CN116490553A - Release agent for plastics - Google Patents
Release agent for plastics Download PDFInfo
- Publication number
- CN116490553A CN116490553A CN202180070886.5A CN202180070886A CN116490553A CN 116490553 A CN116490553 A CN 116490553A CN 202180070886 A CN202180070886 A CN 202180070886A CN 116490553 A CN116490553 A CN 116490553A
- Authority
- CN
- China
- Prior art keywords
- release agent
- mass
- plastics
- component
- alkyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920003023 plastic Polymers 0.000 title claims abstract description 133
- 239000004033 plastic Substances 0.000 title claims abstract description 133
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 66
- -1 fatty acid ester Chemical class 0.000 claims abstract description 145
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 74
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 71
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000000839 emulsion Substances 0.000 claims abstract description 54
- 239000002245 particle Substances 0.000 claims abstract description 37
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 36
- 239000000194 fatty acid Substances 0.000 claims abstract description 36
- 229930195729 fatty acid Natural products 0.000 claims abstract description 36
- 229920001214 Polysorbate 60 Polymers 0.000 claims abstract description 32
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 41
- 125000004432 carbon atom Chemical group C* 0.000 claims description 37
- 235000013305 food Nutrition 0.000 claims description 34
- 125000000217 alkyl group Chemical group 0.000 claims description 30
- 150000005215 alkyl ethers Chemical class 0.000 claims description 23
- 238000004806 packaging method and process Methods 0.000 claims description 22
- 239000000126 substance Substances 0.000 claims description 22
- 150000003839 salts Chemical class 0.000 claims description 14
- XMSXQFUHVRWGNA-UHFFFAOYSA-N Decamethylcyclopentasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 XMSXQFUHVRWGNA-UHFFFAOYSA-N 0.000 claims description 13
- IUMSDRXLFWAGNT-UHFFFAOYSA-N Dodecamethylcyclohexasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 IUMSDRXLFWAGNT-UHFFFAOYSA-N 0.000 claims description 13
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 claims description 13
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 150000008052 alkyl sulfonates Chemical class 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 239000012895 dilution Substances 0.000 abstract description 32
- 238000010790 dilution Methods 0.000 abstract description 32
- 238000000926 separation method Methods 0.000 abstract description 23
- 239000000203 mixture Substances 0.000 description 90
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 51
- 238000003756 stirring Methods 0.000 description 50
- 230000000052 comparative effect Effects 0.000 description 28
- 238000004945 emulsification Methods 0.000 description 22
- 229920000642 polymer Polymers 0.000 description 19
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 18
- 235000010234 sodium benzoate Nutrition 0.000 description 18
- 239000004299 sodium benzoate Substances 0.000 description 18
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 16
- 239000004793 Polystyrene Substances 0.000 description 15
- 238000003860 storage Methods 0.000 description 15
- 230000001804 emulsifying effect Effects 0.000 description 14
- 238000005336 cracking Methods 0.000 description 13
- 229920002223 polystyrene Polymers 0.000 description 13
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 11
- 238000002156 mixing Methods 0.000 description 11
- 239000002736 nonionic surfactant Substances 0.000 description 11
- 239000011734 sodium Substances 0.000 description 11
- 229910052708 sodium Inorganic materials 0.000 description 11
- 229920003169 water-soluble polymer Polymers 0.000 description 10
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 8
- 239000006082 mold release agent Substances 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- 239000011591 potassium Substances 0.000 description 8
- 229910052700 potassium Inorganic materials 0.000 description 8
- 229910019142 PO4 Inorganic materials 0.000 description 7
- 239000004743 Polypropylene Substances 0.000 description 7
- 150000001336 alkenes Chemical class 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 235000021317 phosphate Nutrition 0.000 description 7
- 229920001155 polypropylene Polymers 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 238000009736 wetting Methods 0.000 description 7
- 238000000576 coating method Methods 0.000 description 6
- 239000010452 phosphate Substances 0.000 description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 description 6
- 239000005020 polyethylene terephthalate Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 159000000000 sodium salts Chemical class 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 5
- 229920003002 synthetic resin Polymers 0.000 description 5
- 239000000057 synthetic resin Substances 0.000 description 5
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 4
- 229920002472 Starch Polymers 0.000 description 4
- 150000003863 ammonium salts Chemical class 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 4
- 239000008107 starch Substances 0.000 description 4
- 235000019698 starch Nutrition 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical class OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229960005323 phenoxyethanol Drugs 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 3
- 239000000244 polyoxyethylene sorbitan monooleate Substances 0.000 description 3
- 229920000053 polysorbate 80 Polymers 0.000 description 3
- 238000004804 winding Methods 0.000 description 3
- LQXBZWFNAKZUNM-UHFFFAOYSA-N 16-methyl-1-(16-methylheptadecoxy)heptadecane Chemical compound CC(C)CCCCCCCCCCCCCCCOCCCCCCCCCCCCCCCC(C)C LQXBZWFNAKZUNM-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 2
- 229920002907 Guar gum Polymers 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 2
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229920001213 Polysorbate 20 Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 125000004948 alkyl aryl alkyl group Chemical group 0.000 description 2
- 150000008051 alkyl sulfates Chemical class 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- 229960004365 benzoic acid Drugs 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 235000010417 guar gum Nutrition 0.000 description 2
- 239000000665 guar gum Substances 0.000 description 2
- 229960002154 guar gum Drugs 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000012875 nonionic emulsifier Substances 0.000 description 2
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 2
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- 230000002335 preservative effect Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 235000010199 sorbic acid Nutrition 0.000 description 2
- 239000004334 sorbic acid Substances 0.000 description 2
- 229940075582 sorbic acid Drugs 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- FZGFBJMPSHGTRQ-UHFFFAOYSA-M trimethyl(2-prop-2-enoyloxyethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCOC(=O)C=C FZGFBJMPSHGTRQ-UHFFFAOYSA-M 0.000 description 2
- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- FFJCNSLCJOQHKM-CLFAGFIQSA-N (z)-1-[(z)-octadec-9-enoxy]octadec-9-ene Chemical compound CCCCCCCC\C=C/CCCCCCCCOCCCCCCCC\C=C/CCCCCCCC FFJCNSLCJOQHKM-CLFAGFIQSA-N 0.000 description 1
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 1
- LTSWUFKUZPPYEG-UHFFFAOYSA-N 1-decoxydecane Chemical compound CCCCCCCCCCOCCCCCCCCCC LTSWUFKUZPPYEG-UHFFFAOYSA-N 0.000 description 1
- HXVJQEGYAYABRY-UHFFFAOYSA-N 1-ethenyl-4,5-dihydroimidazole Chemical compound C=CN1CCN=C1 HXVJQEGYAYABRY-UHFFFAOYSA-N 0.000 description 1
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- GGZKJFGVSZKFLD-UHFFFAOYSA-N 1-prop-1-enyl-1h-imidazol-1-ium;chloride Chemical compound [Cl-].CC=CN1C=C[NH+]=C1 GGZKJFGVSZKFLD-UHFFFAOYSA-N 0.000 description 1
- CHHHXKFHOYLYRE-UHFFFAOYSA-M 2,4-Hexadienoic acid, potassium salt (1:1), (2E,4E)- Chemical compound [K+].CC=CC=CC([O-])=O CHHHXKFHOYLYRE-UHFFFAOYSA-M 0.000 description 1
- CDOUZKKFHVEKRI-UHFFFAOYSA-N 3-bromo-n-[(prop-2-enoylamino)methyl]propanamide Chemical compound BrCCC(=O)NCNC(=O)C=C CDOUZKKFHVEKRI-UHFFFAOYSA-N 0.000 description 1
- CFKMVGJGLGKFKI-UHFFFAOYSA-N 4-chloro-m-cresol Chemical compound CC1=CC(O)=CC=C1Cl CFKMVGJGLGKFKI-UHFFFAOYSA-N 0.000 description 1
- 244000215068 Acacia senegal Species 0.000 description 1
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- GHXZTYHSJHQHIJ-UHFFFAOYSA-N Chlorhexidine Chemical compound C=1C=C(Cl)C=CC=1NC(N)=NC(N)=NCCCCCCN=C(N)N=C(N)NC1=CC=C(Cl)C=C1 GHXZTYHSJHQHIJ-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 108010039918 Polylysine Proteins 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- JBRADEZAEHYTGG-UHFFFAOYSA-N S1N=CC(C1)=O.S1N=CC(C1)=O Chemical class S1N=CC(C1)=O.S1N=CC(C1)=O JBRADEZAEHYTGG-UHFFFAOYSA-N 0.000 description 1
- 229920002385 Sodium hyaluronate Polymers 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920006322 acrylamide copolymer Polymers 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 229920001893 acrylonitrile styrene Polymers 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000001204 arachidyl 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])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229960000686 benzalkonium chloride Drugs 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- CADWTSSKOVRVJC-UHFFFAOYSA-N benzyl(dimethyl)azanium;chloride Chemical compound [Cl-].C[NH+](C)CC1=CC=CC=C1 CADWTSSKOVRVJC-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 235000010418 carrageenan Nutrition 0.000 description 1
- 239000000679 carrageenan Substances 0.000 description 1
- 229920001525 carrageenan Polymers 0.000 description 1
- 229940113118 carrageenan Drugs 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229960003260 chlorhexidine Drugs 0.000 description 1
- KXKPYJOVDUMHGS-OSRGNVMNSA-N chondroitin sulfate Chemical compound CC(=O)N[C@H]1[C@H](O)O[C@H](OS(O)(=O)=O)[C@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](C(O)=O)O1 KXKPYJOVDUMHGS-OSRGNVMNSA-N 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000009193 crawling Effects 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 238000004512 die casting Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 description 1
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- ACGUYXCXAPNIKK-UHFFFAOYSA-N hexachlorophene Chemical compound OC1=C(Cl)C=C(Cl)C(Cl)=C1CC1=C(O)C(Cl)=CC(Cl)=C1Cl ACGUYXCXAPNIKK-UHFFFAOYSA-N 0.000 description 1
- 229960004068 hexachlorophene Drugs 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- TWMKXPBVMFGBRH-UHFFFAOYSA-N methanol;terephthalic acid Chemical compound OC.OC.OC(=O)C1=CC=C(C(O)=O)C=C1 TWMKXPBVMFGBRH-UHFFFAOYSA-N 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 229960003742 phenol Drugs 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920000656 polylysine Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 235000010483 polyoxyethylene sorbitan monopalmitate Nutrition 0.000 description 1
- 239000000249 polyoxyethylene sorbitan monopalmitate Substances 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001955 polyphenylene ether 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
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 239000004302 potassium sorbate Substances 0.000 description 1
- 235000010241 potassium sorbate Nutrition 0.000 description 1
- 229940069338 potassium sorbate Drugs 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 229940047670 sodium acrylate Drugs 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 229960003885 sodium benzoate Drugs 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 229940010747 sodium hyaluronate Drugs 0.000 description 1
- YWIVKILSMZOHHF-QJZPQSOGSA-N sodium;(2s,3s,4s,5r,6r)-6-[(2s,3r,4r,5s,6r)-3-acetamido-2-[(2s,3s,4r,5r,6r)-6-[(2r,3r,4r,5s,6r)-3-acetamido-2,5-dihydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-2-carboxy-4,5-dihydroxyoxan-3-yl]oxy-5-hydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-3,4,5-trihydroxyoxane-2- Chemical compound [Na+].CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@H](O3)C(O)=O)O)[C@H](O)[C@@H](CO)O2)NC(C)=O)[C@@H](C(O)=O)O1 YWIVKILSMZOHHF-QJZPQSOGSA-N 0.000 description 1
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 description 1
- HIEHAIZHJZLEPQ-UHFFFAOYSA-M sodium;naphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 HIEHAIZHJZLEPQ-UHFFFAOYSA-M 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- ICUTUKXCWQYESQ-UHFFFAOYSA-N triclocarban Chemical compound C1=CC(Cl)=CC=C1NC(=O)NC1=CC=C(Cl)C(Cl)=C1 ICUTUKXCWQYESQ-UHFFFAOYSA-N 0.000 description 1
- 229960001325 triclocarban Drugs 0.000 description 1
- UZNHKBFIBYXPDV-UHFFFAOYSA-N trimethyl-[3-(2-methylprop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)NCCC[N+](C)(C)C UZNHKBFIBYXPDV-UHFFFAOYSA-N 0.000 description 1
- OEIXGLMQZVLOQX-UHFFFAOYSA-N trimethyl-[3-(prop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCCNC(=O)C=C OEIXGLMQZVLOQX-UHFFFAOYSA-N 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 229940082509 xanthan gum Drugs 0.000 description 1
- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/05—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media from solid polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C33/00—Moulds or cores; Details thereof or accessories therefor
- B29C33/56—Coatings, e.g. enameled or galvanised; Releasing, lubricating or separating agents
- B29C33/60—Releasing, lubricating or separating agents
- B29C33/62—Releasing, lubricating or separating agents based on polymers or oligomers
- B29C33/64—Silicone
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/80—Packaging reuse or recycling, e.g. of multilayer packaging
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Dispersion Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Moulds For Moulding Plastics Or The Like (AREA)
Abstract
The present invention provides a release agent for plastics, which is an emulsion containing the following components (A) to (C) and (E) and having an average particle diameter of more than 200nm and not more than 350 nm: (A) Dynamic viscosity at 25 ℃ of 100 to 100,000mm 2 Organopolysiloxane/s: 100 parts by mass; (B) anionic surfactant: 0.1 to 18.0 parts by mass; (C) polyoxyethylene sorbitan fatty acid ester: 0.1 to 10.0 parts by mass; (E) Water: 50 to 100,000 parts by mass. Thus, a release agent for plastics, which is an organopolysiloxane emulsion, is provided that is excellent in centrifugal separation stability, dilution stability, and mechanical stability, has little edge shrinkage when applied to plastics, and is less likely to crack the plastics.
Description
Technical Field
The invention relates to a release agent for plastics, which is an emulsion composition of organopolysiloxane.
Background
From the standpoint of freshness or hygiene, the food is sold in a form protected by a plastic tray, sheet, film, or the like. Various food container packaging plastics such as polyethylene terephthalate (PET), polypropylene (PP), and Polystyrene (PS) can be used depending on the type of food or the storage temperature.
In the process of producing the plastic for packaging food containers, the plastic is formed into a sheet or film and then wound into a roll. In winding into rolls, a release agent is generally applied to the surface of the sheet or film so that the sheet or film does not adhere to each other.
In addition, when molding into a sheet or film, the molded article is smoothly released from the mold by applying the release agent to the mold, so that stable continuous production is possible.
Further, the molded articles such as a case, a tray, and a cup, which are molded with a sheet or a film, are stacked and stored, and when a release agent is applied thereto, the molded articles can be smoothly removed one by one without sticking.
From the viewpoints of releasability and lubricity, the synthetic resin for packaging food containers preferably has a dynamic viscosity of 100 to 100,000mm at 25 DEG C 2 An organopolysiloxane emulsion composition of/s. When the organopolysiloxane emulsion composition is applied to a plastic as a release agent, dilution with water is performed so that the concentration of the organopolysiloxane becomes 0.1 to 5.0 mass%, and application is performed by spin wetting (rotary wetting), gravure method, or spray method.
Spin wetting, a coating process accompanied by intense agitation, may destroy the emulsion itself and create gels or oils, etc. When the emulsion is applied to plastics in a state where gel and oil slick have been generated, uneven wetting occurs, and there is a problem that the plastics adhere to each other or the appearance is uneven.
Furthermore, if an emulsion of organopolysiloxane containing a large amount of nonionic surfactant is applied to plastics, the following problems may occur: the nonionic surfactant is impregnated into the plastic to cause cracks, and cracks are generated in the molded article. Such cracks are easily generated in plastics, especially in biaxially stretched polystyrene or Polystyrene (PS).
Therefore, an emulsion-type release agent of organopolysiloxane is demanded which is excellent in dilution stability, mechanical stability, storage stability, wettability and which does not crack to plastics.
In japan, the chemical structure of raw materials that can be used for packaging containers for foods has been regulated by the revised food sanitation law applied on the 6 th and 1 th year of 2020. Further, the japanese health olefin and styrene plastic society registers plastic raw materials (affirmative list system) that can be used for container packaging or the like in direct contact with food for each product, and recommends the use of raw material products for which safety has been confirmed in use of container packaging in direct contact with food.
Accordingly, as a release agent for plastics for food container packaging, there has been sought an emulsion using an organopolysiloxane which has a chemical structure approved for use in food sanitation and has been registered in the affirmative list of the japanese sanitary olefin and styrene plastics society, and which can solve the above-mentioned object technical problem.
Heretofore, various methods have been studied in order to solve the above-mentioned problems.
Patent document 1 discloses that an organopolysiloxane emulsion having good stability is obtained by ring-opening polymerization with a strong acid in a state in which a cyclic siloxane oligomer has been emulsified. However, the organopolysiloxane emulsion obtained in this way contains a large amount of octamethyl cyclotetrasiloxane, decamethyl cyclopentasiloxane and dodecamethyl cyclohexasiloxane. In recent years, octamethyl cyclotetrasiloxane, decamethyl cyclopentasiloxane and dodecamethyl cyclohexasiloxane have become candidates for highly interesting substances regulated by REACH regulations in europe, and therefore it has been demanded to reduce the content of the cyclic siloxane oligomer. Further, since the cyclic siloxane oligomer is contained in a large amount, cracks may be easily generated when the cyclic siloxane oligomer is applied to plastics.
Patent document 2 discloses an organopolysiloxane emulsion release agent composition that has excellent wettability and also good transparency. Since polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, or the like is used as the nonionic surfactant in the examples and the blending amount is as high as 1.0% or more, cracks may be generated when used as a mold release agent for PS or biaxially stretched polystyrene. Further, since sodium polyoxyethylene nonylphenyl ether sulfate was used as an anionic surfactant in examples, and nonylphenol as a decomposition product thereof was a substance that may cause environmental burden to living beings or ecological systems, the use as a mold release agent for plastics for food container packaging was not recommended.
Patent document 3 discloses a silicone release agent composition with less whitening of a film. Propylene glycol is contained in the composition of patent document 3. Further, polyoxyethylene lauryl ether was used alone as the nonionic emulsifier in the examples, but when the nonionic emulsifier was used alone, the average particle diameter may not be thinned and the stability may be poor. In addition, in the polyoxyethylene lauryl ether, since a substance having a polyoxyethylene chain of 1 to 6 may crack in a synthetic resin, particularly in PS or biaxially stretched polystyrene, cracks may also occur when the emulsion of the example of patent document 3 is used as a mold release agent for PS or biaxially stretched polystyrene.
Patent document 4 discloses an emulsion having a narrow particle size distribution and excellent stability, in which phenoxyethanol is blended during emulsification, but the average particle diameter of examples is as high as 1 μm or more, and the dilution stability and mechanical stability are predicted to be low.
Patent document 5 is an alkylarylalkyl co-modified silicone emulsion release agent for aluminum die casting. The alkylarylalkyl co-modified silicone has lower releasability from plastics than dimethylpolysiloxane and is not suitable for a release agent for plastics.
Patent document 6 discloses a silicone water-dispersible release agent composition which is used in combination with a sorbitan higher alkyl ester and other nonionic surfactants, and which is suitable for use in vulcanization molding of an acrylic rubber. It is considered that when an anionic surfactant is blended into a silicone emulsion, the negative value of the zeta potential of the emulsion increases, and the electronic repulsion between emulsion particles increases, so that aggregation is less likely to occur, and mechanical stability improves. Patent document 6, in which an anionic surfactant is not blended, predicts that mechanical stability is low.
Patent document 7 discloses an emulsion obtained by emulsifying an organopolysiloxane with a polyoxyethylene alkyl ether having an HLB of 10 or more. As in patent document 6, the mechanical stability is predicted to be low without blending an anionic surfactant.
Patent document 8 discloses a silicone emulsion composition comprising an organopolysiloxane, a polyoxyethylene alkyl ether having an alkyl chain with 8 to 11 carbon atoms, an anionic surfactant, and water. When an emulsion containing a polyoxyethylene alkyl ether having 8 to 11 carbon atoms is applied to a plastic, cracks may occur.
Patent document 9 discloses a silicone emulsion composition obtained by emulsifying an organopolysiloxane with a polyoxyethylene alkyl ether and a sucrose fatty acid ester. In the examples, polyoxyethylene (3) decyl ether was used as the polyoxyethylene alkyl ether, but polyoxyethylene alkyl ether having an alkyl group having 10 or less carbon atoms may crack the plastic.
Patent document 10 discloses an organosilicon emulsion obtained by emulsifying an organopolysiloxane with polyoxyethylene hexyl decyl ether or polyoxyethylene isostearyl ether. The average particle size pair in the examples is relatively large, about 400nm, and dilution stability or mechanical stability may be poor.
Patent document 11 discloses an emulsion obtained by emulsifying organopolysiloxane with an anionic surfactant and a polyol. In general, anionic surfactants or polyols have a lower surface tension-reducing function than nonionic surfactants such as polyoxyethylene alkyl ethers. The emulsion of patent document 11 has a surface tension (25 ℃) of 45mN/m or more after being diluted to 50 times with water, and does not contain a nonionic surfactant, and therefore, when applied to plastics, there is a possibility that the wetting property is poor and edge shrinkage (crawling) occurs.
Prior art literature
Patent literature
Patent document 1: japanese patent publication No. 41-13995
Patent document 2: japanese patent laid-open No. 8-188744
Patent document 3: japanese patent application laid-open No. 2005-281409
Patent document 4: japanese patent laid-open No. 2000-169705
Patent document 5: japanese patent laid-open No. 2006-307009
Patent document 6: japanese patent laid-open No. 8-283771
Patent document 7: japanese patent laid-open No. 2000-143814
Patent document 8: japanese patent laid-open No. 2004-331784
Patent document 9: japanese patent laid-open No. 2004-035820
Patent document 10: japanese patent laid-open No. 2003-073546
Patent document 11: japanese patent laid-open No. 11-148012
Disclosure of Invention
Technical problem to be solved by the invention
The present invention has been made in view of the above circumstances, and an object thereof is to provide a release agent for plastics which is an emulsion of an organopolysiloxane, is excellent in centrifugal separation stability, dilution stability, and mechanical stability, has less edge shrinkage when applied to plastics, and is less likely to cause cracks in plastics.
Technical means for solving the technical problems
In order to achieve the above object, the present invention provides a release agent for plastics, which is an emulsion containing the following components (a) to (C) and (E) and having an average particle diameter of more than 200nm and not more than 350 nm:
(A) An organopolysiloxane represented by the following general formula (1) having a dynamic viscosity of 100 to 100,000mm at 25 DEG C 2 And the content of octamethyl cyclotetrasiloxane, decamethyl cyclopentasiloxane and dodecamethyl cyclohexasiloxane is respectively less than 1 mass%: 100 parts by mass of the components in the total mass,
[ chemical formula 1]
In the formula (1), R 1 Optionally identical or different, R 1 Is any one of hydroxyl, hydrogen atom, unsubstituted straight-chain alkyl with 1-32 carbon atoms and phenyl, L is an integer of 60-1,500;
(B) Anionic surfactant: 0.1 to 18.0 parts by mass;
(C) A polyoxyethylene sorbitan fatty acid ester represented by the following general formula (2): 0.1 to 10.0 parts by mass,
[ chemical formula 2]
In the formula (2), R 2 An alkyl group having 8 to 24 carbon atoms, a, b and c are independently integers of 0 or more, and the total of a+b+c is 8 to 30;
(E) Water: 50 to 100,000 parts by mass.
The release agent for plastics of the present invention can provide a release agent for plastics which is an emulsion of an organopolysiloxane, is excellent in centrifugal separation stability, dilution stability, and mechanical stability, has little edge shrinkage when applied to plastics, and is less likely to cause cracks in plastics.
Further, the release agent for plastics of the present invention may further contain less than 1.0 part by mass of (D) a polyoxyethylene alkyl ether represented by the following general formula (3), preferably the sum of the contents of the (C) component and the (D) component is 0.1 to 10.0 parts by mass,
C m H 2m+1 (OCH 2 CH 2 ) n OH (3)
in the formula (3), m is an integer of 12 to 20, and n is an integer of 4 to 50.
When the total content of the component (C) and the component (D) falls within this range, the average particle diameter of the release agent for plastics of the present invention becomes small, and dilution stability and mechanical stability are likely to be good, and cracking is unlikely to occur.
The release agent for plastic of the present invention tends to have improved storage stability, mechanical stability, dilution stability, and wettability due to the inclusion of the component (D). On the other hand, from the viewpoint of preventing cracking of plastics, the smaller the content of the component (D) is, the more preferable.
Further, the HLB of the component (C) is preferably 12 to 18.
When the HLB of the component (C) is within this range, the average particle diameter of the release agent for plastics of the present invention tends to be small, and dilution stability or mechanical stability tends to be good.
The component (B) is preferably an anionic surfactant selected from 1 or 2 or more of alkyl sulfate, alkyl sulfonate, alkylbenzene sulfonate, alkyl naphthalene sulfonate, alkyl sulfosuccinate, alkyl phosphate, polyoxyethylene alkyl ether sulfate, and polyoxyethylene alkyl ether phosphate.
The reason for this is that the anionic surfactant has been accepted as a material for packaging containers for foods by the japanese food sanitation act, which is carried out on 6/1/2020. Therefore, the release agent for plastic of the present invention is preferable from the viewpoint of safety in use as a food container package or the like.
Further, the pH of the release agent for plastic at 25℃is preferably 4.0 to 10.0.
The reason for this is that, in the case of such a release agent for plastics, the structure of the component (a) changes even when stored at high temperature, and the influence on the releasability of plastics is small.
The release agent for plastic can be particularly suitably used for plastic for packaging food containers.
The reason for this is that the release agent for plastic of the present invention does not contain a substance that may cause environmental burden to living beings or ecological systems due to decomposition products such as nonylphenol or octylphenol, has a structure described in the affirmative list of japanese food sanitation act carried out on 6/1/2020, and can be composed of only raw materials approved by "autonomous standards for packaging of synthetic resin food containers such as polyolefin" and the like, and such release agent for plastic is suitable as a release agent for packaging containers that directly contact food such as food trays, lunch boxes, egg packages and the like.
Effects of the invention
According to the present invention, since the emulsion has a sufficiently small particle diameter, the mold release agent for plastics has excellent dilution stability, mechanical stability, storage stability (centrifugal separation stability), and excellent wettability to plastics, and is less likely to cause stress cracking in plastics. The release agent for plastic of the present invention can be constituted by the materials described in the affirmative list provided by the japan hygienic olefin and styrene plastics society, and is suitable for packaging food containers.
Detailed Description
As described above, there has been a demand for development of an organopolysiloxane emulsion-type release agent which is excellent in dilution stability, mechanical stability, and storage stability, has good wettability, and does not crack plastics.
As a result of intensive studies to achieve the above object, the inventors of the present application have found that a dynamic viscosity at 25℃is 100 to 100,000mm by using an anionic surfactant and a polyoxyethylene sorbitan fatty acid ester having a specific structure 2 The organopolysiloxane/s has an average particle diameter of more than 200nm and not more than 350nm, and can be used for preparing a release agent for plastics which is excellent in dilution stability, mechanical stability, storage stability (centrifugal separation stability), good in wettability and less prone to crack on plastics.
The present invention will be described in detail below, but the present invention is not limited thereto.
[ Release agent for Plastic ]
The release agent for plastics is characterized by comprising the following components (A) - (C) and (E), and having an average particle diameter of more than 200nm and 350nm or less:
(A) An organopolysiloxane represented by the following general formula (1) having a dynamic viscosity of 100 to 100,000mm at 25 DEG C 2 And the content of octamethyl cyclotetrasiloxane, decamethyl cyclopentasiloxane and dodecamethyl cyclohexasiloxane is respectively less than 1 mass%: 100 parts by mass of the components in the total mass,
[ chemical formula 3]
In the formula (1), R 1 Optionally identical or different, R 1 Is any one of a hydroxyl group, a hydrogen atom, an unsubstituted straight-chain alkyl group having 1 to 32 carbon atoms, and a phenyl group, L is an integer of 60 to 1,500;
(B) Anionic surfactant: 0.1 to 18.0 parts by mass;
(C) A polyoxyethylene sorbitan fatty acid ester represented by the following general formula (2): 0.1 to 10.0 parts by mass,
[ chemical formula 4]
In the formula (2), R 2 An alkyl group having 8 to 24 carbon atoms, a, b and c are independently integers of 0 or more, and the total of a+b+c is 8 to 30;
(E) Water: 50 to 100,000 parts by mass.
[ (A) organopolysiloxane ]
(A) An organopolysiloxane represented by the following general formula (1) having a dynamic viscosity of 100 to 100,000mm at 25 DEG C 2 S:100 parts by mass.
[ chemical formula 5]
In the above formula (1), R 1 Optionally identical or different, R 1 Is any one of unsubstituted straight-chain alkyl group having 1 to 32 carbon atoms, phenyl group, hydroxyl group and hydrogen atom. Examples of the straight-chain unsubstituted alkyl group having 1 to 32 carbon atoms include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, and eicosyl. As R 1 The straight-chain unsubstituted alkyl group or phenyl group having 1 to 20 carbon atoms is preferable, and methyl or phenyl is more preferable from the viewpoint of versatility. Further, from the viewpoint of releasability, R in 1 molecule is preferable 1 More than 50mol% of the number of (C) is methyl.
L is an integer of 60 to 1,500, preferably 150 to 1,200.
In the organopolysiloxane (A), the content of octamethyl cyclotetrasiloxane, decamethyl cyclopentasiloxane and dodecamethyl cyclohexasiloxane is less than 1 mass%, preferably less than 0.1 mass%, respectively. If the organopolysiloxane (a) contains a large amount of octamethyl cyclotetrasiloxane, decamethyl cyclopentasiloxane, and dodecamethyl cyclohexasiloxane, the organopolysiloxane may not be easily emulsified, the average particle diameter may be increased, the storage stability, dilution stability, and mechanical stability may be reduced, or cracks may be easily generated when the organopolysiloxane is applied to plastics. The lower limit of each content is preferably smaller, and thus cannot be limited, but may be set to 0.0001%, for example.
(A) The organopolysiloxane of the component (A) has a dynamic viscosity of 100 to 100,000mm at 25 DEG C 2 And/s. If the dynamic viscosity is less than 100mm 2 The resulting composition does not exhibit sufficient release properties. Furthermore, the minimum dynamic viscosity of dimethylpolysiloxane, methylpolysiloxane and methylpolysiloxane registered in the affirmative list of the Japanese society for hygienic olefins and styrene plastics was 100mm 2 And/s. On the other hand, if the organopolysiloxane of component (A) has a dynamic viscosity of greater than 100,000mm 2 And/s, when applied to a film or the like, may give a sticky feel on the surface. Preferably 200 to 50,000mm 2 And/s, more preferably 300 to 15,000mm 2 /s。
The dynamic viscosity is a value of dynamic viscosity at 25℃measured by a Canon-Finsk viscometer (Cannon-Fenske viscometer) described in JIS Z8803:2011. Wherein when the dynamic viscosity is greater than 20,000mm 2 At/s, a value obtained by dividing the value of the viscosity at 25℃measured by the single cylinder rotary viscometer described in the above JIS standard by the value of the measured density at 25℃was used.
(A) The organopolysiloxane of the component (A) may have a dynamic viscosity at 25℃within the above range, and may be used alone or in combination of at least 2.
[ (B) anionic surfactant ]
Examples of the anionic surfactant as the component (B) include alkyl sulfate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkylphenyl ether sulfate, fatty acid alkyl alcohol amide sulfate, alkyl sulfonate, polyoxyethylene alkylphenyl ether sulfonate, alkylbenzenesulfonate, alkylnaphthalene sulfonate, alkyldiphenyl ether disulfonate, and alkane sulfonate; alkyl sulfosuccinates such as monoalkyl sulfosuccinates and dialkyl sulfosuccinates; polyoxyethylene alkyl ether sulfosuccinate; alkyl phosphates such as monoalkyl phosphate and dialkyl phosphate; polyoxyethylene alkyl ether phosphate salts, alpha-sulfo fatty acid ester salts, N-acyl taurates, fatty acid salts, polyoxyethylene alkyl ether carboxylates, N-acyl amino acid salts, and the like. Examples of the salt include sodium salt, potassium salt, ammonium salt, and triethanolamine salt.
In japan, when the release agent for plastic of the present invention is used for plastic for food container packaging, it is necessary to use a substance having a structure described in the affirmative list of japan food sanitation act, which is carried out on 1/6/2020. For example, anionic surfactants having the following structures can be used. The alkyl has 8-22 carbon atoms, and the salt is sodium, potassium or ammonium alkyl sulfate. The alkyl has 8-22 carbon atoms, and the salt is sodium, potassium, calcium or ammonium alkyl sulfonate. The alkyl has 8-22 carbon atoms, and the salt is sodium, magnesium, potassium, calcium, ammonium alkyl benzene sulfonate. Alkyl is 10-20 and the salt is sodium alkyl naphthalene sulfonate. Alkyl sulfosuccinate with alkyl of 4-22 carbon atoms and sodium, magnesium, potassium and calcium salts. The alkyl has 8-22 carbon atoms, and the salt is alkyl phosphate ester salt of potassium or triethanolamine salt. The alkyl has 10-20 carbon atoms, and the salt is sodium or ammonium polyoxyethylene alkyl ether sulfate. The carbon number of the alkyl is 12-18, and the salt is polyoxyethylene alkyl ether phosphate salt of diethanolamine or triethanolamine.
In the japanese food sanitation method, the classification of synthetic resins is defined according to the raw materials of container packaging, and the use restriction amounts of the respective substances described in the affirmative list are defined according to the classification of synthetic resins. Therefore, when the release agent for plastic of the present invention is used for plastic for food container packaging, it is necessary to blend in an amount not exceeding the above-mentioned use limiting amount.
More preferably, the surfactant described in the affirmative list of the society for sanitary olefins and styrene plastics is selected from anionic surfactants conforming to the above-mentioned japanese food sanitation act.
Examples of the application to polypropylene or polystyrene include alkyl sulfonates (having 10 to 20 carbon atoms, sodium, potassium and ammonium salts), alkylbenzene sulfonates (having 9 to 20 carbon atoms, sodium, potassium and ammonium salts), alkylsulfonyl succinates (having 4 to 16 carbon atoms, sodium salt), and alkylsulfate salts (having 8 to 20 carbon atoms, sodium, potassium and ammonium salts).
Examples of the application to polyethylene terephthalate include alkyl sulfonate (having 10 to 20 carbon atoms and sodium salt as salt), alkylbenzenesulfonate (having 9 to 20 carbon atoms and sodium salt as salt), alkyl sulfosuccinate (having 4 to 16 carbon atoms and sodium salt as salt), and alkyl sulfate salt (having 4 to 16 carbon atoms and sodium salt as salt) and the like.
The anionic surfactant as the component (B) of the emulsifier is 0.1 to 18.0 parts by mass per 100 parts by mass of the organopolysiloxane as the component (A). Preferably 0.15 to 15.0 parts by mass, more preferably 0.2 to 12.0 parts by mass. If it is less than 0.1 part by mass, the mechanical stability of the release agent for plastics of the present invention may be lowered. On the other hand, if it exceeds 18.0 parts by mass, releasability may be lowered.
(B) The anionic surfactant of the component (A) may be used alone or in combination of 1 or more than 2.
[ (C) polyoxyethylene sorbitan fatty acid ester ]
(C) A polyoxyethylene sorbitan fatty acid ester represented by the following general formula (2): 0.1 to 10.0 parts by mass.
[ chemical formula 6]
In the formula (2), R 2 Is an alkyl group having 8 to 24 carbon atoms; a. b and c are independently integers of 0 or more, and the total of a+b+c is 8 to 30.
As in the foregoing, when the present invention is appliedWhen the mold release agent for plastic is used for packaging food containers, it is necessary to use a substance described in the affirmative list of Japanese food sanitation act, which corresponds to R of the above formula (2) 2 Has a structure in which the total of a+b+c is 4 or more and the number of carbon atoms is 8 to 24. Further, it is more preferable to select a surfactant described in the affirmative list of the japanese sanitary olefin and styrene plastics society, which corresponds to a structure having 12 to 18 carbon atoms and a+b+c in total of 20 for use in coating of polypropylene, polyethylene terephthalate or polystyrene.
Wherein the sum of a+b+c is 20 and the alkyl groups R 2 The use of polyoxyethylene sorbitan monolaurate having 12 carbon atoms, polyoxyethylene sorbitan monopalmitate having 16 carbon atoms, and polyoxyethylene sorbitan monooleate having 18 carbon atoms as food additives has been approved, and therefore the release agent for plastics of the present invention is suitable for use in plastics for packaging food containers.
If the total of a+b+c is less than 8, the emulsifying property is insufficient and the stability is poor. On the other hand, if the total of a+b+c is more than 30, the viscosity is high or the viscosity becomes solid, and the handleability is lowered.
If the anionic surfactant of the component (B) is used alone, the organopolysiloxane of the component (A) has a weak emulsifying power, and sufficient storage stability, mechanical stability and dilution stability cannot be obtained, but the storage stability, mechanical stability and dilution stability can be improved by blending the nonionic surfactant. Further, it is considered that the nonionic surfactant is liable to generate cracks when applied to plastics, and among them, the polyoxyethylene sorbitan fatty acid ester of the component (C) has an advantage of being relatively less liable to generate cracks.
(C) The polyoxyethylene sorbitan fatty acid ester of the component (A) may be used alone or in combination of 1 or more than 2. (C) The HLB of the polyoxyethylene sorbitan fatty acid ester of the component (A) can be set to 12 to 18, preferably 14 to 18. When HLB is within these ranges, a release agent for plastics having good emulsifying power and good stability can be obtained, and is preferable.
The amount of the polyoxyethylene sorbitan fatty acid ester as the component (C) is 0.1 to 10.0 parts by mass. Preferably 0.2 to 8.0 parts by mass, more preferably 0.5 to 6.0 parts by mass. If the blending amount of the component (C) is less than 0.1 part by mass, the stability of the emulsion obtained by emulsifying the organopolysiloxane as the component (A) may be lowered. On the other hand, if the blending amount of the component (C) is more than 10.0 parts by mass, cracks may occur when the release agent for plastic of the present invention is applied to plastic.
[ (D) polyoxyethylene alkyl ether ]
In the present invention, in addition to the above-mentioned components (A) to (C) and (E), less than 1.0 part by mass of (D) a polyoxyethylene alkyl ether represented by the following general formula (3) may be further added.
C m H 2m+1 (OCH 2 CH 2 ) n OH (3)
In the formula (3), m is an integer of 12 to 20, and n is an integer of 4 to 50.
M in the above formula (3) is an integer of 12 to 20, preferably an integer of 13 to 18, and more preferably an integer of 13 to 16. When m is 12 or more, cracks are less likely to occur in the plastic coated with the release agent for plastic of the present invention. On the other hand, when m is 20 or less, the particle diameter of the release agent for plastics of the present invention tends to be small, and the storage stability, dilution stability, mechanical stability, and wettability tend to be high. The alkyl group may be either a branched chain or a linear chain, and may be selected according to the ease of emulsification of the organopolysiloxane of component (a) or the difficulty of occurrence of cracks when applied to plastics.
N in the formula (3) is an integer of 4 to 50. Preferably 4 to 30, more preferably 4 to 25. When n is 4 or more, cracks are less likely to occur in the plastic coated with the release agent for plastic of the present invention. On the other hand, when n is 50 or less, the polyoxyethylene alkyl ether of the above formula (3) is not solid and is easy to handle.
In addition, when the alkyl group is short and the polyoxyethylene chain is short, cracks are easily generated in the plastic. Therefore, when polyoxyethylene alkyl ethers having short alkyl groups are used, the use of polyoxyethylene chain-short materials should be avoided. Specifically, when m is 12 to 15, n is preferably an integer of 8 to 50, and when m is 16 to 20, n is preferably an integer of 4 to 50.
The component (D) may be used alone or in combination of 1 or more than 2. The HLB of the component (D) can be set to 8 to 18, preferably 10 to 17, and more preferably 13 to 16. When good storage stability, mechanical stability, and dilution stability cannot be obtained, storage stability, mechanical stability, and dilution stability are improved by using a combination of a substance having an HLB of up to 15 to 18 and a substance having an HLB of down to 8 to 12 so that the HLB is 13 to 16. On the other hand, when the component (D) having an HLB of 8 to 12 is contained in a large amount, the blending amount of the component (D) having such a structure in the mold release agent for plastic of the present invention is preferably small in order to prevent occurrence of cracks in the plastic.
Among nonionic surfactants, the component (D) has a characteristic that cracks are more likely to occur when applied to plastics than the component (C). Therefore, for example, when the component (C) is blended to obtain a release agent for plastics having good stability, it is preferable not to blend the component (D). When blended, the upper limit is preferably set to 1.0 part by mass in order to suppress occurrence of cracks.
Specific examples of the component (D) include, but are not limited to, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene hexyl decyl ether, polyoxyethylene isostearyl ether, and polyoxyethylene octyl dodecyl ether.
In the case of using the release agent for plastic of the present invention for plastic for packaging of food containers, the release agent for plastic of the present invention must be used as described in the affirmative list of the japanese food sanitation act, and has a structure in which m is 6 to 20 and n is 4 or more. Further, it is more preferable to select a surfactant described in the affirmative list of the japanese sanitary olefin and styrene plastics society, which corresponds to a structure having 12 to 20 carbon atoms m for use in coating of polypropylene or polystyrene, polyethylene terephthalate.
The total of the component (C) and the component (D) as the nonionic surfactant can be set to 0.1 to 10.0 parts by mass per 100 parts by mass of the component (a). The amount is preferably 0.2 to 8.0 parts by mass, more preferably 0.5 to 6.0 parts by mass, and if it is not less than 0.1 parts by mass, good storage stability, mechanical stability and dilution stability can be obtained, and shrinkage edges are not easily generated when the composition is applied to plastics. On the other hand, it is preferably 10.0 parts by mass or less from the viewpoint of preventing cracks when the release agent for plastics is applied.
[ (E) Water ]
The release agent for plastics of the present invention is an organopolysiloxane emulsion composition, but is characterized by using (E) water as a dispersion medium.
The amount of water to be added as the component (E) is 50 to 100,000 parts by mass. Preferably 500 to 20,000 parts by mass, more preferably 2,000 to 10,000 parts by mass. If the amount of water (E) is less than 50 parts by mass, the release agent for plastics of the present invention may give a sticky feel, uneven coating, and cracks when applied to plastics, and the viscosity of the emulsion composition may be increased, which is not preferable. On the other hand, if the amount of (E) water exceeds 100,000 parts by mass, mechanical stability may be lowered, oil-floating may be generated after dilution and stirring, and if the dilution ratio is high, the amount of the emulsion composition required increases, which is not preferable in terms of economical efficiency.
[ other Components ]
The release agent for plastics of the present invention may contain a water-soluble polymer for the purpose of improving the dispersibility of the organopolysiloxane of component (a). The water-soluble polymer compound is not particularly limited, and examples thereof include nonionic water-soluble polymer compounds, anionic water-soluble polymer compounds, cationic water-soluble polymer compounds, and zwitterionic water-soluble polymer compounds.
Examples of the nonionic water-soluble polymer compound include polymers of vinyl alcohol, copolymers of vinyl alcohol and vinyl acetate, polymers of acrylamide, polymers of vinylpyrrolidone, copolymers of vinylpyrrolidone and vinyl acetate, polyethylene glycol, polymers of isopropylacrylamide, polymers of methyl vinyl ether, starch, methyl cellulose, hydroxyethyl cellulose, hydroxypropyl methylcellulose, guar gum (guar gum), and xanthan gum.
Examples of the anionic water-soluble polymer compound include sodium acrylate polymer, sodium acrylate-sodium maleate copolymer, sodium acrylate-sodium acrylamide copolymer, sodium styrene sulfonate polymer, sodium polyisoprene sulfonate-styrene copolymer, sodium naphthalene sulfonate polymer, carboxymethyl starch, phosphate starch, carboxymethyl cellulose, sodium alginate, gum arabic, carrageenan, sodium chondroitin sulfate, sodium hyaluronate, and the like.
Examples of the cationic water-soluble polymer include polymers of dimethyldiallylammonium chloride, polymers of vinylimidazoline, polymers of methylvinylimidazolium chloride, polymers of acryloyloxyethyl trimethyl ammonium chloride, polymers of methacryloyloxyethyl trimethyl ammonium chloride, polymers of acrylamidopropyl trimethyl ammonium chloride, polymers of methacrylamidopropyl trimethyl ammonium chloride, epichlorohydrin/dimethylamine polymers, polymers of ethyleneimine, quaternized products of ethyleneimine polymers, polymers of allylamine hydrochloride, polylysine, cationic starch, cationized cellulose, chitosan, and derivatives of the above, which are copolymerized with a monomer having a nonionic group or an anionic group.
Examples of the zwitterionic water-soluble polymer compound include a copolymer of acryloyloxyethyl trimethyl ammonium chloride and acrylic acid and acrylamide, a copolymer of methacryloyloxyethyl trimethyl ammonium chloride and acrylic acid and acrylamide, and a Hofmann degradation product of a polymer of acrylamide.
The release agent for plastics of the present invention may contain an antibacterial preservative or an antibacterial agent. Examples of the antibacterial preservative include alkyl p-hydroxybenzoates, benzoic acid, sodium benzoate, sorbic acid, potassium sorbate, phenoxyethanol, isothiazolinone (isothiazolinone) derivatives, and examples of the antibacterial agent include benzoic acid, salicylic acid, phenol, sorbic acid, alkyl p-hydroxybenzoates, parachlorometacresol, hexachlorophene, benzalkonium chloride, chlorhexidine, triclocarban, photosensitizers, phenoxyethanol, and the like. In addition, a perfume, an antioxidant, a rust inhibitor, a dye, a filler, a curing catalyst, an organic powder, an inorganic powder, and the like may be blended.
[ preparation of composition ]
The release agent for plastics of the present invention can be obtained by emulsifying (A) an organopolysiloxane in (E) water using (B) an anionic surfactant, (C) a polyoxyethylene sorbitan fatty acid ester, and optionally (D) a polyoxyethylene alkyl ether. The emulsification may be carried out using a general emulsifying and dispersing machine. Examples of the emulsifying and dispersing machine include a high-speed rotary centrifugal radial mixer such as a homogenizing and dispersing machine, a high-speed rotary shear mixer such as a homogenizing mixer, a high-pressure jet emulsifying and dispersing machine such as a pressure type homogenizer, a colloid mill, and an ultrasonic emulsifying machine.
The temperature at the time of emulsification is preferably 0 to 80 ℃, more preferably 10 to 60 ℃. At a temperature of 10 to 80 ℃, the emulsion is easy to emulsify, and the prepared emulsion is more stable. In emulsification, the pressure may be not only normal pressure but also reduced pressure or increased pressure. When emulsification is performed under reduced pressure or under increased pressure, foam may not be easily mixed and emulsification may be performed effectively. When the pressure is reduced, the pressure is preferably higher than the vapor pressure of the raw material so as not to volatilize the raw material. The emulsification time is not particularly limited, and may be set to a target particle size, and generally, it is preferably 360 minutes or less.
The average particle diameter of the release agent for plastics of the present invention is more than 200nm and not more than 350 nm. Preferably greater than 200nm and 300nm or less, more preferably greater than 200nm and 250nm or less.
If the average particle diameter is larger than 350nm, dilution stability and mechanical stability may be lowered, and oil-retaining or the like may be generated during dilution or stirring. Further, when stored for a long period of time, separation of shade may occur. On the other hand, in order to produce an emulsion having an average particle diameter of 200nm or less, nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters and polyoxyethylene alkyl ethers tend to be contained in an amount larger than that of the organopolysiloxane (A). Therefore, it is difficult to achieve an average particle diameter of 200nm or less within the scope of the present invention of the (C) and/or (D), and if the (C) and the (D) are blended beyond the scope of the present invention, releasability may be lowered or cracks may be generated when applied to plastics.
In the present specification, the average particle diameter means a particle diameter at which the cumulative value in the volume-based particle size distribution measured by the laser diffraction/scattering particle size distribution measuring apparatus is 50%.
The release agent for plastics of the present invention preferably has a pH of 4.0 to 10.0 at 25 ℃. Preferably 4.5 to 9.0, more preferably 4.5 to 8.0. When the pH is in the range of 4.0 to 10.0, the structure of the component (A) changes at a high Wen Baoguan, and the releasability of the plastic is less affected.
The emulsion obtained in the above manner is extremely useful as a mold release agent for plastic sheets for food packaging, molded articles thereof, and the like, or a mold release agent used in molding a mold. For example, the release agent for plastic of the present invention having a content of the component (a) of 0.1 to 2.0 mass% can be applied by spin wetting, gravure method, or spray method. The coating weight is generally suitably from 0.01 to 1.0g/m on a dry basis 2 Particularly preferably 0.02 to 0.2g/m 2 . If it is 0.01g/m 2 As described above, a sufficient releasability can be obtained, and if it is 1.0g/m 2 Hereinafter, it is preferable from the viewpoints of transparency and sticky feeling.
Examples of the plastic for packaging food containers include polyethylene, polypropylene, polymethylpentene, polybutene, ethylene-tetracyclododecene copolymer, ethylene-2-norbornene copolymer, polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-styrene-butadiene copolymer, polyphenylene ether, polyacrylonitrile, polymethacrylylstyrene (polymethylacryl styrene), polymethyl methacrylate, nylon, polyethylene terephthalate, polycarbonate, polyvinyl alcohol, polyacetal, polybutylene terephthalate, polycyclohexane dimethanol terephthalate, polyethylene naphthalate, and polyvinyl chloride.
According to the present invention, by emulsifying an organopolysiloxane in water using an anionic surfactant, a polyoxyethylene sorbitan fatty acid ester, and a polyoxyethylene alkyl ether as required, a release agent for plastics which has excellent releasability, good dilution stability, mechanical stability, storage stability, and wettability, and is less likely to cause stress cracking can be provided.
Examples
The present invention will be specifically described below by way of examples and comparative examples, but the present invention is not limited to the following examples.
The components used in the following examples and comparative examples are as follows.
[ component (A) and organopolysiloxane for comparison ]
(A1) Organopolysiloxane: represented by the following general formula (4), a dynamic viscosity at 25℃of 9,480 mm 2 And L1 is 550, and the content of octamethyl cyclotetrasiloxane, decamethyl cyclopentasiloxane and dodecamethyl cyclohexasiloxane is 100ppm or less.
[ chemical formula 7]
(A2) Organopolysiloxane: represented by the above general formula (4), a dynamic viscosity at 25℃of 1,010mm 2 And L1 is 200, and the content of octamethyl cyclotetrasiloxane, decamethyl cyclopentasiloxane and dodecamethyl cyclohexasiloxane is 100ppm or less.
(A3) Organopolysiloxane: represented by the above general formula (4), the dynamic viscosity at 25℃was 7,420mm 2 And/s, L1 is 550, and the content of octamethyl cyclotetrasiloxane, decamethyl cyclopentasiloxane and dodecamethyl cyclohexasiloxane is about 2 mass%, respectively. (A3) The organopolysiloxane of the component (A1) was obtained by blending octamethyl cyclotetrasiloxane, decamethyl cyclopentasiloxane and dodecamethyl cyclohexasiloxane with the organopolysiloxane of the component (A1) so that each of octamethyl cyclotetrasiloxane, decamethyl cyclopentasiloxane and dodecamethyl cyclohexasiloxane was 2 mass%.
[ component (B) ]
( B1 65% sodium dodecylbenzenesulfonate aqueous solution (trade name: NEOPELEX G-65,Kao Corporation manufacture )
( B2 Sodium lauryl sulfate (trade name: NIKKOL SLS, nikko Chemicals co., ltd )
(B3) 70% aqueous solution of dioctyl sodium sulfosuccinate
Component (C) and comparative polyoxyethylene sorbitan fatty acid ester
(C1) Polyoxyethylene sorbitan monooleate (trade name: RHEODOL TW-O120V, manufactured by Kao Corporation): represented by the following general formula (2), R 2 The sum of a+b+c is 20 and HLB is 15.0, which is an alkyl group having 18 carbon atoms.
(C2) Polyoxyethylene sorbitan monolaurate (trade name: RHEODOL TW-L120, manufactured by Kao Corporation): represented by the following general formula (2), R 2 The sum of a+b+c is 20 and HLB is 16.7, which is an alkyl group having 12 carbon atoms.
(C3) Polyoxyethylene sorbitan monooleate (trade name: RHEODOL TW-O106V, manufactured by Kao Corporation): represented by the following general formula (2), R 2 The sum of a+b+c is 6 and HLB is 10.0, which is an alkyl group having 18 carbon atoms.
[ chemical formula 8]
[ component (D) ]
(D) Polyoxyethylene lauryl ether (trade name: manufactured by EMULGEN 123P,Kao Corporation): by the general formula C m H 2m+1 (OCH 2 CH 2 ) n OH represents m is 12, n is 23, and HLB is 16.9.
[ component (E) ]
(E) Water and its preparation method
[ other Components ]
Sodium benzoate, citric acid
Example 1
60g of (A1) organopolysiloxane, (B1) 4g of anionic surfactant, (B2) 2g of anionic surfactant, (B3) 2g of anionic surfactant, (C1) 2g of polyoxyethylene sorbitan fatty acid ester and (E) 2g of water were added to a plastic container having a capacity of 300mL, and the mixture was emulsified by stirring at 2,000rpm using a homogenizer (PRIMIX Corporation, HOMOGENIZING DISPER Model 2.5.5), and the whole was further stirred at 2,000rpm for 5 minutes after emulsification. To this emulsion, 127.5g of (E) water was further added, and the mixture was diluted by stirring at 1,000rpm for 10 minutes using a homomixer (manufactured by PRIMIX Corporation, HOMOGENIZING MIXER MARK II Model 2.5.5), 0.4g of sodium benzoate and 0.1g of citric acid were added, and the mixture was dissolved by stirring at 1,000rpm for 1 minute using a homomixer (manufactured by PRIMIX Corporation, HOMOGENIZING MIXER MARK II Model 2.5).
Example 2
60g of (A1) organopolysiloxane, (B1) 4g of anionic surfactant, (B2) 2g of anionic surfactant, (B3) 2g of anionic surfactant, (C2) 2g of polyoxyethylene sorbitan fatty acid ester and (E) 2g of water were added to a plastic container having a capacity of 300mL, and the mixture was emulsified by stirring at 2,000rpm using a homogenizer (PRIMIX Corporation, HOMOGENIZING DISPER Model 2.5.5), and the whole was further stirred at 2,000rpm for 5 minutes after emulsification. To this emulsion, 127.5g of (E) water was further added, and the mixture was diluted by stirring at 1,000rpm for 10 minutes using a homomixer (manufactured by PRIMIX Corporation, HOMOGENIZING MIXER MARK II Model 2.5.5), 0.4g of sodium benzoate and 0.1g of citric acid were added, and the mixture was dissolved by stirring at 1,000rpm for 1 minute using a homomixer (manufactured by PRIMIX Corporation, HOMOGENIZING MIXER MARK II Model 2.5).
Example 3
60g of (A1) organopolysiloxane, (B1) 4g of anionic surfactant, (B2) 2g of anionic surfactant, (B3) 2g of anionic surfactant, (C1) 2g of polyoxyethylene sorbitan fatty acid ester, (D) 0.5g of polyoxyethylene alkyl ether and (E) 2g of water were added to a plastic container having a capacity of 300mL, and the mixture was emulsified by stirring at 2,000rpm using a homogenizer (PRIMIX Corporation, HOMOGENIZING DISPER Model 2.5.5), and the whole was further stirred at 2,000rpm for 5 minutes after emulsification. To this emulsion, 127g of (E) water was further added, and the mixture was diluted by stirring at 1,000rpm for 10 minutes using a homomixer (manufactured by PRIMIX Corporation, HOMOGENIZING MIXER MARK II Model 2.5.5), 0.4g of sodium benzoate and 0.1g of citric acid were added, and the mixture was dissolved by stirring at 1,000rpm for 1 minute using a homomixer (manufactured by PRIMIX Corporation, HOMOGENIZING MIXER MARK II model 2.5), to prepare an emulsified composition 3.
Example 4
60g of (A2) organopolysiloxane, (B1) 0.4g of anionic surfactant, (B2) 0.2g of anionic surfactant, (B3) 0.2g of anionic surfactant, (C1) polyoxyethylene sorbitan fatty acid ester 0.2g and (E) 4g of water were added to a plastic container having a capacity of 300mL, and the mixture was emulsified by stirring at 2,000rpm using a homomixer (PRIMIX Corporation), 3.6g of (B1) anionic surfactant, (B2) 1.8g of anionic surfactant, (B3) 1.8g of anionic surfactant and (C1) polyoxyethylene sorbitan fatty acid ester 1.8g were added to the whole, and stirred at 2,000rpm for 5 minutes using a homodispenser (PRIMIX Corporation) (HOMOGENIZING DISPER Model.5). To this emulsion, 125.5g of (E) water was further added, and the mixture was diluted by stirring at 1,000rpm for 10 minutes using a homomixer (manufactured by PRIMIX Corporation, HOMOGENIZING MIXER MARK II Model 2.5.5), 0.4g of sodium benzoate and 0.1g of citric acid were added, and the mixture was dissolved by stirring at 1,000rpm for 1 minute using a homomixer (manufactured by PRIMIX Corporation, HOMOGENIZING MIXER MARK II Model 2.5), to prepare an emulsified composition 4.
Example 5
60g of (A2) organopolysiloxane, (B1) 0.4g of anionic surfactant, (B2) 0.2g of anionic surfactant, (B3) 0.2g of anionic surfactant, (C1) 0.2g of polyoxyethylene sorbitan fatty acid ester and (E) 4g of water were added to a plastic container having a capacity of 300mL, and the mixture was emulsified by stirring at 2,000rpm using a homomixer (PRIMIX Corporation, HOMOGENIZING MIXER MARK II Model 2.5.5), 3.6g of (B1) anionic surfactant, (B2) 1.8g of anionic surfactant, (B3) 1.8g of (C1) polyoxyethylene sorbitan fatty acid ester and (D) 0.5g of polyoxyethylene alkyl ether were added after the whole emulsification, and the mixture was stirred at 2,000rpm for 5 minutes using a homodispenser (PRIMIX Corporation, HOMOGENIZING DISPER Model 2.5.5). To this emulsion, 125g of (E) water was further added, and the mixture was diluted by stirring at 1,000rpm for 10 minutes using a homomixer (manufactured by PRIMIX Corporation, HOMOGENIZING MIXER MARK II Model 2.5.5), 0.4g of sodium benzoate and 0.1g of citric acid were added, and the mixture was dissolved by stirring at 1,000rpm for 1 minute using a homomixer (manufactured by PRIMIX Corporation, HOMOGENIZING MIXER MARK II model 2.5), to prepare an emulsified composition 5.
Comparative example 1
60g of (A3) organopolysiloxane, (B1) 4g of anionic surfactant, (B2) 2g of anionic surfactant, (B3) 2g of anionic surfactant, (C1) 2g of polyoxyethylene sorbitan fatty acid ester and (E) 2g of water were added to a plastic container having a capacity of 300mL, and the mixture was emulsified by stirring at 2,000rpm using a homogenizer (PRIMIX Corporation, HOMOGENIZING DISPER Model 2.5.5), and the whole was further stirred at 2,000rpm for 5 minutes after emulsification. To this emulsion, 127.5g of (E) water was further added, and the mixture was diluted by stirring at 1,000rpm for 10 minutes using a homomixer (manufactured by PRIMIX Corporation, HOMOGENIZING MIXER MARK II Model 2.5.5), 0.4g of sodium benzoate and 0.1g of citric acid were added, and the mixture was dissolved by stirring at 1,000rpm for 1 minute using a homomixer (manufactured by PRIMIX Corporation, HOMOGENIZING MIXER MARK II Model 2.5), to prepare an emulsified composition 6.
Comparative example 2
60g of (A1) organopolysiloxane, (C1) polyoxyethylene sorbitan fatty acid ester 6g and (E) water 2g were added to a plastic container having a capacity of 300mL, and the mixture was emulsified by stirring at 2,000rpm using a homogenizer (manufactured by PRIMIX Corporation, HOMOGENIZING DISPER Model 2.5.5), and further stirred at 2,000rpm for 5 minutes after the whole emulsification. To this emulsion, 131.5g of (E) water was further added, and the mixture was diluted by stirring at 1,000rpm for 10 minutes using a homomixer (manufactured by PRIMIX Corporation, HOMOGENIZING MIXER MARK II Model 2.5.5), 0.4g of sodium benzoate and 0.1g of citric acid were added, and the mixture was dissolved by stirring at 1,000rpm for 1 minute using a homomixer (manufactured by PRIMIX Corporation, HOMOGENIZING MIXER MARK II Model 2.5), to prepare an emulsified composition 7.
Comparative example 3
60g of (A1) organopolysiloxane, (B1) 8g of anionic surfactant, (B2) 4g of anionic surfactant, (B3) 4g of anionic surfactant, (C1) 2g of polyoxyethylene sorbitan fatty acid ester and (E) 2g of water were added to a plastic container having a capacity of 300mL, and the mixture was emulsified by stirring at 2,000rpm using a homogenizer (PRIMIX Corporation, HOMOGENIZING DISPER Model 2.5.5), and the whole was further stirred at 2,000rpm for 5 minutes after emulsification. To this emulsion, 119.5g of (E) water was further added, and the mixture was diluted by stirring at 1,000rpm for 10 minutes using a homomixer (manufactured by PRIMIX Corporation, HOMOGENIZING MIXER MARK II Model 2.5.5), 0.4g of sodium benzoate and 0.1g of citric acid were added, and the mixture was dissolved by stirring at 1,000rpm for 1 minute using a homomixer (manufactured by PRIMIX Corporation, HOMOGENIZING MIXER MARK II Model 2.5), to prepare an emulsified composition 8.
Comparative example 4
To a plastic container having a capacity of 300mL, 60g of (A1) organopolysiloxane, (B1) anionic surfactant 4g, (B2) anionic surfactant 2g, (B3) anionic surfactant 2g and (E) water 2g were added, and the mixture was emulsified by stirring at 2,000rpm using a homogenizer (manufactured by PRIMIX Corporation, HOMOGENIZING DISPER Model 2.5.5), and after the whole was emulsified, the mixture was further stirred at 2,000rpm for 5 minutes. To this emulsion, 129.5g of (E) water was further added, and the mixture was diluted by stirring at 1,000rpm for 10 minutes using a homomixer (manufactured by PRIMIX Corporation, HOMOGENIZING MIXER MARK II Model 2.5.5), 0.4g of sodium benzoate and 0.1g of citric acid were added, and the mixture was dissolved by stirring at 1,000rpm for 1 minute using a homomixer (manufactured by PRIMIX Corporation, HOMOGENIZING MIXER MARK II model 2.5), to prepare an emulsified composition 9.
Comparative example 5
60g of (A1) organopolysiloxane, (B1) 4g of anionic surfactant, (B2) 2g of anionic surfactant, (B3) 2g of anionic surfactant, (D) 0.5g of polyoxyethylene alkyl ether and (E) 2g of water were added to a plastic container having a capacity of 300mL, and the mixture was emulsified by stirring at 2,000rpm using a homogenizer (PRIMIX Corporation, HOMOGENIZING DISPER Model 2.5.5), and the whole was further stirred at 2,000rpm for 5 minutes after emulsification. To this emulsion, 129g of (E) water was further added, and the mixture was diluted by stirring at 1,000rpm for 10 minutes using a homomixer (manufactured by PRIMIX Corporation, HOMOGENIZING MIXER MARK II Model 2.5.5), 0.4g of sodium benzoate and 0.1g of citric acid were added, and the mixture was dissolved by stirring at 1,000rpm for 1 minute using a homomixer (manufactured by PRIMIX Corporation, HOMOGENIZING MIXER MARK II Model 2.5), to prepare an emulsified composition 10.
Comparative example 6
60g of (A1) organopolysiloxane, (B1) 4g of anionic surfactant, (B2) 2g of anionic surfactant, (B3) 2g of anionic surfactant, (D) 2g of polyoxyethylene alkyl ether and (E) 2g of water were added to a plastic container having a capacity of 300mL, and the mixture was emulsified by stirring at 2,000rpm using a homogenizer (manufactured by PRIMIX Corporation), HOMOGENIZING DISPER Model 2.5.5, and further stirred at 2,000rpm for 5 minutes after the whole was emulsified. To this emulsion, 127.5g of (E) water was further added, and the mixture was diluted by stirring at 1,000rpm for 10 minutes using a homomixer (manufactured by PRIMIX Corporation, HOMOGENIZING MIXER MARK II Model 2.5.5), 0.4g of sodium benzoate and 0.1g of citric acid were added, and the mixture was dissolved by stirring at 1,000rpm for 1 minute using a homomixer (manufactured by PRIMIX Corporation, HOMOGENIZING MIXER MARK II Model 2.5), to prepare an emulsified composition 11.
Comparative example 7
60g of (A1) organopolysiloxane, (B1) 4g of anionic surfactant, (B2) 2g of anionic surfactant, (B3) 2g of anionic surfactant, (C3) 2g of polyoxyethylene sorbitan fatty acid ester and (E) 2g of water were added to a plastic container having a capacity of 300mL, and the mixture was emulsified by stirring at 2,000rpm using a homogenizer (PRIMIX Corporation, HOMOGENIZING DISPER Model 2.5.5), and the whole was further stirred at 2,000rpm for 5 minutes after emulsification. To this emulsion, 127.5g of (E) water was further added, and the mixture was diluted by stirring at 1,000rpm for 10 minutes using a homomixer (manufactured by PRIMIX Corporation, HOMOGENIZING MIXER MARK II Model 2.5.5), 0.4g of sodium benzoate and 0.1g of citric acid were added, and the mixture was dissolved by stirring at 1,000rpm for 1 minute using a homomixer (manufactured by PRIMIX Corporation, HOMOGENIZING MIXER MARK II Model 2.5).
Comparative example 8
60g of (A1) organopolysiloxane, (B1) 4g of anionic surfactant, (B2) 2g of anionic surfactant, (B3) 2g of anionic surfactant, (C3) 2g of polyoxyethylene sorbitan fatty acid ester, (D) 0.5g of polyoxyethylene alkyl ether and (E) 2g of water were added to a plastic container having a capacity of 300mL, and the mixture was emulsified by stirring at 2,000rpm using a homogenizer (PRIMIX Corporation, HOMOGENIZING DISPER Model 2.5.5), and the whole was further stirred at 2,000rpm for 5 minutes after emulsification. To this emulsion, 127g of (E) water was further added, and the mixture was diluted by stirring at 1,000rpm for 10 minutes using a homomixer (manufactured by PRIMIX Corporation, HOMOGENIZING MIXER MARK II Model 2.5.5), 0.4g of sodium benzoate and 0.1g of citric acid were added, and the mixture was dissolved by stirring at 1,000rpm for 1 minute using a homomixer (manufactured by PRIMIX Corporation, HOMOGENIZING MIXER MARK II model 2.5), to prepare an emulsified composition 13.
Comparative example 9
60g of (A1) organopolysiloxane, (B1) 4g of anionic surfactant, (B2) 2g of anionic surfactant, (B3) 2g of anionic surfactant, (C1) 7g of polyoxyethylene sorbitan fatty acid ester and (E) 2g of water were added to a plastic container having a capacity of 300mL, and the mixture was emulsified by stirring at 2,000rpm using a homogenizer (PRIMIX Corporation, HOMOGENIZING DISPER Model 2.5.5), and the whole was further stirred at 2,000rpm for 5 minutes after emulsification. To this emulsion, 122.5g of (E) water was further added, and the mixture was diluted by stirring at 1,000rpm for 10 minutes using a homomixer (manufactured by PRIMIX Corporation, HOMOGENIZING MIXER MARK II Model 2.5.5), 0.4g of sodium benzoate and 0.1g of citric acid were added, and the mixture was dissolved by stirring at 1,000rpm for 1 minute using a homomixer (manufactured by PRIMIX Corporation, HOMOGENIZING MIXER MARK II Model 2.5).
Comparative example 10
60g of (A1) organopolysiloxane, (B1) 4g of anionic surfactant, (B2) 2g of anionic surfactant, (B3) 2g of anionic surfactant, (C1) 2g of polyoxyethylene sorbitan fatty acid ester and (E) 4g of water were added to a plastic container having a capacity of 300mL, and the mixture was emulsified by stirring at 2,000rpm using a homogenizer (PRIMIX Corporation, HOMOGENIZING DISPER Model 2.5.5), and the whole was further stirred at 2,000rpm for 5 minutes after emulsification. To this emulsion, 125.5g of (E) water was further added, and the mixture was diluted by stirring at 1,000rpm for 10 minutes using a homomixer (manufactured by PRIMIX Corporation, HOMOGENIZING MIXER MARK II Model 2.5.5), 0.4g of sodium benzoate and 0.1g of citric acid were added, and the mixture was dissolved by stirring at 1,000rpm for 1 minute using a homomixer (manufactured by PRIMIX Corporation, HOMOGENIZING MIXER MARK II Model 2.5), to prepare an emulsified composition 15.
Comparative example 11
60g of (A1) organopolysiloxane, (B1) 4g of anionic surfactant, (B2) 2g of anionic surfactant, (B3) 2g of anionic surfactant, (C1) 5g of polyoxyethylene sorbitan fatty acid ester, (D) 4g of polyoxyethylene alkyl ether and (E) 2g of water were added to a plastic container having a capacity of 300mL, and the mixture was emulsified by stirring at 2,000rpm using a homogenizer (PRIMIX Corporation, HOMOGENIZING DISPER Model 2.5.5), and the whole was further stirred at 2,000rpm for 5 minutes after emulsification. To this emulsion, 120.5g of (E) water was further added, and the mixture was diluted by stirring at 1,000rpm for 10 minutes using a homomixer (manufactured by PRIMIX Corporation, HOMOGENIZING MIXER MARK II Model 2.5.5), 0.4g of sodium benzoate and 0.1g of citric acid were added, and the mixture was dissolved by stirring at 1,000rpm for 1 minute using a homomixer (manufactured by PRIMIX Corporation, HOMOGENIZING MIXER MARK II Model 2.5), to prepare an emulsified composition 16.
The above examples and comparative examples were evaluated for average particle diameter, pH, centrifugal separation stability, water dilution stability, mechanical stability, wettability to PET film, and stress cracking to biaxially stretched polystyrene film. Details of the evaluation method are described below.
[ average particle diameter ]
The average particle diameter was a particle diameter obtained by diluting the emulsified compositions 1 to 16 to 10 times with ion-exchanged water, and the cumulative value in the volume-based particle size distribution measured by a laser diffraction/scattering particle size distribution measuring apparatus (HORIBA, manufactured by ltd., particle LA-960) was 50%.
[pH]
The pH was measured at 25℃using a pH meter (HORIBA, manufactured by Ltd., LAQUA F-52) and an electrode (HORIBA, manufactured by Ltd., 9615S-10D) to obtain the emulsified compositions 1 to 16.
[ stability of centrifugal separation ]
The emulsified compositions 1 to 16 were placed in a polypropylene centrifuge tube (Thermo Fisher Scientific, manufactured by inc.) having a capacity of about 15mL, and the tube was rotated at 3,000rpm (centrifugal force: about 1,000Xg) for 15 minutes using a small-sized table centrifuge (manufactured by Kekusen Co., ltd., H-19 FM), and then 1.0g of each of the upper and lower layers of the centrifuge tube was collected and placed in an aluminum culture dish, and heated at 105℃for 3 hours, whereby a nonvolatile component was calculated according to the following formula (5).
Nonvolatile component (%) = (1-drying decrement (g)/collection amount (g)) ×100 (5)
It is considered that the value obtained by dividing the non-volatile component in the upper layer by the non-volatile component in the lower layer is less likely to cause the separation of the gradation with time and has high storage stability as the value is closer to 1.
O: non-volatile component of upper layer part/non-volatile component of lower layer part of 0.95-1.05
X: the non-volatile component of the upper layer part/the non-volatile component of the lower layer part is less than 0.95
1.05 < non-volatile component of upper layer/non-volatile component of lower layer
In the present specification, "o" is determined to be good, and "x" is determined to be bad.
[ stability to dilution with Water ]
To a 200mL glass beaker was added 2g of the emulsified composition 1 to 16, and further 98g of water for dilution. The appearance after standing at room temperature for 22 hours was confirmed and evaluated according to the following criteria.
O: no shade separation occurred, showing a uniform appearance.
No oil stain or interference film or about 1 to 3 interference films are generated on the surface.
Delta: no shade separation occurred, showing a uniform appearance.
Some oil stains are generated on the surface or about 3 to 6 interference films are generated.
X: a shade separation occurs, showing a non-uniform appearance.
Oil stains are generated on the surface or interference films with the surface area being more than 6 degrees are generated.
In the present specification, "o" and "Δ" are determined to be good, and "x" is determined to be bad.
[ mechanical stability ]
To a plastic container having a capacity of 200mL, 10g of the emulsified composition 1 to 16 was added, and further 90g of water was added, and the mixture was stirred at 3,000rpm for 10 minutes using a homomixer (manufactured by PRIMIX Corporation, HOMOGENIZING MIXER MARK II Model 2.5.5). The appearance after standing at room temperature for 22 hours was confirmed and evaluated according to the following criteria.
O: no shade separation occurred, showing a uniform appearance.
No oil stain or interference film or about 1 to 3 interference films are generated on the surface.
Delta: no shade separation occurred, showing a uniform appearance.
Some oil stains are generated on the surface or about 3 to 6 interference films are generated.
X: a shade separation occurs, showing a non-uniform appearance.
Oil stains are generated on the surface or interference films with the surface area being more than 6 degrees are generated.
In the present specification, "o" and "Δ" are determined to be good, and "x" is determined to be bad.
[ wettability ]
The emulsified compositions 1 to 16 were diluted 10 times with ion-exchanged water, and coated on a PET film (trade name: lumirrorS-10 (thickness: 50 μm), manufactured by TORAY INDUSTRIES, INC.) using a bar No.3 (manufactured by R.D.Specialties, U.S.A). The occurrence of the edge shrinkage was visually confirmed.
O: wetting the whole.
Delta: a fringing occurs at a portion.
X: shrinkage edges occur on the whole immediately after coating.
In the present specification, "o" and "Δ" are determined to be good, and "x" is determined to be bad.
[ cracking Property ]
The emulsified compositions 1 to 16 were diluted to 20 times with ion-exchanged water, and coated on a biaxially stretched polystyrene film (trade name: OPS sheet, manufactured by Asahi Kasei corporation) with gauze. The OPS sheet coated with the emulsified composition was wound around a cylinder having a diameter of 40mm, and whether or not cracks were generated was visually confirmed.
O: no cracks were generated within 300 seconds after winding on the drum
X: cracking within 300 seconds after winding on a tube
In the present specification, "o" is determined to be good, and "x" is determined to be bad.
The evaluation results are shown in Table 1. In the following, "parts" refers to parts by mass. The compositions of the component (B1) and the component (B3) are described in parentheses as the blending parts as the effective components in addition to the blending parts as the product. For example, since the active ingredient of the component (B1) is 65%, the blending of 2 parts is described as "2 (1.3)".
From the above evaluation results, it was found that the release agent for plastics of the present invention is excellent in centrifugal separation stability, dilution stability, and mechanical stability, has relatively good wettability, and is less likely to cause cracks in plastics.
In comparative example 1 in which the component (a) contains about 2% of octamethyl cyclotetrasiloxane, decamethyl cyclopentasiloxane and dodecamethyl cyclohexasiloxane, respectively, mechanical stability and the like are slightly lowered, and cracking property is poor.
In comparative example 2 in which component (B) was not contained and component (a) was emulsified with only component (C), although wettability was improved, centrifugal separation stability, water dilution stability, mechanical stability, and cracking property were poor. On the other hand, in comparative example 3 in which the emulsification was performed with an excessive amount of component (B), the cracking property was good, but the centrifugal separation stability and wettability were poor.
In comparative example 4 in which component (a) was emulsified with only component (B) and comparative example 5 in which component (a) was emulsified with component (B) and component (D), the particle size was increased, and the centrifugal separation stability, the water dilution stability, the mechanical stability, and the wettability were poor. In comparative example 6 in which component (a) was emulsified with component (B) and component (D) in a larger amount than comparative example 5, the particle size was reduced, and the centrifugal separation stability, water dilution stability, mechanical stability and wettability were improved, but the cracking property was poor.
In comparative example 7 in which component (A) was emulsified with component (B) and a polyoxyethylene sorbitan fatty acid ester different from component (C) of the present invention, the particle diameter became large and the centrifugal separation stability was poor, and the polyoxyethylene sorbitan fatty acid ester was represented by the following general formula (2), wherein R in formula (2) 2 The sum of a+b+c is 6, which is an alkyl group having 18 carbon atoms. In comparative example 8 in which component (a) was emulsified with component (D) in addition to the surfactant used in comparative example 7, the centrifugal separation stability was poor although the particle size was small.
[ chemical formula 9]
In comparative example 9 in which component (A) was emulsified with component (B) and an excessive amount of component (C), the cracking was poor.
In comparative example 10, which had the same blend composition as in example 1, but had an average particle diameter of more than 350nm by increasing the blend fraction of component (E), the centrifugal separation stability and mechanical stability were poor. On the other hand, in comparative example 11 in which the average particle diameter was smaller than 200nm, the cracking was poor by increasing the blending proportion of the component (D).
In addition, the present invention is not limited to the above embodiments. The above embodiments are examples, and all embodiments having substantially the same constitution and exhibiting the same effects as the technical idea described in the claims of the present invention are included in the scope of the present invention.
Claims (6)
1. A release agent for plastics, which is an emulsion having an average particle diameter of more than 200nm and 350nm or less, and contains the following components (A) to (C) and (E):
(A) An organopolysiloxane represented by the following general formula (1) having a dynamic viscosity of 100 to 100,000mm at 25 DEG C 2 And the content of octamethyl cyclotetrasiloxane, decamethyl cyclopentasiloxane and dodecamethyl cyclohexasiloxane is respectively less than 1 mass%: 100 parts by mass of the components in the total mass,
[ chemical formula 1]
In the formula (1), R 1 Optionally identical or different, R 1 Is any one of hydroxyl, hydrogen atom, unsubstituted straight-chain alkyl with 1-32 carbon atoms and phenyl, L is an integer of 60-1,500;
(B) Anionic surfactant: 0.1 to 18.0 parts by mass;
(C) A polyoxyethylene sorbitan fatty acid ester represented by the following general formula (2): 0.1 to 10.0 parts by mass,
[ chemical formula 2]
In the formula (2), R 2 An alkyl group having 8 to 24 carbon atoms, a, b and c are independently integers of 0 or more, and the total of a+b+c is 8 to 30;
(E) Water: 50 to 100,000 parts by mass.
2. The release agent for plastic according to claim 1, further comprising less than 1.0 part by mass of (D) a polyoxyethylene alkyl ether represented by the following general formula (3), wherein the total content of the (C) component and the (D) component is 0.1 to 10.0 parts by mass,
C m H 2m+1 (OCH 2 CH 2 ) n OH(3)
in the formula (3), m is an integer of 12 to 20, and n is an integer of 4 to 50.
3. The release agent for plastics according to claim 1 or 2, wherein the HLB of the component (C) is 12 to 18.
4. The release agent for plastics according to any one of claims 1 to 3, wherein the component (B) is an anionic surfactant selected from 1 or 2 or more of alkyl sulfate salts, alkyl sulfonate salts, alkylbenzenesulfonate salts, alkyl naphthalene sulfonate salts, alkyl sulfosuccinate salts, alkyl phosphate salts, polyoxyethylene alkyl ether sulfate salts, polyoxyethylene alkyl ether phosphate salts.
5. The release agent for plastic according to any one of claims 1 to 4, wherein the pH of the release agent for plastic at 25 ℃ is 4.0 to 10.0.
6. The release agent for plastic according to any one of claims 1 to 5, wherein the plastic is used for food container packaging.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2020179356A JP7181915B2 (en) | 2020-10-27 | 2020-10-27 | Release agent for plastic |
| JP2020-179356 | 2020-10-27 | ||
| PCT/JP2021/036029 WO2022091684A1 (en) | 2020-10-27 | 2021-09-30 | Release agent for plastic |
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|---|---|
| CN116490553A true CN116490553A (en) | 2023-07-25 |
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| CN202180070886.5A Pending CN116490553A (en) | 2020-10-27 | 2021-09-30 | Release agent for plastics |
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| JP (1) | JP7181915B2 (en) |
| KR (1) | KR20230095067A (en) |
| CN (1) | CN116490553A (en) |
| TW (1) | TW202219129A (en) |
| WO (1) | WO2022091684A1 (en) |
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| JPH0791529B2 (en) * | 1993-12-27 | 1995-10-04 | 東レ・ダウコーニング・シリコーン株式会社 | Emulsion type release agent |
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| JP3916740B2 (en) * | 1997-11-07 | 2007-05-23 | 信越化学工業株式会社 | Aqueous dispersion of spherical silicone rubber |
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| JP4630435B2 (en) * | 2000-09-18 | 2011-02-09 | サンディック株式会社 | Styrenic resin anti-fog sheet |
| JP4828054B2 (en) | 2001-08-31 | 2011-11-30 | 東レ・ダウコーニング株式会社 | Oil-in-water organopolysiloxane emulsion |
| JP2004035820A (en) | 2002-07-05 | 2004-02-05 | Ge Toshiba Silicones Co Ltd | Silicone emulsion composition and releasing agent |
| JP2004331784A (en) | 2003-05-07 | 2004-11-25 | Ge Toshiba Silicones Co Ltd | Silicone emulsion composition |
| JP2005281409A (en) | 2004-03-29 | 2005-10-13 | Ge Toshiba Silicones Co Ltd | Silicone mold release agent composition |
| JP4722542B2 (en) | 2005-04-28 | 2011-07-13 | モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社 | Silicone emulsion composition |
| JP6767742B2 (en) | 2014-11-14 | 2020-10-14 | ダイセルポリマー株式会社 | Aqueous surface treatment agent and coating sheet and method for improving coatability |
| JP6476980B2 (en) | 2015-02-20 | 2019-03-06 | 信越化学工業株式会社 | Release agent for tire bladder, tire bladder and pneumatic tire |
| JP6387885B2 (en) | 2015-04-06 | 2018-09-12 | 信越化学工業株式会社 | Organopolysiloxane emulsion composition for release paper or release film, method for producing the same, release paper and release film |
| JP6877819B2 (en) | 2015-12-25 | 2021-05-26 | 旭化成ワッカーシリコーン株式会社 | Oil-in-water silicone emulsion composition for release coating and release film using this |
-
2020
- 2020-10-27 JP JP2020179356A patent/JP7181915B2/en active Active
-
2021
- 2021-09-30 WO PCT/JP2021/036029 patent/WO2022091684A1/en active Application Filing
- 2021-09-30 CN CN202180070886.5A patent/CN116490553A/en active Pending
- 2021-09-30 KR KR1020237012275A patent/KR20230095067A/en unknown
- 2021-10-04 TW TW110136824A patent/TW202219129A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| WO2022091684A1 (en) | 2022-05-05 |
| JP7181915B2 (en) | 2022-12-01 |
| KR20230095067A (en) | 2023-06-28 |
| TW202219129A (en) | 2022-05-16 |
| JP2022070338A (en) | 2022-05-13 |
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