限界以上の
添加量では、限界を超えた量の殆んどが成形品の表面上
に吹出して微細に結晶化し白化するので、優れた外部滑
性を与える反面、成形品が光沢を失い不透明化し商品価
値を著しく低下させる欠点がある。更に、相溶性限界付
近で透明性と外部滑性を同時満足する該滑剤の添加量の
範囲が極めて狭いので、熱可塑性樹脂が元来持つ透明性
を保持すると同時に、優れた外部滑性も持つ成形品を得
ることが極めて困難な状況である。However, higher fatty acids and amide derivatives of the fatty acids,
When adding aliphatic higher alkaline earth metal soaps, polyethylene waxes, etc. to thermoplastic resins, if the amount of the lubricant added is below the compatibility limit of the thermoplastic resin, most of the lubricant will be added to the molded product. Since the lubricant is compatible with the lubricant in a transparent state, a surface layer of the lubricant is not formed on the surface of the molded product, and therefore no external lubricating effect is exhibited, but if the amount added exceeds the compatibility limit, Most of the amount exceeding the limit blows out onto the surface of the molded product, crystallizes finely, and turns white, which provides excellent external lubricity, but on the other hand, the molded product loses its luster and becomes opaque, significantly reducing its commercial value. There are drawbacks. Furthermore, since the range of the amount of lubricant added that satisfies both transparency and external lubricity at the same time near the compatibility limit is extremely narrow, the thermoplastic resin retains its original transparency and at the same time has excellent external lubricity. It is extremely difficult to obtain molded products.
また、スリップ剤またはアンチブロッキング剤としてシ
リカ、クレー、珪藻土、タルク、澱粉等を添加する場合
、該添加剤で成形品の表面が凹凸化されるので比較的容
易に外部滑性が得られるが、熱可塑性樹脂との相溶性が
実質的になく、微細な粒子として分散しているに過ぎな
いので成形品全体が白色に不透明化する欠点がある。ま
た、後散布する方法では、成形品の表面に粘着性を引起
す、例えば、液状可塑剤等の浸出による薄い液状膜が存
在していても１．該散布剤で吸収、吸着されて非粘着性
の乾いた表面に変るほかに、該表面を該散布剤が微細な
粉末法状態で覆うので、特に優れた外部滑性が得られる
。しかし、散布方法そのものに欠陥があり、散布量の調
節が困難で均一に行なわれないため必然的に濃淡部が発
生し外観を損ねるほか、例えばフィルム等に後散布した
場合、濃く散布された部分では印刷に際してインクむら
、あるいはシール加工に際してはシール強度の低下等を
引起す欠点がある。In addition, when adding silica, clay, diatomaceous earth, talc, starch, etc. as a slip agent or anti-blocking agent, the surface of the molded product is roughened by the additive, so external slipperiness can be obtained relatively easily. Since it has virtually no compatibility with the thermoplastic resin and is only dispersed as fine particles, it has the disadvantage that the entire molded product becomes white and opaque. In addition, in the post-spraying method, even if a thin liquid film is present on the surface of the molded product that causes stickiness, for example, due to leaching of liquid plasticizer, etc. In addition to being absorbed and adsorbed by the dusting agent to form a non-stick, dry surface, the surface is coated with the dusting agent in a finely powdered form, resulting in particularly good external slipperiness. However, there are flaws in the spraying method itself, and it is difficult to control the amount of spraying and it is not done uniformly, which inevitably results in dark and light areas, which impairs the appearance. However, there are drawbacks such as ink unevenness during printing and a decrease in seal strength during seal processing.
成形品が外部滑性に劣るとき、例えば成形品がフィルム
でありロール巻き状態で貯蔵される場合等は、該フィル
ム相互が経時変化で密着し使用不能化する問題を引起す
。また、外部滑性に劣るフィルムを印刷、製袋、包装等
の種々の加工を行う場合、フィルム相互または装置との
間の摩擦が大きいため印刷時のインクずれや、製袋では
フィルムが蛇行しシール線が一直線に美しく仕上がらな
かったり、例え製袋が出来てもフィルム相互が密着して
いるため該袋中に包装物等を入れることが著しく困難化
したり、また包装等においては、該フィルムが包装装置
と粘着し包装作業能率を低下させたり、更には引掛かり
で該フィルムの切れ、破れ等のフィルムの使用を不能化
させる種々の厄介な問題を引起す。同様に熱可塑性樹脂
を成形品に成形する際にも、該成形品が外部滑性に劣る
ときは、金型や成形装置等と粘着を起し、成形困難化す
ることが容易に理解されよう。When a molded article has poor external lubricity, for example, when the molded article is a film and is stored in a rolled state, there is a problem that the films adhere to each other over time and become unusable. In addition, when performing various processing such as printing, bag making, and packaging on films with poor external lubricity, the friction between the films and the equipment is large, resulting in ink misalignment during printing and meandering of the film during bag making. The seal lines may not be beautifully finished in a straight line, or even if bags can be made, the films are in close contact with each other, making it extremely difficult to put packages into the bag. They stick to the packaging equipment and reduce packaging efficiency, and furthermore, they cause various troublesome problems such as cutting or tearing of the film due to snagging, making the film unusable. Similarly, when molding a thermoplastic resin into a molded product, it is easy to understand that if the molded product has poor external lubricity, it will stick to the mold, molding equipment, etc., making molding difficult. .
成形品に透明性と外部滑性を同時に付与するために解決
すべきこれらの問題は、溶液流延法で成形されるビニル
樹脂、アクリル樹脂等の場合、特に複雑化し、解決が困
難になる。These problems to be solved in order to impart transparency and external lubricity to a molded article at the same time become particularly complicated and difficult to solve in the case of vinyl resins, acrylic resins, etc. that are molded by solution casting.
例えば、溶液流延法で塩化ビニル樹脂をフィルムに成形
する場合について述べると、溶液流延法では塩化ビニル
樹脂を溶剤（例えばテトラヒドロフラン、メチルエチル
ケトン、アセトン、シクロヘキサノン等）に加熱溶解し
、例えばステンレスベルト状に流延後、該溶剤を乾燥し
てフィルムに成形するが、添加する滑剤は該溶剤に実質
的に溶解している必要がある。このため所謂、溶融押出
法、カレンダー法等で通常使用される金属石ケン類、ポ
リエチレンワックス類や前記せるスリップ剤またはアン
デブロッキング剤等の溶剤に難溶な滑剤は使用出来ず、
滑剤の選択には著しい制限を受ける。実質的に溶解しな
い滑剤を使用するときは、必然的にフィルム中に該滑性
による不透明斑点が生じ商品価値を著しく阻害する。For example, in the case of molding vinyl chloride resin into a film using the solution casting method, vinyl chloride resin is heated and dissolved in a solvent (e.g., tetrahydrofuran, methyl ethyl ketone, acetone, cyclohexanone, etc.), and then formed into a stainless steel belt. After casting, the solvent is dried and formed into a film, but the lubricant added must be substantially dissolved in the solvent. For this reason, it is not possible to use lubricants that are poorly soluble in solvents, such as metal soaps, polyethylene waxes, and the above-mentioned slip agents or undeblocking agents that are normally used in the so-called melt extrusion method, calendar method, etc.
The choice of lubricant is subject to significant limitations. When a substantially insoluble lubricant is used, opaque spots are inevitably produced in the film due to the lubricant, which significantly impairs commercial value.
更に、溶液流延性塩化ビニル樹脂フィルム原反には完全
に除去困難な溶剤（例えば５％）が残存し、これが経時
変化で添加された可塑剤等と共にフィルム原反表面へ浸
出し、粘着を引起す原因となる液状膜を形成するので優
れた外部滑性を得ることが橿めて困難になる。Furthermore, solvent (e.g. 5%), which is difficult to completely remove, remains in the solution castable vinyl chloride resin film, and as time passes, this leaches out to the surface of the film together with the added plasticizer, etc., causing adhesion. As a result, it becomes difficult to obtain excellent external lubricity.
また、従来より一般に用いられている高級脂肪酸および
該脂肪酸のアミド誘導体類、高級アルコール類等の滑剤
は、フィルム側反中の残存溶剤が浸出するとき該滑剤を
伴ってフィルム表面へ浸出するので、所謂、溶融押出法
、カレンダー法等でフィルム表面に外部滑性を付与する
ために使用される添加量より少量（例えば１７５量以下
）でも著しくフィルム表面が白化する。更に、該滑剤の
フィルム表面へ滲出する度合いは、フィルム原反中の残
存溶剤量の多少によっても異るので、添加すべき適量を
きめることも極めて困難になる。In addition, lubricants such as higher fatty acids, amide derivatives of these fatty acids, and higher alcohols, which have been commonly used in the past, are leached to the film surface along with the lubricants when the residual solvent in the film side leaches out. Even if the amount added is smaller than that used to impart external lubricity to the film surface in the so-called melt extrusion method, calender method, etc. (for example, 175 or less), the film surface will noticeably whiten. Furthermore, since the degree to which the lubricant oozes out onto the film surface varies depending on the amount of solvent remaining in the original film, it is extremely difficult to determine the appropriate amount to add.
本発明者等は、熱可塑性樹脂成形品、特に溶液流延法に
よる熱可塑性樹脂成形品に、透明性と外部滑性を同時に
付与すべく詳細な種々の研究を行った結果、従来一般に
使用されていた滑剤と全く異る新規な特定組成と特定平
均分子量を有する熱可塑性樹脂滑剤の特定量が熱可塑性
樹脂に含まれた新規な熱可塑性樹脂組成物を使用するこ
とで一挙に解決し得ることを見出した。The present inventors have conducted various detailed studies in order to simultaneously impart transparency and external lubricity to thermoplastic resin molded products, particularly thermoplastic resin molded products made by solution casting, and have found that they have developed a method that has not been commonly used in the past. A specific amount of a thermoplastic resin lubricant having a new specific composition and specific average molecular weight that is completely different from conventional lubricants can be solved at once by using a new thermoplastic resin composition contained in a thermoplastic resin. I found out.
即ち、本発明の目的は、熱可塑性樹脂成形品に優れた透
明性を与え、且つ熱可塑性樹脂から成形品に成形する場
合に優れた外部滑性を示すと共に、成形された成形品の
印刷、製袋、包装等の二次加工に際して優れた外部滑性
、換言すれば優れた作業性を付与する熱可塑性樹脂滑剤
を含有してなる易滑性熱可塑性樹脂組成物を提供するに
ある。That is, the object of the present invention is to provide a thermoplastic resin molded article with excellent transparency, exhibit excellent external lubricity when molded from the thermoplastic resin, and provide printing and printing of the molded article. An object of the present invention is to provide a slippery thermoplastic resin composition containing a thermoplastic resin lubricant that provides excellent external lubricity, in other words, excellent workability during secondary processing such as bag making and packaging.
本発明は、（イ）熱可塑性樹脂１００重量部に対して（
ロ）下記のａ成分６０〜９０重量％、ｂ成分４０〜１０
重量％の割合で主単量体単位として含有し、平均分子量
が５．０００を越え１，０００，０００以下の共重合体
０．１〜５重量部、
ａ成分、アクリル酸、メタクリル酸、炭素原子数が１〜
２個のアルキル基をもつアクリル酸エステル、炭素原子
数が１〜２個のアルキル基をもつメタクリル酸エステル
、の群より選ばれた一または二辺上の単量体
す成分、炭素原子数が１１〜２０個のアルキル基をもつ
アクリル酸エステル、炭素原子数が１１〜２０個のアル
キル基をもつα置換アクリル酸エステル、の群より選ば
れた一または二辺上の単量体。The present invention provides (a) based on 100 parts by weight of thermoplastic resin (a)
b) 60 to 90% by weight of the following component a, 40 to 10% of component b
0.1 to 5 parts by weight of a copolymer containing as the main monomer unit in a proportion of % by weight and having an average molecular weight of more than 5.000 and less than 1,000,000, component a, acrylic acid, methacrylic acid, carbon Number of atoms is 1~
A monomer component on one or two sides selected from the group of acrylic esters having two alkyl groups and methacrylic esters having an alkyl group having 1 to 2 carbon atoms, A monomer on one or two sides selected from the group of acrylic esters having 11 to 20 alkyl groups and α-substituted acrylic esters having alkyl groups having 11 to 20 carbon atoms.
を含有することを特徴とする易滑性熱可塑性樹脂組成物
に関するものである。The present invention relates to a slippery thermoplastic resin composition characterized by containing the following.
本発明に用いる熱可塑性樹脂滑剤の驚くべき透明性と外
部滑性の作用は：透明性については、熱可塑性樹脂成形
品の表面に形成される表面層は、成形品の表面上に吹出
して微細に結晶化し白化する従来の単分子または低分子
量の滑剤と異り、透明性に富み、且つ適度の平均分子量
を存する白化しない固体の共重合体層であること；外部
滑性については、構造的に熱可塑性樹脂と比較的に相溶
性を有するアクリル酸、メタクリル酸の共重合体部分が
熱可塑性樹脂に食い込む、所謂アンカ一部の存在に均衡
し、熱可塑性樹脂と比較的に非相溶性を有し外部滑性作
用を発揮する特定の高級アルキル基部分が、熱可塑性樹
脂成形品の表面から主に食→み出した形で滑性層を形成
すること、しかも、例え熱可塑性樹脂成形品の表面に、
該熱可塑性樹脂の性能向上等の目的等で添加された液状
の可塑剤、液状の安定剤等が浸出しても、それらの液状
物に対して特定の高級アルキル基部分が、適度の耐溶剤
性を有するために浸出した液状物を吸収、吸着し粘着を
引起す液状膜の形成を防止し滑性化することに基（もの
と推定される。The surprising transparency and external lubricity of the thermoplastic resin lubricant used in the present invention are as follows: In terms of transparency, the surface layer formed on the surface of the thermoplastic resin molded product is blown onto the surface of the molded product to form fine particles. Unlike conventional monomolecular or low molecular weight lubricants that crystallize and whiten, it is a solid copolymer layer that is highly transparent and has an appropriate average molecular weight and does not whiten; The copolymer portion of acrylic acid and methacrylic acid, which is relatively compatible with the thermoplastic resin, bites into the thermoplastic resin, which is balanced by the existence of a so-called anchor portion, and the copolymer portion is relatively incompatible with the thermoplastic resin. A specific higher alkyl group moiety that exhibits an external lubricating effect mainly protrudes from the surface of a thermoplastic resin molded article to form a slippery layer, and even if the thermoplastic resin molded article on the surface of
Even if liquid plasticizers, liquid stabilizers, etc. added for the purpose of improving the performance of the thermoplastic resin are leached out, the specific higher alkyl group moieties will provide adequate solvent resistance to those liquids. It is assumed that this is because it absorbs and adsorbs leached liquid substances due to its properties, prevents the formation of a liquid film that causes adhesion, and makes it slippery.
更に、本発明に用いる熱可塑性樹脂滑剤は、適度の平均
分子量を有する共重合体であるので、熱可塑性樹脂の性
能向上等の目的等で添加された液状の可塑剤、液状の安
定剤等の変性剤等や、溶液流延法で使用された溶剤と共
に該成形品の表面に実質的に浸出しないから、該成形品
の表面上における本発明の熱可塑性樹脂滑剤の分布が経
時的に実質的に不変で、そのため外部滑性を得るために
添加すべき量の把掴が容易である利点がある。Furthermore, since the thermoplastic resin lubricant used in the present invention is a copolymer with a moderate average molecular weight, it is free from liquid plasticizers, liquid stabilizers, etc. added for the purpose of improving the performance of the thermoplastic resin. Since the thermoplastic resin lubricant of the present invention is not substantially leached onto the surface of the molded product together with the modifier and the solvent used in the solution casting method, the distribution of the thermoplastic resin lubricant of the present invention on the surface of the molded product is substantially constant over time. does not change, so it has the advantage that it is easy to determine the amount to be added to obtain external lubricity.
本発明でいうａ成分とは、アクリル酸、メタクリル酸、
アクリル酸メチル、メタクリル酸メチル、アクリル酸エ
チル、メタクリル酸エチル、の群より選ばれた一または
二以上の単量体を称する。In the present invention, component a refers to acrylic acid, methacrylic acid,
Refers to one or more monomers selected from the group of methyl acrylate, methyl methacrylate, ethyl acrylate, and ethyl methacrylate.
更に本発明でいうｂ成分とは、炭素原子数が１１〜２０
個の高級アルキル基を有する高級アルコールと、アクリ
ル酸、メタクリル酸、またはエタアクリル酸の高級アル
キルエステルで、これらの高級アルキルエステルの群よ
り選ばれた一または二以上の単量体を称する。Furthermore, component b as used in the present invention refers to a component having 11 to 20 carbon atoms.
A higher alcohol having a higher alkyl group, and a higher alkyl ester of acrylic acid, methacrylic acid, or ethacrylic acid, and refers to one or more monomers selected from the group of these higher alkyl esters.
“上記せる高級アルキルエステルは、主に天然に産出す
る原料から製造される脂肪族高級アルコールや、主に化
学反応で製造される合成高級アルコール等の高級アルコ
ールと、アクリル酸、メタアクリル酸、エタアクリル酸
との反応で、いづれも容易に作ることが出来る。これら
の高級アルコールを例挙すると、ラウリルアルコール、
ミリスチルアルコール、セチルアルコール、ステアリル
アルコール、ウンデシルアルコール、ドデシルアルコー
ル、ペンタデシルアルコール、ヘプタデシルアルコール
、ノナデシルアルコール、等があるが、経済的に安価で
入手が容易なこと、および透明性、外部滑性の観点から
、高級アルコールとしてラウリルアルコール、ドデシル
アルコール、ミリスチルアルコール、セチルアルコール
、ステアリルアルコールを使用することが好ましい。ま
た、アクリル酸、メタクリル酸、エタアクリル酸のなか
では、経済的であり、且つエステル化反応、共重合反応
等が容易なアクリル酸、メタクリル酸を使用することが
好ましく、例えばアクリル酸高級アルキルエステルとし
ては、アクリル酸ラウリル、アクリル酸トリデシル、ア
クリル酸ミリスチル、アクリル酸セチル、アクリル酸ス
テアリル等、メタクリル、酸高級アルキルエステルとし
ては、メタクリル酸ラウリル、メタクリル酸トリデシル
、メタクリル酸ミリスチル、メタクリル酸セチル、メタ
クリル酸ステアリル等の使用が好ましい。“The above-mentioned higher alkyl esters are mainly aliphatic higher alcohols manufactured from naturally occurring raw materials, higher alcohols such as synthetic higher alcohols mainly manufactured by chemical reactions, acrylic acid, methacrylic acid, ethyl alcohol, etc. All of these can be easily produced by reaction with acrylic acid. Examples of these higher alcohols include lauryl alcohol,
Myristyl alcohol, cetyl alcohol, stearyl alcohol, undecyl alcohol, dodecyl alcohol, pentadecyl alcohol, heptadecyl alcohol, nonadecyl alcohol, etc. From the viewpoint of properties, it is preferable to use lauryl alcohol, dodecyl alcohol, myristyl alcohol, cetyl alcohol, and stearyl alcohol as the higher alcohol. Furthermore, among acrylic acid, methacrylic acid, and ethacrylic acid, it is preferable to use acrylic acid and methacrylic acid, which are economical and easy to undergo esterification reactions, copolymerization reactions, etc. For example, acrylic acid higher alkyl esters Examples include lauryl acrylate, tridecyl acrylate, myristyl acrylate, cetyl acrylate, stearyl acrylate, etc., and acid higher alkyl esters include lauryl methacrylate, tridecyl methacrylate, myristyl methacrylate, cetyl methacrylate, methacrylate. Preferably, stearyl acid is used.
本発明でいう熱可塑性樹脂は特に制限されるものではな
く、例えばビニル樹脂、アクリル樹脂、ポリアミド樹脂
、繊維素誘導体樹脂、石油系樹脂、スチロール樹脂、ア
セタール樹脂、テレフタル酸系樹脂、ポリカーボネート
樹脂等の熱硬化性樹脂以外の樹脂の一または二以上から
なる樹脂で、加熱で可塑性になるが常温に戻すと変化し
難い状態になるような樹脂等をいう、これらの樹脂中で
主なものを列挙すると、ビニル樹脂には、塩化ビニル樹
脂、酢酸ビニル樹脂、ビニルアルコール樹脂、ビニルア
セタール樹脂、塩化ビニリデン樹脂等；アクリル樹脂に
は、アクリル酸エステル樹脂（アルキル基の炭素原子数
が１０個以下）、メタクリル酸エステル樹脂（アルキル
基の炭素原子数が１０個以下）、アクリルニトリル樹脂
、アクリル酸樹脂、アクリルアミド樹脂等；ポリアミド
樹脂には、ポリカプラミド樹脂、ポリヘキサメチレンア
ジパミド樹脂、ポリへキサメチレンセパテート樹脂、そ
の他、所謂７ナイロン樹脂、８ナイロン樹脂、９ナイロ
ン樹脂、１０ナイロン樹脂、１１ナイロン樹脂、１２ナ
イロン樹脂、芳香族ナイロン樹脂、含窒素環ポリアミド
樹脂等；繊維素誘導体樹脂には、硝酸繊維素樹脂、酢酸
繊維素樹脂、プロピオン酸繊維素樹脂、エチル繊維素樹
脂等１万油系樹脂には、ポリエチレン、ポリプロピレン
、ポリブテン、ポリブタジェン、ポリイソブチレン等；
スチロール樹脂には、ポリスチロール、ＡＢＳ樹脂、Ａ
ｓ樹脂等；アセタール樹脂には、ホルマル樹脂、プチラ
ル樹脂等；テレフタル酸系樹脂には、ポリブチレンテレ
フタレート樹脂、ポリブチレンテレフタレート樹脂、テ
レフタル酸フェノールエステル′樹脂等；ポリカーボネ
ート樹脂には、ジオキシジフェニルメタンカーボネート
樹脂、ジオキシジフェニルエタンカーボネート樹脂、グ
オキシフェニルー２，２−プロパンカーボネート樹脂等
がある。The thermoplastic resin referred to in the present invention is not particularly limited, and includes, for example, vinyl resin, acrylic resin, polyamide resin, cellulose derivative resin, petroleum resin, styrene resin, acetal resin, terephthalic acid resin, polycarbonate resin, etc. A resin consisting of one or more resins other than thermosetting resins, which becomes plastic when heated but does not easily change when returned to room temperature.Main types of these resins are listed. Then, vinyl resins include vinyl chloride resin, vinyl acetate resin, vinyl alcohol resin, vinyl acetal resin, vinylidene chloride resin, etc.; acrylic resins include acrylic ester resins (alkyl group has 10 or less carbon atoms), Methacrylic acid ester resins (alkyl group has 10 or less carbon atoms), acrylonitrile resins, acrylic acid resins, acrylamide resins, etc.; polyamide resins include polycapramide resins, polyhexamethylene adipamide resins, polyhexamethylene separators, etc. Tate resin, and other so-called 7 nylon resins, 8 nylon resins, 9 nylon resins, 10 nylon resins, 11 nylon resins, 12 nylon resins, aromatic nylon resins, nitrogen-containing ring polyamide resins, etc.; For cellulose derivative resins, nitric acid 10,000 oil-based resins such as cellulose resin, acetic acid cellulose resin, propionate cellulose resin, ethyl cellulose resin, etc. include polyethylene, polypropylene, polybutene, polybutadiene, polyisobutylene, etc.;
Styrene resin includes polystyrene, ABS resin, A
s resin, etc.; acetal resins include formal resin, petral resin, etc.; terephthalic acid resins include polybutylene terephthalate resin, polybutylene terephthalate resin, terephthalic acid phenol ester resin, etc.; polycarbonate resin includes dioxydiphenylmethane carbonate resin, dioxydiphenylethane carbonate resin, goxyphenyl-2,2-propane carbonate resin, etc.
合で通常の重合方法、例えば有機過酸化物や有機アゾ化
合物等の触媒を用いた縣濁重合法や、クメン、イソプロ
ビールアルコール等の溶媒中において重合開始剤を用い
たラジカル重合法や、その他イオン重合法等の方法で、
平均分子量が５．０００を越え１，０００，０００以下
の固体の熱可塑性樹脂滑剤にすることが出来る。For example, suspension polymerization using a catalyst such as an organic peroxide or an organic azo compound, a radical polymerization method using a polymerization initiator in a solvent such as cumene or isopropyl alcohol, and others. By methods such as ionic polymerization,
It can be made into a solid thermoplastic resin lubricant having an average molecular weight of more than 5.000 and less than 1,000,000.
本発明で、熱可塑性樹脂滑剤の平均分子量を５．０００
を越えたものとしたのは、５．０００以下の低分子量で
は常温で液状またはペースト状であり、熱可塑性樹脂に
該共重合体を添加し成形品に成形しても、該成形品の表
面に浸出しやすく、且つ薄い液状またはペースト状膜を
形成し、かえって粘着性を増加させるからである。また
、平均分子量を１，０００，０００以下としたのは、１
，０００．０００を越えては熱可塑性樹脂との相溶性が
悪くなり、該共重合体を熱可塑性樹脂に添加し成形品に
成形した場合、該成形品中にあっては不透明化を起した
り、或は該成形品の表面上にあっては不透明な被膜状物
を形成し１．商品価値を低下させ好ましくないからであ
る。In the present invention, the average molecular weight of the thermoplastic resin lubricant is 5.000.
The reason why the copolymer has a low molecular weight of 5.000 or less is liquid or paste-like at room temperature, and even if the copolymer is added to a thermoplastic resin and molded into a molded product, the surface of the molded product is This is because it easily leaches out and forms a thin liquid or paste-like film, which actually increases stickiness. In addition, the average molecular weight was set to 1,000,000 or less because 1
. or forming an opaque film-like substance on the surface of the molded product; 1. This is because it lowers the product value and is undesirable.
本発明に用いる熱可塑性樹脂滑剤の平均分子量は５，０
００を越え、１，０００，０００以下のものであれば、
いづれのものでも使用出来るが、平均分子量が１０．０
００を越え２００．０００以下の熱可塑性樹脂滑剤の場
合、熱可塑性樹脂と適度の相溶性等を示し、成形品に特
に優れた透明性と外部滑性を同時に与えるので特に好ま
しい。The average molecular weight of the thermoplastic resin lubricant used in the present invention is 5.0
If it is more than 00 and less than 1,000,000,
Any one can be used, but the average molecular weight is 10.0.
A thermoplastic resin lubricant having a molecular weight of more than 0.00 and less than 200.000 is particularly preferable because it exhibits appropriate compatibility with the thermoplastic resin and provides particularly excellent transparency and external lubricity to the molded product at the same time.
次に、本発明に用いる熱可塑性樹脂滑剤の組成で、ｂ成
分の共重合割合をａ成分６０〜９０重量％に対して、４
０〜ｌＯ重量％と限定した理由を述べると、ｂ成分１０
重量％未満ではａ成分との相溶性がよく、得られる共重
合自体の透明がよい。Next, in the composition of the thermoplastic resin lubricant used in the present invention, the copolymerization ratio of component b is 4% to 60 to 90% by weight of component a.
To explain the reason why it is limited to 0 to 10% by weight, component b is 10%.
When the amount is less than % by weight, the compatibility with component a is good, and the resulting copolymer itself is transparent.
しかし、該共重合体を熱可塑性樹脂に添加し成形品に成
形しても透明性が満足されるが、外部滑性が不十分とな
るからである。またｂ成分４０重量％以下とした理由は
、４０重量％を越えては外部滑性が満足されるが、ａ成
分との相溶性が悪くなり、該共重合体を熱可塑性樹脂に
添加し成形しても該成形品の透明性が不十分になるから
である。However, even if the copolymer is added to a thermoplastic resin and molded into a molded article, the transparency will be satisfied, but the external lubricity will be insufficient. The reason why component b is set to be 40% by weight or less is that if it exceeds 40% by weight, the external lubricity is satisfied, but the compatibility with component a becomes poor, so the copolymer is added to the thermoplastic resin and molded. This is because the transparency of the molded product will be insufficient even if the molded product is used.
ｂ成分の共重合割合が３０〜１５重量％の熱可塑性樹脂
滑性のとき、成形品に特に優れた透明性と外部滑性を付
与するので好ましい。When the copolymerization ratio of component b is 30 to 15% by weight, it is preferable that the thermoplastic resin has a lubricating property because it imparts especially excellent transparency and external lubricating property to the molded product.
なお、本発明でａ成分６０〜９０重量％、ｂ成分４０〜
１０重量％の割合で主単量体単位として含有するとは、
ａ成分６０〜９０重量％、ｂ成分４０〜１０重量％の割
合よりなるものが、熱可塑性樹脂滑剤の組成中８０重量
％以上、好ましくは９０重重景以上含有する意味で用い
るもので、他の成分として、本発明で用いる熱可塑性樹
脂滑剤の透明性と外部滑性作用に大きな影響を与えない
程度の、例えばアクリルアマイド、メタクリルアマイド
、アクリロニトリル、メタアクリロニトリル、塩化ビニ
ル、塩化ビニリデン、酢酸ビニル、スチレン、ブタジェ
ン等を適宜、共重合してもよい。In addition, in the present invention, the a component is 60 to 90% by weight, and the b component is 40 to 90% by weight.
Containing as the main monomer unit in a proportion of 10% by weight means
The composition of the thermoplastic resin lubricant is composed of 60 to 90% by weight of component a and 40 to 10% by weight of component b, and is used in the sense that it contains 80% by weight or more, preferably 90% by weight or more, in the composition of the thermoplastic resin lubricant. Ingredients include acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, vinyl acetate, and styrene to an extent that does not significantly affect the transparency and external lubricity of the thermoplastic resin lubricant used in the present invention. , butadiene, etc. may be appropriately copolymerized.
次に、本発明において、熱可塑性樹脂１００重量部に対
し、本発明に用いる熱可塑性樹脂滑剤を０．１〜５重量
部に限定した理由を述べれば、０．１重量部未満であれ
ば熱可塑性樹脂に該滑剤を添加し。Next, in the present invention, the reason why the thermoplastic resin lubricant used in the present invention is limited to 0.1 to 5 parts by weight per 100 parts by weight of the thermoplastic resin is that if it is less than 0.1 part by weight, The lubricant is added to the plastic resin.
Ｗ成形品に成形しても、該成形品の表面に分布される該
滑剤の濃度が少いため十分な外部滑性が得られず、例え
ばフィルム滑性、耐ブロッキング性が不十分になるから
である。また、該滑剤の使用量が５重量部を越える場合
は、十分な外部滑性が得られるが、該成形品の透明性が
減退し、商品価値を低下させるので好ましくなく、且つ
不経済である。本発明に用いる熱可塑性樹脂滑剤の添加
量は、熱可塑性樹脂１００重量部に対して、１〜５重量
部範囲が最も透明性、外部滑性の両性能を発揮しやすく
好ましい。Even if it is molded into a W molded product, sufficient external lubricity cannot be obtained because the concentration of the lubricant distributed on the surface of the molded product is low, resulting in insufficient film lubricity and blocking resistance, for example. be. Furthermore, when the amount of the lubricant used exceeds 5 parts by weight, sufficient external lubricity can be obtained, but the transparency of the molded product decreases and the commercial value decreases, which is undesirable and uneconomical. . The addition amount of the thermoplastic resin lubricant used in the present invention is preferably in the range of 1 to 5 parts by weight based on 100 parts by weight of the thermoplastic resin, since it is most likely to exhibit both performance of transparency and external lubricity.
本発明に用いる熱可塑性樹脂滑剤は、前記した種々の熱
可塑性樹脂に添加され、成形品に優れた透明性と外部滑
性効果を与えるものであるが、熱可塑性樹脂の成形品で
外部滑性が問題の塩化ビニル樹脂、アクリル樹脂、ポリ
アミド樹脂、特に半硬質、軟質塩化ビニル樹脂、メタク
リル酸エステル樹脂に優れた効果を発揮する。The thermoplastic resin lubricant used in the present invention is added to the various thermoplastic resins mentioned above to give molded products excellent transparency and external lubricity. It exhibits excellent effects on vinyl chloride resins, acrylic resins, and polyamide resins, especially semi-rigid and soft vinyl chloride resins, and methacrylic acid ester resins.
ここでいう塩化ビニル樹脂とは、塩化ビニル単独重合体
、および少くとも７５重重景の塩化ビニルと２５重量％
までの酢酸ビニル、アクリロニトリル、アクリル酸エチ
ル、塩化ビニリデンおよびジエチルマレートのような塩
化ビニルと共重合性の１種またはそれ以上のエチレン状
不飽和単量体との共重合体をいい、半硬質塩化ビニル樹
脂とは、ＤＯＰをはじめとする各種可塑剤を前記塩化ビ
ニル樹脂１００重量部に対し約１０〜３０重量部添加さ
れたものをいい、軟質塩化ビニル樹脂とは、各種可塑性
を約３０〜５０重量部添加されたものをいう。また、ア
クリル樹脂とは、アクリル酸、アクリル酸エステル（ア
ルキル基の炭素原子数が１０個以下）、アクリルアミド
、アクリルニトリル、メタクリル酸、メタクリル酸エス
テル（アルキル基の炭素原子数が１０個以下）、などの
重合体、および樹脂改質のためスチレンなど他の単量酸
エステル樹脂がある。またポリアミド樹脂とは分子中に
アミド基（−ＮＨＣＯ−）をもつ重合体で、ラクタムの
開環重合、アミノカルボン酸の自己縮合、ジアミンと有
機二塩基酸との縮合、等で得られ、一般式、（−ＮＨ−
Ｒ’−Ｃｏ−）Ｘおよび（−ＮＨ−Ｒ” −ＮＨＣＯ−
Ｒ” −Ｃｏ） 、！で表されるものである。代表的な
ものとして前者にはナイロン６、ナイロン１１、ナイロ
ン１２等があり、後者にはナイロン６６、ナイロン６１
０がある。更に、これらの構造単位を有するものには、
他の重合体と同様に２種以上の単量体からなる共重合体
、例えばナイロン６の単量体とナイロン１２の単量体と
からなる共重合体も含まれる。The vinyl chloride resin herein refers to a vinyl chloride homopolymer and at least 75% by weight of vinyl chloride.
A semi-rigid copolymer of vinyl chloride and one or more copolymerizable ethylenically unsaturated monomers, such as vinyl acetate, acrylonitrile, ethyl acrylate, vinylidene chloride, and diethyl maleate. Vinyl chloride resin refers to one in which about 10 to 30 parts by weight of various plasticizers such as DOP are added to 100 parts by weight of the vinyl chloride resin, and soft vinyl chloride resin refers to one in which various plasticizers including DOP are added to about 30 to 30 parts by weight. 50 parts by weight is added. In addition, acrylic resins include acrylic acid, acrylic ester (alkyl group has 10 or less carbon atoms), acrylamide, acrylonitrile, methacrylic acid, methacrylic ester (alkyl group has 10 or less carbon atoms), and other monomeric acid ester resins such as styrene for resin modification. Polyamide resin is a polymer with an amide group (-NHCO-) in the molecule, and is obtained by ring-opening polymerization of lactam, self-condensation of aminocarboxylic acid, condensation of diamine and organic dibasic acid, etc. Formula, (-NH-
R'-Co-)X and (-NH-R''-NHCO-
R”-Co), ! Typical examples of the former include nylon 6, nylon 11, and nylon 12, and examples of the latter include nylon 66 and nylon 61.
There is 0. Furthermore, those having these structural units include
Like other polymers, copolymers made of two or more types of monomers, such as copolymers made of nylon 6 monomers and nylon 12 monomers, are also included.
本発明に用いる熱可塑性樹脂滑剤は、熱可塑性樹脂に対
し前記した添加範囲で、通常用いられる混合方法、混合
装置等で混合することによって容易に本発明の易滑性熱
可塑性樹脂組成物とすることが出来る。これらには多種
多様あるが代表的混合装置を挙げると、リボンブレンダ
ー、■ブレンダー、パンバリミキサー、高速流動式ミキ
サー（スーパーミキサー）、ボールミル、らい潰機等が
あるが、高品質の組成物を得るには使用する混合装置の
特徴、条件を把掴し、可及的に均一に熱可塑性樹脂滑剤
を分散することが好ましい。The thermoplastic resin lubricant used in the present invention can be easily made into the slippery thermoplastic resin composition of the present invention by mixing the thermoplastic resin within the above-mentioned addition range using a commonly used mixing method, mixing device, etc. I can do it. There are a wide variety of these devices, but typical mixing devices include ribbon blenders, blenders, Pan Bali mixers, high-speed fluid mixers (super mixers), ball mills, and crushers. In order to obtain this, it is preferable to understand the characteristics and conditions of the mixing device used and to disperse the thermoplastic resin lubricant as uniformly as possible.
また、本発明の易滑性熱可塑性樹脂組成物には、各種の
加工方法に適するように更に適宜、可塑剤、安定剤、界
面活性剤、帯電防止剤、紫外線吸収剤、抗酸化剤、充填
剤、染料等を添加して所謂溶融押出法、カレンダー法ま
たは溶液流延法等によって成形品に成形し得る。ただし
、適宜加えられるべき可塑剤、安定剤、充填剤、染料等
による成形品の外観および機械的性質等における効果に
対して使用される変性剤は本発明の組成物の本質的な成
分ではない。In addition, the easily slippery thermoplastic resin composition of the present invention may further contain plasticizers, stabilizers, surfactants, antistatic agents, ultraviolet absorbers, antioxidants, fillers, etc. in order to be suitable for various processing methods. It is possible to add additives, dyes, etc. and mold the product into a molded article by a so-called melt extrusion method, a calender method, a solution casting method, or the like. However, modifiers used for effects on the appearance, mechanical properties, etc. of molded products by plasticizers, stabilizers, fillers, dyes, etc., which should be added as appropriate, are not essential components of the composition of the present invention. .
更に、本発明に用いる熱可塑性樹脂滑剤は、単独で使用
しても、従来の滑剤では得られない優れた透明性と外部
滑性を有する成形品を与えるものであるが、溶融押出法
、カレンダー法、溶液流延法等の種々の加工方法におい
て、該滑剤以外に、熱可塑性樹脂の溶融粘度を下げ流動
性を改善するための内部滑剤あるいは例えば流延面上に
形成したフィルムの剥離性の向上のための滑剤等として
従来一般に使用されていた炭化水素、脂肪酸系、脂肪酸
アミド系、エステル系滑剤等を、本発明に用いる熱可塑
性樹脂滑剤と併用することも出来る。Furthermore, even when used alone, the thermoplastic resin lubricant used in the present invention provides molded products with excellent transparency and external lubricity that cannot be obtained with conventional lubricants. In various processing methods such as casting method and solution casting method, in addition to the lubricant, internal lubricants are used to lower the melt viscosity of the thermoplastic resin and improve fluidity, or for example, to improve the peelability of the film formed on the casting surface. Hydrocarbon, fatty acid-based, fatty acid amide-based, ester-based lubricants, etc., which have been conventionally commonly used as lubricants for improving the quality of water, can also be used in combination with the thermoplastic resin lubricant used in the present invention.
次に、本発明を更に詳細に説明するために実施例を挙げ
るが、本発明はこれらの実施例により限定されるもので
はない。Next, Examples will be given to explain the present invention in more detail, but the present invention is not limited to these Examples.
熱可塑性樹脂滑剤の調製
参考例１
メタクリル酸メチル７７重量％とメタクリル酸ステアリ
ル２３重量％に対して、ラウリルパーオキシド３．３重
量％を混合した混合液を、ポリビニールアルコール（日
本合成化学（株）製ゴーセノ濁させ、反応器内を窒素ガ
スで置換し、７５°Ｃ２に加熱し、５時間攪拌反応した
。その後、決過、′乾燥後、メタクリル酸メチルとメタ
クリル酸ステア、リルを主成分とするパール状で固体の
平均分子量約１００．０００の熱可塑性樹脂滑剤を得た
。Reference Example 1 Preparation of Thermoplastic Resin Lubricant A mixture of 77% by weight of methyl methacrylate, 23% by weight of stearyl methacrylate, and 3.3% by weight of lauryl peroxide was mixed with polyvinyl alcohol (Nippon Gosei Kagaku Co., Ltd.). ), the reactor was purged with nitrogen gas, heated to 75°C, and reacted with stirring for 5 hours. After filtering and drying, the main components were methyl methacrylate, stear methacrylate, and lyl. A pearl-like solid thermoplastic resin lubricant having an average molecular weight of about 100,000 was obtained.
参考例２〜１０及び比較参考例１
参考例１において、ラウリルパーオキサイドの使用量、
反応温度及び反応時間を変えた以外は同様にして、第１
表に示す平均分子量約７．０００〜約１，２００，００
０の固体の熱可塑性樹脂滑剤を得た。Reference Examples 2 to 10 and Comparative Reference Example 1 In Reference Example 1, the amount of lauryl peroxide used,
The first step was carried out in the same manner except that the reaction temperature and reaction time were changed.
Average molecular weight shown in the table: about 7.000 to about 1,200,00
A solid thermoplastic resin lubricant of 0 was obtained.
比較参考例２
参考例１と同様の反応器を用い、窒素雰囲気下で、メタ
クリル酸メチル７７重量％とメタクリル酸ステアリル２
３重量％の合計１００重量％に対してＬ−ブチルパーオ
キシピバレート１重量％をン昆合し、これをイソプロビ
ールアルコール重量％の入った７５°Ｃに加熱された反
応器中に攪拌下に２時間で滴下し、さらに６時間攪拌反
応させた。この反応液を４００重量％の水中に滴下し、
が過乾燥後第１表に示す平均分子量約２．０００の液状
共重合体を得た。Comparative Reference Example 2 Using the same reactor as Reference Example 1, 77% by weight of methyl methacrylate and 2 stearyl methacrylate were mixed in a nitrogen atmosphere.
1% by weight of L-butyl peroxypivalate was added to a total of 100% by weight of 3% by weight, and this was added to a reactor heated to 75°C containing % by weight of isoprobil alcohol under stirring. The mixture was added dropwise over a period of 2 hours, and the mixture was stirred and reacted for an additional 6 hours. This reaction solution was dropped into 400% by weight water,
After over-drying, a liquid copolymer having an average molecular weight of about 2.000 as shown in Table 1 was obtained.
参考例１１．１２及び比較参考例３．４参考例１におい
て、メタクリル酸メチルを５５〜９３重量％に、メタク
リル酸ステアリール４５〜７重量％に変えた外に、ラウ
リルパーオキシドの使用量と反応時間を若干変えた以外
は参考例１と同様にして、第１表に示す平均分子量約１
２５．０００の固体の熱可塑性樹脂滑剤を得た。Reference Example 11.12 and Comparative Reference Example 3.4 In Reference Example 1, in addition to changing methyl methacrylate to 55 to 93% by weight and changing stearyl methacrylate to 45 to 7% by weight, the amount of lauryl peroxide used and The average molecular weight shown in Table 1 was about 1 in the same manner as in Reference Example 1 except that the reaction time was slightly changed.
25,000 solid thermoplastic lubricants were obtained.
参考例１３〜１５
参考例１において、メタクリル酸メチルを７０〜７５重
量％に変えメタクリル酸ステアリル２３重■％の代りに
メタクリル酸ラウリル、メタクリル酸ドデシル、メタク
リル酸セチルを２５〜３０重量％を用い、更にラウリル
パーオキシドの使用量と反応時間を若干変える以外は参
考例１と同様にして、第１表に示す平均分子量約ａｏ，
ｏｏｏ〜約１８０、０００の固体の熱可塑性樹脂滑剤を
得た。Reference Examples 13 to 15 In Reference Example 1, methyl methacrylate was changed to 70 to 75% by weight, and 25 to 30% by weight of lauryl methacrylate, dodecyl methacrylate, and cetyl methacrylate were used instead of 23% by weight of stearyl methacrylate. , Further, the average molecular weight as shown in Table 1 was about ao,
ooo to about 180,000 solid thermoplastic resin lubricant was obtained.
参考例１６
参考例１いおいて、メタクリル酸メチル７７重量％の代
りにメタクリル酸エチル７５重量部を、メタクリル酸ス
テアリル２３重量部の代りにメタクリル酸ラウリル２５
重量部を用い、更にラウリルパーオキシドの使用量と反
応時間を若干変えて、第１表に示す平均分子量約１９０
． ０００の固体の熱可塑性樹脂滑剤を得た。Reference Example 16 In Reference Example 1, 75 parts by weight of ethyl methacrylate was used instead of 77 parts by weight of methyl methacrylate, and 25 parts by weight of lauryl methacrylate was used instead of 23 parts by weight of stearyl methacrylate.
By using parts by weight and slightly changing the amount of lauryl peroxide used and the reaction time, the average molecular weight shown in Table 1 was about 190.
．． 000 solid thermoplastic resin lubricant was obtained.
参考例１７
参考例１において、第１表に示すようにメタクリル酸メ
チルの代りにアクリル酸エチル８０重量％とし、メタク
リル酸ステアリルの代りにアクリル酸ステアリル２０重
量％とし、その他反応温度を若干変えた以外は参考例１
と同様な方法で平均分子量約１６０，０００の固体の熱
可塑性樹脂滑剤を得た。Reference Example 17 In Reference Example 1, as shown in Table 1, 80% by weight of ethyl acrylate was used instead of methyl methacrylate, 20% by weight of stearyl acrylate was used instead of stearyl methacrylate, and the reaction temperature was slightly changed. Other than that, reference example 1
A solid thermoplastic resin lubricant having an average molecular weight of about 160,000 was obtained in the same manner as above.
参考例１８
参考例１において、メタクリル酸メチル７７重量％及び
メタクリル酸ステアリル２３重量％の代りに、メタクリ
ル酸メチル５０重量％、メタクリル酸２７重量％及びメ
タクリル酸ステアリル２３重量％に変えた以外は参考例
１と同様な方法で平均分子量約１５０． ０００の固体
の熱可塑性樹脂滑剤を得た。Reference Example 18 Reference Example 1 except that 77% by weight of methyl methacrylate and 23% by weight of stearyl methacrylate were replaced with 50% by weight of methyl methacrylate, 27% by weight of methacrylic acid, and 23% by weight of stearyl methacrylate. Using the same method as in Example 1, the average molecular weight was approximately 150. 000 solid thermoplastic resin lubricant was obtained.
以上の参考例１〜１８で得られた熱可塑性樹脂滑剤は、
いずれも固体の透明性のよい共重合物であり、特に参考
例１〜７および１１〜１８で得られた熱可塑性樹脂滑剤
の透明性が優れていた。The thermoplastic resin lubricants obtained in Reference Examples 1 to 18 above were:
All of them were solid copolymers with good transparency, and the thermoplastic resin lubricants obtained in Reference Examples 1 to 7 and 11 to 18 had particularly excellent transparency.
一方、比較参考例１で得られたものは固体であるが該共
重合体の平均分子量が大きく、参考例１〜１８で得られ
た熱可塑性樹脂滑剤のどれよりも透明性に劣っており、
また、比較参考例２で得られたものは液状の共重合体で
あった。On the other hand, although the copolymer obtained in Comparative Reference Example 1 is a solid, the average molecular weight of the copolymer is large, and the transparency is inferior to any of the thermoplastic resin lubricants obtained in Reference Examples 1 to 18.
Furthermore, the product obtained in Comparative Reference Example 2 was a liquid copolymer.
これらの熱可塑性樹脂滑剤と液状および固体の共重合体
の、共重合における主成分の重量％、平均分子量及び性
能の対照のために成形品に適用した参考例と比較参考例
をまとめて第１表に示す。Reference examples and comparative examples of these thermoplastic resin lubricants and liquid and solid copolymers applied to molded products for comparison of the weight percent of the main component in copolymerization, average molecular weight, and performance are summarized in Part 1. Shown in the table.
なお、平均分子量は下記の測定方法から求めた。In addition, the average molecular weight was calculated|required from the following measuring method.
平均分子量
試料濃度０．４重量％のテトラヒドロフラン溶液５００
ｄを、昭和電工（株）製ショウデックスＡ型及び島津製
作所（株）製ＨＳＧ型のカラム、Ｒ１シツウデックスＳ
Ｅ−１１検出器を装備した、ウォーターズ社製６０００
Ａ型ゲルパーミニジョンクロマトグラフ装置に注入し
たのち、室温でテトラヒドロフランの流速ＩＩｄＺ分の
展開条件で分離する．試料の平均分子量はスチレン換算
の重量平均分子量として算出する。Tetrahydrofuran solution with average molecular weight sample concentration 0.4% by weight 500
d is a column of Showa Denko Co., Ltd.'s Showdex A type and Shimadzu Corporation's HSG type column, R1 Situdex S.
Waters 6000 equipped with E-11 detector
After injecting it into a type A gel perminiscence chromatography device, it is separated at room temperature under the development conditions of tetrahydrofuran at a flow rate of IIdZ. The average molecular weight of the sample is calculated as the weight average molecular weight in terms of styrene.
ｒ：ｔＳ１表
滑剤の共重合割合及び平均分子景
熱可塑性樹脂滑剤の成形品への適用
実施例１〜４及び比較例１〜４
塩化ビニル樹脂（夏日（株）製、商品名５Ｃ−１１００
、平均重合度１１００）１００重量部、ジオクチルセバ
ケート２０重量部に、参考例１で得たメタクリル酸メチ
ル（７７）とメタクリル酸ステアリル（２３）の平均分
子量約１００．０００の熱可塑性樹脂滑剤を下記第２表
に示す量で添加したのち、メチルエチルケトンとトルエ
ンの混合溶媒（メチルエチルケトン対トルエンの重量比
、８対２）を４００重量部加え、オートクレプ中撹拌し
つつ１００℃、３０分で完全溶解した。この溶液を冷却
及び脱泡して６０℃でステンレス製の流延面に厚さ６０
ミクロンのフィルムが生成するように流延して平均９０
℃の熱風で２０分間乾燥後、流延面よりフィルムを剥離
しフィルム原反を得た。r: tS1 Copolymerization ratio and average molecular profile of lubricant Application of thermoplastic resin lubricant to molded products Examples 1 to 4 and Comparative Examples 1 to 4 Vinyl chloride resin (manufactured by Natsuga Co., Ltd., trade name 5C-1100)
, an average polymerization degree of 1100), and 20 parts by weight of dioctyl sebacate, a thermoplastic resin lubricant having an average molecular weight of about 100.000 consisting of methyl methacrylate (77) and stearyl methacrylate (23) obtained in Reference Example 1 was added. After adding the amounts shown in Table 2 below, 400 parts by weight of a mixed solvent of methyl ethyl ketone and toluene (weight ratio of methyl ethyl ketone to toluene, 8:2) was added and completely dissolved at 100°C for 30 minutes while stirring in an autoclave. . This solution was cooled and degassed, and cast onto a stainless steel casting surface at 60°C to a thickness of 60°C.
Cast to produce a film with an average diameter of 90 microns
After drying with hot air at .degree. C. for 20 minutes, the film was peeled off from the casting surface to obtain an original film.
次に、このフィルム原反を１０５℃に維持した延伸機中
に入れフィルムが該温度と平衡に達した後、３０秒で縦
横各々２倍に２軸延伸して厚み１５ミクロンの延伸フィ
ルムを得た。。Next, this original film was placed in a stretching machine maintained at 105°C, and after the film reached equilibrium with the temperature, it was biaxially stretched to twice the length and width in 30 seconds to obtain a stretched film with a thickness of 15 microns. Ta. .
かくした得られた延伸フィルムは、優れた透明性と外部
滑性を示し皺の全くないきれいな状態でロールフィルム
として巻取ることが出来た。また、これらのロールフィ
ルムを長期間貯蔵したが、ブロッキングや透明性が減退
することがなく長期間借れた透明性と外部滑性を持続す
ると共に、印刷加工、製袋加工、熱収縮包装に使用の際
に加工機械等との摩擦がなく、印刷インクずれ、印刷イ
ンクの接着不良、シール線の蛇行、包装中のフィルム破
れ、不完全熱収縮等の包装不良品の発生がなく美しいも
のに加工することが出来た。The thus obtained stretched film exhibited excellent transparency and external slipperiness, and could be wound up as a roll film in a clean state with no wrinkles. In addition, even when these roll films are stored for a long period of time, they maintain their transparency and external smoothness for a long time without blocking or deterioration of transparency, and are suitable for printing processing, bag making processing, and heat shrink packaging. There is no friction with processing machines, etc. during use, and there is no occurrence of packaging defects such as misalignment of printing ink, poor adhesion of printing ink, meandering of seal lines, film tearing during packaging, or incomplete heat shrinkage, resulting in beautiful products. I was able to process it.
また、実施例１〜４で、第２表に示すように、熱可塑性
樹脂滑剤の添加量を変えたこと、及び熱可塑性樹脂滑剤
の代りにステアリン酸アミド０．６重量部、ステアリン
酸カルシウム０．６重量部に変えたこと以外は全く同じ
方法で、比較例１〜２、比較例３〜４の延伸フィルムを
得た。以上の実施例１〜４、比較例１〜４に使用した滑
剤の種類、添加量と共に、これらの延伸フィルムの曇り
度、静止摩擦、ブロッキングを試験した結果も合せて第
２表に示す。Further, in Examples 1 to 4, as shown in Table 2, the amount of the thermoplastic resin lubricant added was changed, and instead of the thermoplastic resin lubricant, 0.6 parts by weight of stearamide and 0.6 parts by weight of calcium stearate were added. Stretched films of Comparative Examples 1 and 2 and Comparative Examples 3 and 4 were obtained in exactly the same manner except that the amount was changed to 6 parts by weight. Table 2 shows the types and amounts of lubricants used in Examples 1 to 4 and Comparative Examples 1 to 4, as well as the results of testing the haze, static friction, and blocking of these stretched films.
なお、第２表及び後記の第３〜６表に記載した各試験方
法は次のようにして行った。In addition, each test method described in Table 2 and Tables 3 to 6 below was performed as follows.
１、曇り度
フィルム調製後、２５℃、相対湿度５５％の恒温恒温室
に１５日間貯蔵したのち、３ｃｍＸ２ｃｍの試験片を採
取し、積分球式濁度計でＪＩＳ、に−６７１４に準じて
曇り度（％）を測定する。1. After preparing the cloudiness film, it was stored in a thermostatic chamber at 25°C and 55% relative humidity for 15 days, and then a 3cm x 2cm test piece was taken and the cloudiness was determined using an integrating sphere turbidimeter according to JIS-6714. Measure the degree (%).
２、静止摩擦
フィルム調製後、２５°Ｃ１相対湿度５５％の恒温恒温
室に４０時間貯蔵したのち、２５ｃｍＸ３０ｃｍの試験
片を採取し、摩擦試験機でＡＳＴＭ、Ｄ１８９４−７５
に準じて静止摩擦係数を測定する。2. After preparing the static friction film, it was stored in a thermostatic chamber at 25°C and 55% relative humidity for 40 hours, and then a 25cm x 30cm test piece was taken and tested using a friction tester according to ASTM, D1894-75.
Measure the coefficient of static friction according to .
３、 ブロッキング
フィルム調製後、２５°Ｃ１相対湿度５５％の恒温恒温
室に３０ＣＩＩＸ４０Ｃ１１の試験片を２枚重ね合せ、
ｌｃｊ当り２５ｇの荷重をかけ４０時間貯蔵したのち、
その２枚重ね合せた試験片を２５ｃ＋＋＋ｘ３０Ｃ１に
切りブロッキング試験１でＡＳＴＭ、Ｄ１８９３−６７
に準じてブロッキングを測定する。3. After preparing the blocking film, stack two 30CIIX40C11 test pieces in a constant temperature room at 25°C and 55% relative humidity.
After storing for 40 hours with a load of 25g per lcj,
The two stacked test pieces were cut into 25c+++x30C1 and tested according to ASTM D1893-67 in blocking test 1.
Measure blocking according to .
第２表
熱可塑性樹脂滑剤の添加量を変えた托伸フィルム及び従
来の滑剤を添加した延伸フィルム前記第２表の試験結果
より明らかなように実施例１〜４の延伸フィルムは透明
性、フィルム滑性、耐ブロッキング性に著しく優れ、該
フィルムを使用して印刷、製袋、自動包装した際には、
従来の滑剤では得られない優れた作業性等も得られた。Table 2 Stretched films with different amounts of thermoplastic resin lubricant added and Stretched films with conventional lubricant added As is clear from the test results in Table 2 above, the stretched films of Examples 1 to 4 had a high transparency, It has excellent slipperiness and blocking resistance, and when this film is used for printing, bag making, and automatic packaging,
Excellent workability, etc., which cannot be obtained with conventional lubricants, was also obtained.
一方、比較例１では透明性はよいが、粘着性、ブロッキ
ング性が大きく、ロールフィルムに巻取る時に多数の皺
が発生し、長期間貯蔵したところ特に皺のある部分が著
しくブロッキングが増加した。On the other hand, in Comparative Example 1, the transparency was good, but the adhesiveness and blocking property were large, many wrinkles were generated when the film was wound into a roll film, and when stored for a long period of time, the blocking increased particularly in the wrinkled areas.
また、粘着が強く印刷、製袋、自動包装等の加工に適さ
なかつた０例え、無理に製袋しチューブに加工してもフ
ィルム相互が密着し、袋中に包装物を入れることが出来
ず（開口性不良）全く使用出来なかった。In addition, the adhesive is strong and is not suitable for processing such as printing, bag making, and automatic packaging.For example, even if you forcefully make bags and process them into tubes, the films will stick to each other and you will not be able to put the packaged items in the bag. (Poor opening property) Could not be used at all.
また、比較例２ではフィルム滑性、耐ブロッキング性に
は満足すべき結果が得られたが、不透明性が強く包装内
容物を一層美しく鮮明に見せ購買欲を高める包装フィル
ムとして不十分であった。In Comparative Example 2, satisfactory results were obtained in terms of film slipperiness and anti-blocking properties, but the film was highly opaque and was insufficient as a packaging film that would make the packaged contents more beautiful and clear and increase purchase desire. .
比較３．４ではフィルム調製初期ではフィルム滑性がな
く粘着が強いため、ロールフィルムに多数巻取ることが
出来なかった。また比較例４のフィルムは、溶剤に不溶
性の滑剤を添加したため、フィルム中に微細な不透明滑
剤斑点が発生した。更に、比較例３，４のフィルムを長
期間貯蔵したところ、経時変化によってフィルム表面に
著しく吹出した滑剤で黴が発生したような大きな斑点が
生じ透明性と外観が全く阻害され、この欠点だけでも包
装フィルムとして不適であった。また、印刷した後、イ
ンクの接着性試験をしたところ、殆んど完全に剥離し不
適であり、シール加工後、シール強度試験をしたところ
、シール強度に強弱が生じ、包装品の運搬中に弱い部分
から破袋が生じた。In Comparison 3.4, the film had no slipperiness and had strong adhesion at the initial stage of film preparation, so it was not possible to wind it into a roll film in large numbers. Further, in the film of Comparative Example 4, fine opaque lubricant spots were generated in the film because an insoluble lubricant was added to the solvent. Furthermore, when the films of Comparative Examples 3 and 4 were stored for a long period of time, large mold-like spots appeared on the surface of the film due to significant blown-out lubricant, completely impairing transparency and appearance. It was unsuitable as a packaging film. In addition, when we conducted an ink adhesion test after printing, we found that the ink had almost completely peeled off and was unsuitable.After seal processing, we conducted a seal strength test, and found that the seal strength varied. The bag broke from a weak point.
実施例５〜１２及び比較例５．６
実施例１〜４において、参考例１で得たメタクリル酸メ
チル（７７）とメタクリル酸ステアリル（２３）の平均
分子量約１００．０００の熱可塑性樹脂滑剤の代りに、
下記第３表に示す参考例２〜４及び６〜１０で得た平均
分子量の異なる熱可塑性樹脂滑剤を２．２重量部使用す
る以外は全く同じにして、厚み１５ミクロンの塩化ビニ
ル樹脂延伸フィルムを得た。Examples 5 to 12 and Comparative Example 5.6 In Examples 1 to 4, methyl methacrylate (77) and stearyl methacrylate (23) obtained in Reference Example 1 were used as thermoplastic resin lubricants having an average molecular weight of about 100.000. Instead,
A polyvinyl chloride resin stretched film with a thickness of 15 microns was prepared using the same method except that 2.2 parts by weight of the thermoplastic resin lubricants having different average molecular weights obtained in Reference Examples 2 to 4 and 6 to 10 shown in Table 3 below were used. I got it.
かくして得られた延伸フィルムは、優れた透明性と外部
滑性を該フィルムの調製の初期から長期間貯蔵した後も
維持すると共に、印刷加工、製袋加工、熱収縮包装等の
使用に際にはその優れた性能を発揮した。The stretched film thus obtained maintains excellent transparency and external slipperiness from the initial stage of film preparation even after long-term storage, and is also suitable for use in printing processing, bag making processing, heat shrink packaging, etc. demonstrated its excellent performance.
また、上記実施例５〜１２で、参考例２〜４及び６〜ｌ
Ｏで得た平均分子量の異る熱可塑性樹脂滑剤の代りに、
比較参考例２で調製した平均分子量約２．０００の液状
共重合体、及び比較参考例１で調製した平均分子量約１
．２００，０００の固体共重合体を使用する以外は全く
同じ方法で、比較例５及び比較例６の延伸フィルムを得
た。In addition, in Examples 5 to 12 above, Reference Examples 2 to 4 and 6 to 1
Instead of thermoplastic resin lubricants with different average molecular weights obtained with O,
A liquid copolymer with an average molecular weight of about 2.000 prepared in Comparative Reference Example 2 and an average molecular weight of about 1 prepared in Comparative Reference Example 1.
．． Stretched films of Comparative Example 5 and Comparative Example 6 were obtained in exactly the same manner except that 200,000 solid copolymer was used.
以上の実施例５〜１２、比較例５，６に使用した滑剤の
種類、平均分子量と共に、これらの延伸フィルムの試験
結果も合わせて第３表に示す。Table 3 shows the types and average molecular weights of the lubricants used in Examples 5 to 12 and Comparative Examples 5 and 6, as well as the test results of these stretched films.
％以下、余白）
ｔｔＳ３表
種′々の平均分子量の滑剤２．Ｚ ｆｉｔ ｆｔ部添加
した延伸フィルム
上記第３表の試験結果より明らかなように実施例５〜１
２の延伸フィルムは透明性、フィルム滑性、耐ブロッキ
ング性に優れていたが、実施例６〜９では曇り度が１．
２〜１．５であり、静止摩擦は０．２〜０．６であり、
ブロッキングは０．９〜１．３と特に優れた透明性と外
部滑剤を共有する延伸フィルムを与えた。一方、比較例
５では、平均分子量が小さい液状共重合体のため延伸フ
ィルムの表面は、該液状共重合体の浸出でかえってベタ
ツキが多くなりフィルム調製の初期から長期貯蔵後も粘
着が強く、フィルムとして全く使用し得なかった。% or less, margin) ttS3 table types' average molecular weight lubricants 2. Stretched film containing ft part of Z fit As is clear from the test results in Table 3 above, Examples 5 to 1
The stretched film of No. 2 was excellent in transparency, film slipperiness, and blocking resistance, but in Examples 6 to 9, the degree of haze was 1.
2 to 1.5, static friction is 0.2 to 0.6,
Blocking gave stretched films that shared particularly good transparency and external lubricant of 0.9 to 1.3. On the other hand, in Comparative Example 5, since the liquid copolymer has a small average molecular weight, the surface of the stretched film becomes more sticky due to leaching of the liquid copolymer, and the film remains sticky from the initial stage of film preparation to after long-term storage. It could not be used at all.
また比較例６では、フィルム滑性に優れていたが平均分
子量が高過ぎるため半硬質塩化ビニル樹脂との相溶性が
低下し、ポリエチレン状の不透明な外観を与え包装用の
用途には適さなかった。また、経時変化によってシール
強度の低下及び不透明性の増加が若干認められた。In Comparative Example 6, the film had excellent slipperiness, but the average molecular weight was too high, so its compatibility with semi-rigid vinyl chloride resin decreased, giving it an opaque appearance similar to polyethylene, making it unsuitable for packaging applications. . In addition, a decrease in seal strength and a slight increase in opacity were observed due to changes over time.
実施例１３．１４及び比較例７．８
塩化ビニル樹脂（夏日■製、商品名５Ｇ１３００゜平均
重合度１３００） １００重量部、ジオクチルアゼレ
ート１５重量部、ジオクチール錫マレート０．０５重量
部に、参考例１１及び１２で得た下記第４表に示す平均
分子量約１２５．０００の熱可塑性樹脂滑剤を１．８重
量部添加したのち、メチルエチルケトン４２０重量部加
えオートクレーブ中撹拌しつつ１０５℃、２０分で完全
溶解した。この溶液を冷却及び脱泡して６０−℃でステ
ンレス製の流延面に厚さ６０ミクロンのフィルムが生成
するように流延したのち、以後実施例１〜４と全く同じ
方法で乾燥、剥離、延伸して厚さ１５ミクロンの延伸フ
ィルムを得た。か（して得られた延伸フィルムは、実施
例１−１２の延伸フィルムと同様にフィルム調製初期か
ら優れた透明性と外部滑性を維持した。Example 13.14 and Comparative Example 7.8 100 parts by weight of vinyl chloride resin (manufactured by Natsuhi ■, trade name 5G1300°, average degree of polymerization 1300), 15 parts by weight of dioctyl azelate, 0.05 parts by weight of dioctyltin malate, After adding 1.8 parts by weight of the thermoplastic resin lubricant obtained in Reference Examples 11 and 12 and having an average molecular weight of about 125.000 shown in Table 4 below, 420 parts by weight of methyl ethyl ketone was added and the mixture was heated at 105°C for 20 minutes while stirring in an autoclave. completely dissolved. This solution was cooled and degassed and cast on a stainless steel casting surface at 60-℃ to form a 60 micron thick film, then dried and peeled off in the same manner as in Examples 1 to 4. , to obtain a stretched film with a thickness of 15 microns. The stretched film obtained in this manner maintained excellent transparency and external slipperiness from the initial stage of film preparation, similar to the stretched film of Examples 1-12.
また、上記実施例１３．１４で、参考例１１及び１２で
得た熱可塑性樹脂滑剤の代りに、比較参考例７及び８で
得た平均分子量約１２５，０００の固体共重合体を使用
する以外は全く同じ方法で比較例７及び比較例８の延伸
フィルムを得た。In addition, in Examples 13 and 14 above, the solid copolymers having an average molecular weight of about 125,000 obtained in Comparative Reference Examples 7 and 8 were used instead of the thermoplastic resin lubricants obtained in Reference Examples 11 and 12. Stretched films of Comparative Example 7 and Comparative Example 8 were obtained in exactly the same manner.
以上の実施例１３．１４及び比較例７．８に使用した滑
剤の種類、共重合割合と共に、これらの延伸フィルムの
試験結果も含めて第４表に示す。Table 4 shows the types and copolymerization ratios of the lubricants used in Examples 13 and 14 and Comparative Examples 7 and 8, as well as the test results of these stretched films.
第４表
種々、の共重合割合の平均分子１１１２．５刀の滑剤１
．８ ！ｉ量郡部添加た延伸フイルム上記第４表の試験
結果より明らかなように実施例１３及び１４の延伸フィ
ルムは透明性、フィルム滑剤、耐ブロッキング性、すべ
てに優れ包装フィルムとして好適であったが、比較例７
では実施例１３．１４の熱可塑性樹脂滑剤の平均分子量
と同等の平均分子量を有する固体の共重合体を添加した
にもかかわらず、外部滑性作用を発揮するステアリル基
の成分が少く、外観的には透明性が実施例２４の延伸フ
ィルムと略同等で優れていた反面、フィルム滑剤、耐ブ
ロッキング性が不十分でやや粘着性を帯び、該フィルム
の加工に際しては印刷、製袋、包装等における作業性が
不十分であった。また、比較例８では、ステアリル基の
成分が多いためフィルム滑性、耐ブロッキング性に優れ
、該フィルムの加工に際しては満足すべき性能が発揮さ
れたが、前記比較例６の延伸フィルムと同様に、透明性
に劣りポリエチレン状の不透明な外観を与える等、包装
には適しなかった。Table 4 Average molecular weight of various copolymerization ratios: 1112.5 Sword lubricant 1
．． 8! Stretched film containing a certain amount of I As is clear from the test results in Table 4 above, the stretched films of Examples 13 and 14 were excellent in transparency, film lubricant, and blocking resistance, and were suitable as packaging films. Comparative example 7
In this case, although a solid copolymer having an average molecular weight equivalent to that of the thermoplastic resin lubricant of Example 13.14 was added, the stearyl group component that exerts an external lubricating effect was small, and the appearance was poor. Although the film had excellent transparency, almost the same as that of the stretched film of Example 24, the film had insufficient lubricant and anti-blocking properties, making it slightly sticky. Workability was insufficient. In addition, in Comparative Example 8, the film had excellent slipperiness and anti-blocking properties due to the large amount of stearyl group components, and satisfactory performance was exhibited during processing of the film, but as with the stretched film of Comparative Example 6, However, it was not suitable for packaging because it had poor transparency and an opaque appearance similar to polyethylene.
実施例１５
実施例１３及び１４において、参考例１１及び１２で得
た熱可塑性樹脂の代りに、参考例１８で得た平均分子量
約１５０，０００の熱可塑性樹脂滑剤を使用する以外は
全く同じ方法で厚さ１５ミクロンの塩化ビニル樹脂延伸
フィルムを得た。Example 15 In Examples 13 and 14, the same method was used except that the thermoplastic resin lubricant having an average molecular weight of about 150,000 obtained in Reference Example 18 was used instead of the thermoplastic resin obtained in Reference Examples 11 and 12. A vinyl chloride resin stretched film having a thickness of 15 microns was obtained.
かくして得られた延伸フィルムは、曇り度１．８、静止
摩擦１．０、ブロッキング１．２で、実施例１３及び１
４延伸フイルムと同様にフィルム調製初期から優れた透
明性と外部滑性を示した。The stretched film thus obtained had a haze of 1.8, a static friction of 1.0, and a blocking of 1.2, as in Examples 13 and 1.
Similar to the 4-stretched film, it exhibited excellent transparency and external slipperiness from the initial stage of film preparation.
実施例１６〜２０
実施例１３及び１４において、熱可塑性樹脂滑剤の代り
に、下記第５表に示す参考例１３〜１８で得た熱可塑性
樹脂滑剤を各々２重量部使用する以外は同様の方法で厚
さ１５ミクロンの塩化ビニル樹脂延伸フィルムを得た。Examples 16 to 20 In Examples 13 and 14, the same method was used except that 2 parts by weight of each of the thermoplastic resin lubricants obtained in Reference Examples 13 to 18 shown in Table 5 below was used instead of the thermoplastic resin lubricant. A vinyl chloride resin stretched film having a thickness of 15 microns was obtained.
上記実施例１６〜２０に使用した熱可塑性樹脂滑剤の共
重合割合、平均分子量と共に、これらの延伸フィルムの
試験結果も合わせて第５表に示す。Table 5 shows the copolymerization ratio and average molecular weight of the thermoplastic resin lubricants used in Examples 16 to 20, as well as the test results of these stretched films.
（以下、余白）
第５表
上記第５表の試験結果より明らかなように実施例１６〜
２０の延伸フィルムは、２重量部添加した熱可塑性樹脂
滑剤のいづれもが、該滑剤の共重合成分でａ成分が７０
〜８０重量％、ｂ成分が３０〜２０重量％で且つ平均分
子量が８０．０００〜１９０、０００で、熱可塑性樹脂
に対し特に優れた透明性と外部滑性を与える範囲内にあ
るため、フィルム調製初期から長期間の貯蔵後も、透明
性、フィルム滑性、耐ブロッキング性等に経時変化もな
く、印刷、製袋、包装等の加工等の際には優れた性能を
発揮した。(Hereinafter, blank space) Table 5 As is clear from the test results in Table 5 above, Examples 16-
In the stretched film of No. 20, both of the thermoplastic resin lubricants added in 2 parts by weight were copolymerized components of the lubricants, and component a was 70%.
-80% by weight, component b is 30-20% by weight, and the average molecular weight is 80.000-190,000, which is within the range that provides particularly excellent transparency and external slipperiness for thermoplastic resins, so the film Even after long-term storage from the initial stage of preparation, there was no change in transparency, film slipperiness, blocking resistance, etc. over time, and it exhibited excellent performance during processing such as printing, bag making, and packaging.
実施例２１及び２２
メタクリル酸メチル７０重量％とアクリル酸ブチル３０
重量％共重合のアクリル樹脂（平均分子量約８０．００
０） ８０重量部と、セルローズアセテートブチレート
樹脂（イーストマンコダック社製、商品名テナイトブチ
レート、平均分子量約２０，０００）の２０重量部、合
計１００重量部の熱可塑性樹脂に対して、参考例５で得
た平均分子量約ｓｏ、 ｏｏｏＯ熱可塑性樹脂滑剤を下
記第６表に示す量で添加したのち、テトラヒドロフラン
５７０重量部を加え、オートクレーブ中撹拌しっつｉｏ
ｏ’ｔ’、２０分で完全溶解した。この溶液を冷却及び
脱泡して６０℃でステンレス製の流延面に厚さ５０ミク
ロンのフィルムが生成するように流延して平均９５℃で
２５分間乾燥後、流延面よりフィルムを剥離しアクリル
樹脂系フィルム原反を得た。かくして得られたアクリル
樹脂系フィルム原反の試験結果も含め第６表に示す。Examples 21 and 22 70% by weight of methyl methacrylate and 30% by weight of butyl acrylate
Weight% copolymerized acrylic resin (average molecular weight approximately 80.00
0) 80 parts by weight and 20 parts by weight of cellulose acetate butyrate resin (manufactured by Eastman Kodak Company, trade name Tenite Butyrate, average molecular weight approximately 20,000), for a total of 100 parts by weight of thermoplastic resin, as a reference. After adding the thermoplastic resin lubricant having an average molecular weight of about so, ooo obtained in Example 5 in the amount shown in Table 6 below, 570 parts by weight of tetrahydrofuran was added, and the mixture was stirred in an autoclave.
Completely dissolved in 20 minutes. This solution was cooled and degassed, then cast on a stainless steel casting surface at 60°C to form a film with a thickness of 50 microns. After drying at an average temperature of 95°C for 25 minutes, the film was peeled off from the casting surface. An original acrylic resin film was obtained. Table 6 also includes the test results for the acrylic resin film material thus obtained.
（以下、余白）
第６表
平均分子量約８万の熱可塑性８４１１１滑剤添加アクリ
ル［＝系フィルム原反
上記第６表の試験結果より明らかなように、実施例２１
．２２のフィルム原反は透明性と外部滑性に優れ、従来
の高級脂肪酸や高級脂肪酸のアミド誘導体、その他一般
に使用されている滑剤に見られる吹出しによる透明性、
光沢性の減衰がなく、長期間の貯蔵後も調製直後の著し
く優れた透明性、光沢性を維持する一方、ロールフィル
ムとして長期間貯蔵したが、フィルム滑性に優れている
ので、該フィルムの印刷に際して巻戻しが極めて円滑で
あり、装置等の摩擦が極めて小さいのでインクずれが全
くなく、且つインクの接着性が極めて良好で、従来の滑
剤では不能であった高級美術模様の印刷をすることが出
来た。(Hereinafter, blank space) Table 6 Thermoplastic 84111 lubricant-added acrylic film with an average molecular weight of approximately 80,000 As is clear from the test results in Table 6 above, Example 21
．． The raw film No. 22 has excellent transparency and external lubricity, and has the same transparency and external lubricity as seen in conventional higher fatty acids, amide derivatives of higher fatty acids, and other commonly used lubricants.
There is no decline in gloss, and even after long-term storage, the film maintains its outstanding transparency and glossiness immediately after preparation, and even after long-term storage as a roll film, the film has excellent slipperiness. During printing, rewinding is extremely smooth, the friction of equipment etc. is extremely small, so there is no ink slippage at all, and the ink has extremely good adhesion, making it possible to print high-quality artistic patterns that were impossible with conventional lubricants. was completed.
実施例２３
塩化ビニル樹脂（夏日■製、商品名ＳＧ８００、平均重
合度８００）１００重量部、ジオクチルフタレート１２
重量部、エポキシ化大豆油３重量部、オクチル錫系安定
剤３重量部に、参考例５で得た平均分子量約８０．００
０の熱可塑性樹脂滑剤４重量部を添加し、リボンブレン
ダーで混合しコンパウンドを調製した。このコンパウン
ドを４０ｍ押出機及び３００Ｍ巾のＴダイスを用い、シ
リンダ温度１８０℃、ダイス温度１８５℃、押出量１０
ｋｇ／Ｈの条件で厚さ６０ミクロンのフィルム原反とな
し、次いでこのフィルム原反を１００℃に維持した延伸
機中に入れ、フィルムが該温度と平衡に達した後、３０
秒間で縦横各々２倍に２軸延伸して厚み１５ミクロンの
延伸フィルムを得た。かくして得られた延伸フィルムは
、透明性、外部滑性に優れ、曇り度は２．３、静止摩擦
は０．３、ブロッキングは０．８で、この性能はフィル
ム調製直後も長期間貯蔵後も経時変化することがなく、
優れた透明性と外部滑性を維持した。Example 23 100 parts by weight of vinyl chloride resin (Natsuhi ■, trade name SG800, average degree of polymerization 800), dioctyl phthalate 12
parts by weight, 3 parts by weight of epoxidized soybean oil, 3 parts by weight of octyltin stabilizer, average molecular weight of about 80.00 obtained in Reference Example 5.
0 thermoplastic resin lubricant was added thereto and mixed using a ribbon blender to prepare a compound. This compound was processed using a 40 m extruder and a 300 m wide T-die at a cylinder temperature of 180°C, a die temperature of 185°C, and an extrusion amount of 10.
kg/h to form a film with a thickness of 60 microns, then put this film into a stretching machine maintained at 100°C, and after the film reached equilibrium with the temperature,
The film was biaxially stretched twice in length and width in seconds to obtain a stretched film with a thickness of 15 microns. The stretched film thus obtained has excellent transparency and external slipperiness, with a haze of 2.3, a static friction of 0.3, and a blocking of 0.8. Does not change over time,
Excellent transparency and external lubricity were maintained.
以上の実施例からも理解されるように本発明の熱可塑性
樹脂滑剤及び易滑性熱可塑性樹脂組成物を用いると、従
来の方法に基く熱可塑性樹脂成形品に比較して著しく優
れた透明性と外部滑性を共有するものを極めて容易に製
造し得ることが解る。As can be understood from the above examples, when the thermoplastic resin lubricant and slippery thermoplastic resin composition of the present invention are used, transparency is significantly superior to that of thermoplastic resin molded products based on conventional methods. It can be seen that it is extremely easy to manufacture a product that shares the same external lubricity as .
この特徴は、特に溶液流延法で製造されるビニル樹脂、
アクリル樹脂において顕著な効果を発揮するものである
、そして従来より、成形直後から長期間の経時後も優れ
た透明性と外部滑性を付与する単一の滑性がなく、滑剤
の複雑な種類の組合せ、量的調整等の方法等で不十分な
がらも成形品が製造されて来たことを考えると、本発明
の熱可塑性樹脂滑剤及び易滑性熱可塑性樹脂組成物の意
義は極めて大きい。This feature is particularly important for vinyl resins manufactured by the solution casting method.
Acrylic resins exhibit remarkable effects, and conventionally, there is no single type of lubricant that provides excellent transparency and external lubricity immediately after molding and even after a long period of time, and complex types of lubricants have been used. Considering that molded products have been produced by methods such as combinations and quantitative adjustment, etc., although insufficient, the thermoplastic resin lubricant and easily slippery thermoplastic resin composition of the present invention are extremely significant.
６９．補正の内容
手 続 補 正 書
昭和６３年５月 ６日
特許庁長官 小 川 邦 夫 殿
昭和６３年４月９日提出の特許廟
２、発明の名称
易滑性熱可塑性樹脂組成物
３、補正をする者
事件との関係 特許出願人
４、補正命令の日付
な し
く１）明細書の第１４頁第９行〜第１Ｏ行に、「ポリブ
チレンテレフタレート樹脂、ポリブチレンテレフタレー
ト樹脂、」
とあるを、
「ポリエチレンテレフタレート樹脂、ポリブチレンテレ
フタレート樹脂、」
と訂正する。69. Contents of the amendment Procedures Amendment Written on May 6, 1988 Kunio Ogawa, Commissioner of the Patent Office To: Patent Temple 2 submitted on April 9, 1988, Title of invention: Easy-sliding thermoplastic resin composition 3, Amendment Patent applicant 4, without date of amendment order 1) On page 14, lines 9 to 10 of the specification, there is a statement that says "polybutylene terephthalate resin, polybutylene terephthalate resin." , corrected to ``Polyethylene terephthalate resin, polybutylene terephthalate resin.''
（２）同第２２頁下から第２行に、 「オキサイド」とあるを、 「オキシド」と訂正する。(2) In the second line from the bottom of page 22, It says "Oxide", "Oxide" I corrected.
（３）同第２８頁第１１行に、 「オートクレブ」とあるを、 ［オートクレーブｊと訂正する。(3) On page 28, line 11, It says "autoclave", [Corrected as autoclave j.
（４）同第４１頁第５表の実施例２０の滑剤の欄に、［
アクリル酸エチル （７５）メタクリル酸
ステアリル （２５）」とあるを、
「アクリル酸エチル （８０）アクリル酸
ステアリル （２０）Ｊと訂正する。(4) In the lubricant column of Example 20 in Table 5 on page 41, [
"Ethyl acrylate (75) Stearyl methacrylate (25)" should be corrected to "Ethyl acrylate (80) Stearyl acrylate (20) J."
以上that's all
Claims (1)
のａ成分６０〜９０重量％、ｂ成分４０〜１０重量％の
割合で主単量体単位として含有し、平均分子量が５，０
００を越え１，０００，０００以下の共重合体０．１〜
５重量部、 ａ成分、アクリル酸、メタクリル酸、炭素原子数が１〜
２個のアルキル基をもつアクリル酸エステル、炭素原子
数が１〜２個のアルキル基をもつメタクリル酸エステル
、の群より選ばれた一または二以上の単量体。 ｂ成分、炭素原子数が１１〜２０個のアルキル基をもつ
アクリル酸エステル、炭素原子数が１１〜２０個のアル
キル基をもつα置換アクリル酸エステル、の群より選ば
れた一または二以上の単量体。 を含有することを特徴とする易滑性熱可塑性樹脂組成物
。(1) B. Contains the following component a as a main monomer unit at a ratio of 60 to 90% by weight and component b 40 to 10% by weight based on 100 parts by weight of the thermoplastic resin, and has an average molecular weight of 5, 0
Copolymer of more than 00 and less than 1,000,000 from 0.1 to
5 parts by weight, component a, acrylic acid, methacrylic acid, number of carbon atoms is 1 to
One or more monomers selected from the group of acrylic esters having two alkyl groups and methacrylic esters having an alkyl group having 1 to 2 carbon atoms. component b, one or more selected from the group of acrylic esters having an alkyl group having 11 to 20 carbon atoms, and α-substituted acrylic esters having an alkyl group having 11 to 20 carbon atoms; Monomer. An easily slippery thermoplastic resin composition comprising:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8628188A JPS63284264A (en) | 1988-04-09 | 1988-04-09 | Easily lubricative thermoplastic resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8628188A JPS63284264A (en) | 1988-04-09 | 1988-04-09 | Easily lubricative thermoplastic resin composition |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7220979A Division JPS55164209A (en) | 1979-06-11 | 1979-06-11 | Thermoplastic resin lubricant and lubricating thermoplastic resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63284264A true JPS63284264A (en) | 1988-11-21 |
| JPH0262589B2 JPH0262589B2 (en) | 1990-12-26 |
Family
ID=13882445
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8628188A Granted JPS63284264A (en) | 1988-04-09 | 1988-04-09 | Easily lubricative thermoplastic resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63284264A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0393851A (en) * | 1989-08-30 | 1991-04-18 | Bayer Ag | Polycarbonate molding material and its manufacture and use |
| JP2005199576A (en) * | 2004-01-16 | 2005-07-28 | Toppan Printing Co Ltd | Fitting component made of plastic material |
| WO2010116823A1 (en) * | 2009-04-09 | 2010-10-14 | コニカミノルタオプト株式会社 | Optical film, method for producing optical film, liquid crystal panel and image display device |
-
1988
- 1988-04-09 JP JP8628188A patent/JPS63284264A/en active Granted
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0393851A (en) * | 1989-08-30 | 1991-04-18 | Bayer Ag | Polycarbonate molding material and its manufacture and use |
| JP2005199576A (en) * | 2004-01-16 | 2005-07-28 | Toppan Printing Co Ltd | Fitting component made of plastic material |
| JP4635441B2 (en) * | 2004-01-16 | 2011-02-23 | 凸版印刷株式会社 | Mating parts for plastic contents extraction |
| WO2010116823A1 (en) * | 2009-04-09 | 2010-10-14 | コニカミノルタオプト株式会社 | Optical film, method for producing optical film, liquid crystal panel and image display device |
| JPWO2010116823A1 (en) * | 2009-04-09 | 2012-10-18 | コニカミノルタアドバンストレイヤー株式会社 | Optical film, method of manufacturing optical film, liquid crystal panel, and image display device |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0262589B2 (en) | 1990-12-26 |
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