JP2021023891A - Defoaming agent and vinyl chloride resin manufacturing method - Google Patents
Defoaming agent and vinyl chloride resin manufacturing method Download PDFInfo
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- JP2021023891A JP2021023891A JP2019144834A JP2019144834A JP2021023891A JP 2021023891 A JP2021023891 A JP 2021023891A JP 2019144834 A JP2019144834 A JP 2019144834A JP 2019144834 A JP2019144834 A JP 2019144834A JP 2021023891 A JP2021023891 A JP 2021023891A
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- Prior art keywords
- polyether compound
- defoaming agent
- vinyl chloride
- chloride resin
- parts
- 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.)
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- 239000002518 antifoaming agent Substances 0.000 title claims abstract description 63
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims description 44
- 229920005989 resin Polymers 0.000 title claims description 39
- 239000011347 resin Substances 0.000 title claims description 39
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 104
- 229920000570 polyether Polymers 0.000 claims abstract description 104
- 150000001875 compounds Chemical class 0.000 claims abstract description 103
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 4
- 125000006353 oxyethylene group Chemical group 0.000 claims abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 84
- 230000002209 hydrophobic effect Effects 0.000 claims description 33
- 239000000377 silicon dioxide Substances 0.000 claims description 30
- 239000002199 base oil Substances 0.000 claims description 20
- 125000004432 carbon atom Chemical group C* 0.000 claims description 20
- 239000002002 slurry Substances 0.000 claims description 20
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- -1 oxypropylene group Chemical group 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 8
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 abstract description 14
- 238000005187 foaming Methods 0.000 abstract description 14
- 239000006185 dispersion Substances 0.000 abstract description 8
- 239000002245 particle Substances 0.000 abstract description 8
- 239000007788 liquid Substances 0.000 abstract description 7
- 229940126062 Compound A Drugs 0.000 abstract 2
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 abstract 2
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 abstract 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 12
- 239000012085 test solution Substances 0.000 description 10
- 235000005956 Cosmos caudatus Nutrition 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 8
- 239000006260 foam Substances 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 235000019198 oils Nutrition 0.000 description 7
- 229920001451 polypropylene glycol Polymers 0.000 description 7
- 229910002012 Aerosil® Inorganic materials 0.000 description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- 235000011187 glycerol Nutrition 0.000 description 6
- 239000002480 mineral oil Substances 0.000 description 6
- 229920001296 polysiloxane Polymers 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 239000011118 polyvinyl acetate Substances 0.000 description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 description 5
- 230000002265 prevention Effects 0.000 description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- QGHUMKWGRCLYQU-UHFFFAOYSA-N butan-1-ol;2-methyloxirane Chemical compound CC1CO1.CCCCO QGHUMKWGRCLYQU-UHFFFAOYSA-N 0.000 description 4
- 239000013530 defoamer Substances 0.000 description 4
- 239000004205 dimethyl polysiloxane Substances 0.000 description 4
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 235000010446 mineral oil Nutrition 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229920002689 polyvinyl acetate Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000007127 saponification reaction Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 101150096839 Fcmr gene Proteins 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000003925 fat Substances 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229920002545 silicone oil Polymers 0.000 description 3
- 229920002050 silicone resin Polymers 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 235000019482 Palm oil Nutrition 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical group CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 230000003254 anti-foaming effect Effects 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 229940105990 diglycerin Drugs 0.000 description 2
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 235000019197 fats Nutrition 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 239000008235 industrial water Substances 0.000 description 2
- KDQIFKKWPMBNOH-UHFFFAOYSA-N methyl 16-methylheptadecanoate Chemical compound COC(=O)CCCCCCCCCCCCCCC(C)C KDQIFKKWPMBNOH-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000002540 palm oil Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 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
- AKUNSTOMHUXJOZ-UHFFFAOYSA-N 1-hydroperoxybutane Chemical compound CCCCOO AKUNSTOMHUXJOZ-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000005529 alkyleneoxy group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- IYYIVELXUANFED-UHFFFAOYSA-N bromo(trimethyl)silane Chemical compound C[Si](C)(C)Br IYYIVELXUANFED-UHFFFAOYSA-N 0.000 description 1
- 230000005587 bubbling Effects 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
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- BAAAEEDPKUHLID-UHFFFAOYSA-N decyl(triethoxy)silane Chemical compound CCCCCCCCCC[Si](OCC)(OCC)OCC BAAAEEDPKUHLID-UHFFFAOYSA-N 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- OSXYHAQZDCICNX-UHFFFAOYSA-N dichloro(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](Cl)(Cl)C1=CC=CC=C1 OSXYHAQZDCICNX-UHFFFAOYSA-N 0.000 description 1
- GNEPOXWQWFSSOU-UHFFFAOYSA-N dichloro-methyl-phenylsilane Chemical compound C[Si](Cl)(Cl)C1=CC=CC=C1 GNEPOXWQWFSSOU-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- QYDYPVFESGNLHU-UHFFFAOYSA-N elaidic acid methyl ester Natural products CCCCCCCCC=CCCCCCCCC(=O)OC QYDYPVFESGNLHU-UHFFFAOYSA-N 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 235000021323 fish oil Nutrition 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- QYDYPVFESGNLHU-KHPPLWFESA-N methyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC QYDYPVFESGNLHU-KHPPLWFESA-N 0.000 description 1
- 229940073769 methyl oleate Drugs 0.000 description 1
- 239000005055 methyl trichlorosilane Substances 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
- WIBFFTLQMKKBLZ-SEYXRHQNSA-N n-butyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCCCC WIBFFTLQMKKBLZ-SEYXRHQNSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 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 description 1
- 239000004006 olive oil Substances 0.000 description 1
- 235000008390 olive oil Nutrition 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- BCNZYOJHNLTNEZ-UHFFFAOYSA-N tert-butyldimethylsilyl chloride Chemical compound CC(C)(C)[Si](C)(C)Cl BCNZYOJHNLTNEZ-UHFFFAOYSA-N 0.000 description 1
- ZOYFEXPFPVDYIS-UHFFFAOYSA-N trichloro(ethyl)silane Chemical compound CC[Si](Cl)(Cl)Cl ZOYFEXPFPVDYIS-UHFFFAOYSA-N 0.000 description 1
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 1
- 239000005052 trichlorosilane Substances 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- NMEPHPOFYLLFTK-UHFFFAOYSA-N trimethoxy(octyl)silane Chemical compound CCCCCCCC[Si](OC)(OC)OC NMEPHPOFYLLFTK-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002349 well water Substances 0.000 description 1
- 235000020681 well water Nutrition 0.000 description 1
Abstract
Description
本発明は、消泡剤及びこれを用いる塩化ビニル系樹脂の製造方法に関する。 The present invention relates to an antifoaming agent and a method for producing a vinyl chloride resin using the same.
ポリオキシアルキレン化合物を含有する消泡剤として、疎水性シリカと−５０〜２℃の流動点を有する炭化水素油とを含んでなる疎水性シリカ分散液、ポリオキシアルキレン化合物及びポリオキシアルキレン多価アルコール脂肪酸エステルを含有することを特徴とする消泡剤（特許文献１）や、Ｒ１Ｏ（ＡＯ）ｎＨ（Ｒ１は炭素数８〜２２のアルキル基、アルケニル基、または炭素数６〜３０のアリール基を示し、ＡＯは炭素数２〜４のアルキレンオキシ基、ｎは１〜１００の整数を示す。）で表され、グリフィンのＨＬＢが１〜６のアルキレンオキサイド付加物を含有するクラフトパルプ製造工程用消泡剤（特許文献２）が知られている。
また、塩化ビニル系樹脂の製造方法において、発泡防止成分として、（１）部分ケン化ポリ酢酸ビニル、（２）高粘度エーテル（高粘度の水溶性セルロースエーテル又はポリアルキレンオキサイド（ポリエチレンオキサイド、エチレンオキサイド・プロピレンオキサイド共重合体；高粘度エーテルは、上記の部分ケン化ポリ酢酸ビニルと併用することが重要である。）、（３）消泡剤（部分ケン化ポリ酢酸ビニルと高粘度エーテルと併用することにより、発泡防止の向上を図ることができる；アセチレングリコール等のポリアルキレングリコール系消泡剤；ポリアルキレンアマイド等のアマイド系消泡剤、シリコーン消泡剤）を特定の添加条件（添加開始時期及び添加量）で行う方法（特許文献３の００１２〜００１４段落等）が知られている。
As a defoaming agent containing a polyoxyalkylene compound, a hydrophobic silica dispersion containing hydrophobic silica and a hydrocarbon oil having a flow point of −50 to 2 ° C., a polyoxyalkylene compound and a polyoxyalkylene polyvalent An antifoaming agent (Patent Document 1) containing an alcohol fatty acid ester, R 1 O (AO) n H (R 1 is an alkyl group having 8 to 22 carbon atoms, an alkenyl group, or 6 to 6 carbon atoms). A craft containing an aryl group of 30, AO representing an alkyleneoxy group having 2 to 4 carbon atoms, n representing an integer of 1 to 100), and an alkylene oxide adduct having an HLB of Griffin of 1 to 6. A defoaming agent for a pulp manufacturing process (Patent Document 2) is known.
Further, in the method for producing a vinyl chloride resin, as foaming prevention components, (1) partially saponified polyvinyl acetate, (2) high viscosity ether (high viscosity water-soluble cellulose ether or polyalkylene oxide (polyethylene oxide, ethylene oxide)) -Propropylene oxide copolymer; it is important that the high-viscosity ether is used in combination with the above-mentioned partially saponified polyvinyl acetate), (3) Defoamer (in combination with the partially saponified polyvinyl acetate and high-viscosity ether). By doing so, it is possible to improve the prevention of foaming; a polyalkylene glycol defoamer such as acetylene glycol; an amide defoamer such as polyalkylene amide, a silicone defoamer) under specific addition conditions (start of addition). A method (paragraphs 0012 to 0014 of Patent Document 3 and the like) is known.
特許文献３の００１０段落に、「本件の場合、発泡防止成分として、通常の消泡剤を用いたのでは、十分な発泡防止は不可能である。即ち、本件の発泡は、懸濁（分散）剤に起因する泡（懸濁剤の泡）と塩化ビニル系重合体の粉末を多く含有する泡（重合体の泡）が複雑に絡み合っているために、消泡剤の作用が十分に発揮されないという特段の事由が想定される。このため、本件の場合、上記の複雑に絡み合っている泡、即ち、「懸濁剤の泡」と「重合体の泡」の凝集を阻止することが必要になるが、本発明が発泡防止成分として採用した、水溶性の部分ケン化ポリ酢酸ビニルと高粘度エーテルは、その添加条件と相俟って、両泡の分散を促し、凝集を防止して、該泡の成長を阻止するという作用を十分に発揮することにより、問題となる発泡防止に寄与しているものと考えられる。」と記載されているように、発泡成分及び懸濁粒子を含む発泡性分散液体（特に塩化ビニル系樹脂スラリー）に対して、従来の消泡剤では、消泡性が不十分であるという問題がある。
本発明の目的は、発泡成分及び懸濁粒子を含む発泡性分散液体（特に塩化ビニル系樹脂スラリー）に対しても優れた消泡性を発揮する消泡剤を提供することである。
In paragraph 0010 of Patent Document 3, "In this case, it is impossible to sufficiently prevent foaming by using an ordinary antifoaming agent as the foaming prevention component. That is, the foaming of the present case is suspended (dispersed). ) The foam caused by the agent (suspension foam) and the foam containing a large amount of vinyl chloride polymer powder (polymer foam) are intricately intertwined, so that the defoaming agent works sufficiently. Therefore, in this case, it is necessary to prevent the agglomeration of the above-mentioned intricately intertwined bubbles, that is, "suspension agent bubbles" and "polymer bubbles". However, the water-soluble partially saponified polyvinyl acetate and high-viscosity ether adopted as the foaming prevention component in the present invention promote the dispersion of both bubbles and prevent aggregation in combination with the addition conditions. , It is considered that it contributes to the prevention of foaming, which is a problem, by sufficiently exerting the action of inhibiting the growth of the foam. As described in the above, there is a problem that the conventional defoaming agent has insufficient defoaming property with respect to the effervescent dispersed liquid (particularly vinyl chloride resin slurry) containing the effervescent component and the suspended particles. There is.
An object of the present invention is to provide a defoaming agent that exhibits excellent defoaming properties even for a foaming dispersion liquid (particularly a vinyl chloride resin slurry) containing a foaming component and suspended particles.
本発明の消泡剤は、一般式（１）で表されるポリエーテル化合物（Ａ）、一般式（２）で表されるポリエーテル化合物（Ｂ）及び一般式（３）で表されるポリエーテル化合物（Ｃ）を含有し、
ポリエーテル化合物（Ａ）の含有量が１〜１５重量％、ポリエーテル化合物（Ｂ）の含有量が２０〜５９重量％、ポリエーテル化合物（Ｃ）の含有量が４０〜７９重量％であることを特徴とする。
The defoaming agent of the present invention is a polyether compound (A) represented by the general formula (1), a polyether compound (B) represented by the general formula (2), and a poly represented by the general formula (3). Contains the ether compound (C)
The content of the polyether compound (A) is 1 to 15% by weight, the content of the polyether compound (B) is 20 to 59% by weight, and the content of the polyether compound (C) is 40 to 79% by weight. It is characterized by.
Ｒ１Ｏ-（ＰＯ）ｎ-Ｈ （１）
ＨＯ-（ＰＯ）ｍ-Ｈ （２）
Ｒ２-｛（ＰＯ）ｑ-（ＥＯ）ｐ-Ｈ｝ｓ （３）
R 1 O- (PO) n -H (1)
HO- (PO) m -H (2)
R 2 -{(PO) q- (EO) p -H} s (3)
Ｒ１は炭素数１〜４のアルキル基、Ｒ２は炭素数３〜６のｓ価アルコールの反応残基、ＰＯはオキシプロピレン基、ＥＯはオキシエチレン基を表し、ｎは１〜５０の整数、ｍは３〜１００の、ｑは１〜３０の整数、ｐは１〜１０の整数であり、ｓは３または４の整数でｓ個の｛（ＰＯ）ｍ-（ＥＯ）ｐ-Ｈ｝はそれぞれ同じでも異なっていてもよい。 R 1 is an alkyl group having 1 to 4 carbon atoms, R 2 is a reaction residue of an s-valent alcohol having 3 to 6 carbon atoms, PO is an oxypropylene group, EO is an oxyethylene group, and n is an integer of 1 to 50. , M is 3 to 100, q is an integer of 1 to 30, p is an integer of 1 to 10, s is an integer of 3 or 4, and s {(PO) m- (EO) p -H} May be the same or different.
本発明の塩化ビニル系樹脂の製造方法の特徴は、上記の消泡剤の存在下で単量体を重合させて塩化ビニル系樹脂スラリーを得る重合工程を含む点；または上記の消泡剤の存在下で塩化ビニル系樹脂スラリーから残留モノマーを回収及び／又は除去する脱モノマー工程を含む点を要旨とする。 The feature of the method for producing a vinyl chloride resin of the present invention is that it includes a polymerization step of polymerizing a monomer in the presence of the above-mentioned antifoaming agent to obtain a vinyl chloride-based resin slurry; or the above-mentioned antifoaming agent. The gist is that it includes a demonomerization step of recovering and / or removing the residual monomer from the vinyl chloride resin slurry in the presence.
本発明の消泡剤は、消泡性に優れ、発泡成分及び懸濁粒子を含む発泡性分散液体（特に塩化ビニル系樹脂スラリー）に対しても優れた消泡性を発揮する。 The defoaming agent of the present invention has excellent defoaming properties, and also exhibits excellent defoaming properties for effervescent dispersed liquids (particularly vinyl chloride resin slurries) containing effervescent components and suspended particles.
本発明の塩化ビニル系樹脂の製造方法は、上記の消泡剤を用いるので生産性に優れ、得られる塩化ビニル系樹脂の物性が優れる。 Since the above-mentioned defoaming agent is used in the method for producing a vinyl chloride resin of the present invention, the productivity is excellent, and the physical properties of the obtained vinyl chloride resin are excellent.
＜一般式（１）で表されるポリエーテル化合物（Ａ）＞
炭素数１〜４のアルキル基（Ｒ１）としては、メチル、エチル、プロピル、イソブチル及びｎ−ブチルが含まれる。これらのうち、消泡性の観点から、ブチル及びメチルが好ましく、さらに好ましくはｎ−ブチルである。
<Polyether compound (A) represented by the general formula (1)>
Alkyl groups (R 1 ) having 1 to 4 carbon atoms include methyl, ethyl, propyl, isobutyl and n-butyl. Of these, butyl and methyl are preferable, and n-butyl is more preferable, from the viewpoint of defoaming property.
ｎは、１〜５０の整数であり、消泡性の観点から、２〜４６の整数が好ましく、さらに好ましくは３〜４３の整数、特に好ましくは４〜４０の整数である。 n is an integer of 1 to 50, preferably an integer of 2 to 46 from the viewpoint of defoaming property, more preferably an integer of 3 to 43, and particularly preferably an integer of 4 to 40.
ポリエーテル化合物（Ａ）の好ましい例としては、ｎ−ブタノールのプロピレンオキシド（５モル）付加物、ｎ−ブタノールのプロピレンオキシド（２５モル）付加物、ｎ−ブタノールのプロピレンオキシド（４０モル）付加物及びメタノールのプロピレンオキシド（６モル）付加物等が挙げられる。 Preferred examples of the polyether compound (A) are n-butanol propylene oxide (5 mol) adduct, n-butanol propylene oxide (25 mol) adduct, n-butanol propylene oxide (40 mol) adduct. And propylene oxide (6 mol) adduct of methanol and the like.
ポリエーテル化合物（Ａ）の含有量（重量％）は、ポリエーテル化合物（Ａ）、ポリエーテル化合物（Ｂ）及びポリエーテル化合物（Ｃ）の重量に基づいて、１〜１５が好ましく、さらに好ましくは２〜１４、特に好ましくは３〜１３、最も好ましくは４〜１２である。 The content (% by weight) of the polyether compound (A) is preferably 1 to 15, more preferably 1 to 15 based on the weights of the polyether compound (A), the polyether compound (B) and the polyether compound (C). It is 2 to 14, particularly preferably 3 to 13, and most preferably 4 to 12.
＜一般式（２）で表されるポリエーテル化合物（Ｂ）＞
ｍは、３〜１００の整数であり、消泡性の観点から、６〜９０の整数が好ましく、さらに好ましくは１０〜８０の整数、特に好ましくは１６〜６９の整数である。
<Polyether compound (B) represented by the general formula (2)>
m is an integer of 3 to 100, preferably an integer of 6 to 90, more preferably an integer of 10 to 80, and particularly preferably an integer of 16 to 69 from the viewpoint of defoaming property.
ポリエーテル化合物（Ｂ）の好ましい例としては、ポリプロピレンオキシド（数平均分子量６００（ｍ＝１０））、ポリプロピレンオキシド（数平均分子量９５０（ｍ＝１６））、ポリプロピレンオキシド（数平均分子量２０００（ｍ＝３４）及びポリプロピレンオキシド（数平均分子量４０００（ｍ＝６９）等が挙げられる。 Preferred examples of the polyether compound (B) are polypropylene oxide (number average molecular weight 600 (m = 10)), polypropylene oxide (number average molecular weight 950 (m = 16)), polypropylene oxide (number average molecular weight 2000 (m = 10)). 34) and polypropylene oxide (number average molecular weight 4000 (m = 69)) and the like.
ポリエーテル化合物（Ｂ）の含有量（重量％）は、ポリエーテル化合物（Ａ）、ポリエーテル化合物（Ｂ）及びポリエーテル化合物（Ｃ）の重量に基づいて、２０〜５９が好ましく、さらに好ましくは２５〜５５、特に好ましくは２７〜５３、最も好ましくは３０〜５０である。 The content (% by weight) of the polyether compound (B) is preferably 20 to 59, more preferably 20 to 59, based on the weights of the polyether compound (A), the polyether compound (B) and the polyether compound (C). It is 25 to 55, particularly preferably 27 to 53, and most preferably 30 to 50.
＜一般式（３）で表されるポリエーテル化合物（Ｃ）＞
炭素数３〜６のｓ価アルコールの反応残基（Ｒ２）を構成できる炭素数３〜６のｓ価アルコールとしては、３価アルコール（グリセリン、トリメチロールプロパン及びトリメチロールエタン等）、及び４価アルコール（ソルビタン、ペンタエリスリトール及びジグリセリン等）が挙げられる。
<Polyether compound (C) represented by the general formula (3)>
Examples of the s-valent alcohol having 3 to 6 carbon atoms that can form the reaction residue (R 2 ) of the s-valent alcohol having 3 to 6 carbon atoms include trihydric alcohols (glycerin, trimethylolpropane, trimethylolethane, etc.) and 4 Valuable alcohols (sorbitan, pentaerythritol, diglycerin, etc.) can be mentioned.
ｑは、１〜３０の整数であり、消泡性の観点から、３〜２７の整数が好ましく、さらに好ましくは５〜２５の整数、特に好ましくは７〜２３の整数である。 q is an integer of 1 to 30, and from the viewpoint of defoaming property, an integer of 3 to 27 is preferable, an integer of 5 to 25 is preferable, and an integer of 7 to 23 is particularly preferable.
ｐは、１〜１０の整数であり、消泡性の観点から、２〜９の整数が好ましく、さらに好ましくは２〜８の整数、特に好ましくは３〜７の整数である。 p is an integer of 1 to 10, and from the viewpoint of defoaming property, an integer of 2 to 9 is preferable, an integer of 2 to 8 is more preferable, and an integer of 3 to 7 is particularly preferable.
ポリエーテル化合物（Ｃ）の好ましい例としては、グリセリンのプロピレンオキシド（２１モル）エチレンオキシド（９モル）付加物、グリセリンのプロピレンオキシド（４０モル）エチレンオキシド（１４モル）付加物及びトリメチロールプロパンのプロピレンオキシド（６８モル）エチレンオキシド（２１モル）付加物等が挙げられる。 Preferred examples of the polyether compound (C) are propylene oxide (21 mol) ethylene oxide (9 mol) adduct of glycerin, propylene oxide (40 mol) ethylene oxide (14 mol) adduct of glycerin and propylene oxide of trimethylolpropane. Examples thereof include (68 mol) ethylene oxide (21 mol) adducts.
ポリエーテル化合物（Ｃ）の含有量（重量％）は、ポリエーテル化合物（Ａ）、ポリエーテル化合物（Ｂ）及びポリエーテル化合物（Ｃ）の重量に基づいて、４０〜７９が好ましく、さらに好ましくは４３〜７３、特に好ましくは４４〜７０、最も好ましくは４６〜６６である。 The content (% by weight) of the polyether compound (C) is preferably 40 to 79, more preferably 40 to 79, based on the weights of the polyether compound (A), the polyether compound (B) and the polyether compound (C). It is 43 to 73, particularly preferably 44 to 70, and most preferably 46 to 66.
本発明の消泡剤は、さらに疎水性シリカ（Ｄ）を含むことが好ましい。 The defoaming agent of the present invention preferably further contains hydrophobic silica (D).
疎水性シリカ（Ｄ）としては、シリカ粉末を疎水化剤で疎水化処理した疎水性シリカが含まれる。 The hydrophobic silica (D) includes hydrophobic silica obtained by hydrophobizing silica powder with a hydrophobic agent.
疎水化剤としては、シリコーンオイル、変性シリコーンオイル、シリコーン樹脂、ハロシラン、シラザン及びアルコキシシラン等が含まれる。シリコーンオイルとしては、動粘度１０〜３０００（ｍｍ２／ｓ、２５℃）のジメチルポリシロキサン等が挙げられ、オクタメチルシクロテトラシロキサン等も使用できる。変性シリコーンとしては、上記のジメチルポリシロキサンのメチル基の一部を炭素数２〜６のアルキル基、炭素数２〜４のアルコキシル基、フェニル基、水素原子及び／又はハロゲン（塩素及び臭素等）原子等に置き換えたもの等が含まれる。シリコーン樹脂としては、ＲｎＳｉＯ（４−ｎ）／２（式中、Ｒは炭素数１〜４の炭化水素基又はフェニル基、ｎは０〜３の整数を表し、Ｒ３ＳｉＯ１／２単位、Ｒ２ＳｉＯ単位、ＲＳｉＯ３／２単位及び／又はＳｉＯ２単位の適当な組み合わせから構成される樹脂である。）で表されるシリコーン樹脂等が挙げられる。ハロシランとしては、炭素数１〜１２のアルキル基及び／又はアリール基を有するアルキルハロシラン及びアリールハロシランが含まれ、メチルトリクロロシラン、ジメチルジクロロシラン、トリメチルクロロシラン、トリメチルブロモシラン、エチルトリクロロシラン、フェニルトリクロロシラン、ジフェニルジクロロシラン、メチルフェニルジクロロシラン及びｔ−ブチルジメチルクロロシラン等が挙げられる。アルコキシシランとしては、炭素数１〜１２のアルキル基若しくはアリール基及び炭素数１〜２のアルコキシ基を有するアルコキシシラン、並びに炭素数１〜２のアルコキシ基を有するアルコキシシランが含まれ、メチルトリメトキシシラン、ジメチルジメトキシシラン、フェニルトリメトキシシラン、ジフェニルジメトキシシラン、オクチルトリメトキシシラン、メチルトリエトキシシラン、フェニルトリエトキシシラン及び／又はデシルトリエトキシシラン等が挙げられる。 Examples of the hydrophobizing agent include silicone oil, modified silicone oil, silicone resin, halosilane, silazane, alkoxysilane and the like. Examples of the silicone oil include dimethylpolysiloxane having a kinematic viscosity of 10 to 3000 (mm 2 / s, 25 ° C.), and octamethylcyclotetrasiloxane and the like can also be used. As the modified silicone, a part of the methyl group of the above dimethylpolysiloxane is an alkyl group having 2 to 6 carbon atoms, an alkoxyl group having 2 to 4 carbon atoms, a phenyl group, a hydrogen atom and / or a halogen (chlorine, bromine, etc.). Includes those replaced with atoms and the like. As the silicone resin, RnSiO (4-n) / 2 (in the formula, R represents a hydrocarbon group or a phenyl group having 1 to 4 carbon atoms, n represents an integer of 0 to 3, and R 3 SiO 1/2 unit, R 2 SiO units, a resin composed of an appropriate combination of RSiO 3/2 units and / or SiO 2 units. the silicone resin represented by) and the like. The halosilane includes an alkylhalosilane having an alkyl group and / or an aryl group having 1 to 12 carbon atoms and an arylhalosilane, and includes methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, trimethylbromosilane, ethyltrichlorosilane, and phenyl. Examples thereof include trichlorosilane, diphenyldichlorosilane, methylphenyldichlorosilane and t-butyldimethylchlorosilane. The alkoxysilane includes an alkyl group having 1 to 12 carbon atoms or an aryl group, an alkoxysilane having an alkoxy group having 1 to 2 carbon atoms, and an alkoxysilane having an alkoxy group having 1 to 2 carbon atoms, and is methyltrimethoxy. Examples thereof include silane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, octyltrimethoxysilane, methyltriethoxysilane, phenyltriethoxysilane and / or decyltriethoxysilane.
疎水性シリカとしては、市場からも容易に入手でき、たとえば、商品名として、Ｎｉｐｓｉｌ ＳＳ−１０、ＳＳ−４０、ＳＳ−５０及びＳＳ−１００（東ソー・シリカ株式会社、「Ｎｉｐｓｉｌ」は東ソー・シリカ株式会社 の登録商標である。）、ＡＥＲＯＳＩＬ Ｒ９７２、ＲＸ２００及びＲＹ２００（日本アエロジル株式会社、「ＡＥＲＯＳＩＬ」はエボニック デグサ ゲーエムベーハーの登録商標である。 ）、ＳＩＰＥＲＮＡＴ Ｄ１０、Ｄ１３及びＤ１７（エボニックジャパン株式会社、「ＳＩＰＥＲＮＡＴ」はエボニック デグサ ゲーエムベーハーの登録商標である。 ）、ＴＳ−５３０、ＴＳ−６１０、ＴＳ−７２０（キャボットカーボン社）、ＡＥＲＯＳＩＬ Ｒ２０２，Ｒ８０５及びＲ８１２（エボニックジャパン株式会社）、ＲＥＯＬＯＳＩＬ ＭＴ−１０、ＤＭ−１０及びＤＭ−２０Ｓ （株式会社トクヤマ、「ＲＥＯＬＯＳＩＬ」は同社の登録商標である。）、並びにＳＹＬＯＰＨＯＢＩＣ１００、７０２、５０５及び６０３（富士シリシア化学株式会社、「ＳＹＬＯＰＨＯＢＩＣ」は同社の登録商標である。）等が挙げられる。 As hydrophobic silica, it is easily available from the market. For example, as trade names, Nippil SS-10, SS-40, SS-50 and SS-100 (Toso Silica Co., Ltd., "Nippil" is Toso Silica. (Registered Trademarks of Co., Ltd.), AEROSIL R972, RX200 and RY200 (Aerosil Japan Co., Ltd., "AEROSIL" is a registered trademark of Evonik Degussa Game Beher), SIPERANT D10, D13 and D17 (Evonik Japan Co., Ltd., " "SIPERANT" is a registered trademark of Evonik Degussa Game Beher), TS-530, TS-610, TS-720 (Cabot Carbon), AEROSIL R202, R805 and R812 (Evonik Japan Co., Ltd.), REOLOSIL MT-10, DM -10 and DM-20S (Tokuyama Co., Ltd., "REOLOSIL" is a registered trademark of the company), and SYLPHOBIC 100, 702, 505 and 603 (Fuji Silicia Chemical Co., Ltd., "SYLPHOBIC" are registered trademarks of the company. ) Etc. can be mentioned.
疎水性シリカ（Ｄ）を含む場合、疎水性シリカ（Ｄ）の含有量（重量％）は、ポリエーテル化合物（Ａ）、ポリエーエル化合物（Ｂ）及びポリエーテル化合物（Ｃ）重量に基づいて、０．１〜１０が好ましく、さらに好ましくは０．３〜９、特に好ましくは０．５〜８、最も好ましくは０．７〜７である。 When hydrophobic silica (D) is included, the content (% by weight) of hydrophobic silica (D) is 0 based on the weight of the polyether compound (A), the polyear compound (B) and the polyether compound (C). It is preferably 1 to 10, more preferably 0.3 to 9, particularly preferably 0.5 to 8, and most preferably 0.7 to 7.
本発明の消泡剤は、さらに基油（Ｅ）を含むことが好ましい。
基油（Ｅ）としては、鉱油、油脂、モノアルコール脂肪酸エステル及びジメチルシリコーンが含まれる。
The defoaming agent of the present invention preferably further contains a base oil (E).
The base oil (E) includes mineral oil, fats and oils, monoalcohol fatty acid ester and dimethyl silicone.
鉱油としては、減圧蒸留、油剤脱れき、溶剤抽出、水素化分解、溶剤脱ろう、硫酸洗浄、白土精製及び水素化精製等を適宜組み合わせて精製したものを用いることができ、商品名として、コスモピュアスピンＧ、コスモピュアスピンＥ、コスモＳＰ−１０、コスモニュートラル７００及びコスモＳＣ２２（以上、コスモ石油株式会社、「コスモ」及び「ピュアスピン」は同社の登録商標である。）、ＭＣオイル Ｐ−２２、Ｓ−１０Ｓ（以上、出光興産株式会社）、並びにスタノール４０（エクソンモービルコーポレーション）等が挙げられる。 As the mineral oil, those purified by appropriately combining vacuum distillation, oil removal, solvent extraction, hydrocracking, solvent dewaxing, sulfuric acid washing, white clay refining, hydrorefining, etc. can be used, and as a trade name, Cosmo Pure Spin G, Cosmo Pure Spin E, Cosmo SP-10, Cosmo Neutral 700 and Cosmo SC22 (Cosmo Oil Co., Ltd., "Cosmo" and "Pure Spin" are registered trademarks of the same company), MC Oil P- 22, S-10S (above, Idemitsu Kosan Co., Ltd.), Stanol 40 (Exxon Mobile Corporation) and the like.
油脂としては、炭素数６〜２２の脂肪酸又はこの混合物とグリセリンとのエステルが含まれ、植物油（なたね油、大豆油、パーム油、ヤシ油、オリーブ油等）、中鎖脂肪酸グリセライド（商品名として、たとえば、パナセート８７５；日油株式会社、「パナセート」は同社の登録商標である。）、魚油等が挙げられる。 The fats and oils include fatty acids having 6 to 22 carbon atoms or esters of a mixture thereof and glycerin, and are vegetable oils (rapeseed oil, soybean oil, palm oil, palm oil, olive oil, etc.) and medium-chain fatty acid glyceride (as a trade name, for example , Panaceto 875; Nichiyu Co., Ltd., "Panasate" is a registered trademark of the company.), Fish oil and the like.
モノアルコール脂肪酸エステルとしては、炭素数６〜２２の脂肪酸と炭素数１〜２２のモノアルコールとのエステルが含まれ、オレイン酸メチル、オレイン酸ブチル及びイソステアリン酸メチル等が挙げられる。 Examples of the monoalcohol fatty acid ester include an ester of a fatty acid having 6 to 22 carbon atoms and a monoalcohol having 1 to 22 carbon atoms, and examples thereof include methyl oleate, butyl oleate, and methyl isostearate.
ジメチルシリコーンとしては、動粘度１０〜１００００（ｍｍ２／ｓ、２５℃）のポリジメチルシロキサン等が挙げられる。 Examples of the dimethyl silicone include polydimethylsiloxane having a kinematic viscosity of 10 to 10000 (mm 2 / s, 25 ° C.).
これらの基油（Ｅ）のうち、鉱油、油脂及びシリコーンが好ましく、さらに好ましくは鉱油である。 Of these base oils (E), mineral oils, fats and oils and silicones are preferable, and mineral oils are more preferable.
基油（Ｅ）を含む場合、基油（Ｅ）の含有量（重量％）は、ポリエーテル化合物（Ａ）、ポリエーエル化合物（Ｂ）及びポリエーテル化合物（Ｃ）重量に基づいて、１０〜６０が好ましく、さらに好ましくは１５〜５７、特に好ましくは１７〜５５、最も好ましくは２０〜５０である。 When the base oil (E) is contained, the content (% by weight) of the base oil (E) is 10 to 60 based on the weights of the polyether compound (A), the polyether compound (B) and the polyether compound (C). Is preferable, more preferably 15 to 57, particularly preferably 17 to 55, and most preferably 20 to 50.
本発明の消泡剤は、さらに水（Ｆ）を含むことができる。
水（Ｆ）としては、蒸留水、イオン交換水、水道水、工業用水、井戸水、湧き水及び河川水等が使用できる。これらのうち、水道水、工業用水、イオン交換水及び蒸留水が好ましく、さらに好ましくはイオン交換水及び蒸留水である。水（Ｆ）を含有させることにより、引火危険性を低減させ取扱上の安全性を高める効果及び消泡剤の低温流動性を改良する効果がある。
The antifoaming agent of the present invention can further contain water (F).
As the water (F), distilled water, ion-exchanged water, tap water, industrial water, well water, spring water, river water and the like can be used. Of these, tap water, industrial water, ion-exchanged water and distilled water are preferable, and ion-exchanged water and distilled water are more preferable. By containing water (F), there is an effect of reducing the risk of ignition and enhancing handling safety and an effect of improving the low temperature fluidity of the defoaming agent.
水（Ｆ）を含有する場合、水（Ｆ）の含有量（重量％）は、ポリエーテル化合物（Ａ）、ポリエーテル化合物（Ｂ）及びポリエーテル化合物（Ｃ）の重量に基づいて、１〜１０が好ましく、さらに好ましくは１．５〜８、特に好ましくは２〜６である。 When water (F) is contained, the content (% by weight) of water (F) is 1 to 1 based on the weights of the polyether compound (A), the polyether compound (B) and the polyether compound (C). 10 is preferable, more preferably 1.5 to 8, and particularly preferably 2 to 6.
本発明の消泡剤は、ポリエーテル化合物（Ａ）、ポリエーテル化合物（Ｂ）及びポリエーテル化合物（Ｃ）を均一に混合することにより製造することができる。 The defoaming agent of the present invention can be produced by uniformly mixing the polyether compound (A), the polyether compound (B) and the polyether compound (C).
本発明の消泡剤に疎水性シリカ（Ｄ）を含む場合、ポリエーテル化合物（Ａ）、ポリエーテル化合物（Ｂ）及びポリエーテル化合物（Ｃ）を均一混合してから、この混合物（ＡＢＣ）と疎水性シリカ（Ｄ）とを均一混合することが好ましい。 When the defoaming agent of the present invention contains hydrophobic silica (D), the polyether compound (A), the polyether compound (B) and the polyether compound (C) are uniformly mixed, and then the mixture (ABC) and the mixture (ABC) are mixed. It is preferable to uniformly mix the hydrophobic silica (D).
本発明の消泡剤に疎水性シリカ（Ｄ）及び基油（Ｅ）を含む場合、ポリエーテル化合物（Ａ）、ポリエーテル化合物（Ｂ）及びポリエーテル化合物（Ｃ）を均一混合して混合物（ＡＢＣ）を調製し、一方、疎水性シリカ（Ｄ）及び基油（Ｅ）とを均一混合して混合物（ＤＥ）を調製してから、混合物（ＡＢＣ）及び混合物（ＤＥ）を混合してもよい。 When the defoaming agent of the present invention contains hydrophobic silica (D) and base oil (E), the polyether compound (A), the polyether compound (B) and the polyether compound (C) are uniformly mixed and mixed ( ABC) may be prepared, while the hydrophobic silica (D) and the base oil (E) may be uniformly mixed to prepare a mixture (DE), and then the mixture (ABC) and the mixture (DE) may be mixed. Good.
本発明の消泡剤に水（Ｆ）を含む場合、他の成分を混合してから最後に混合することが好ましいが、消泡剤として各組成が均一に混合されていれば、各成分の混合順に制限はない。 When water (F) is contained in the defoaming agent of the present invention, it is preferable to mix the other components and then mix them at the end, but if each composition is uniformly mixed as the defoaming agent, each component There is no limit to the mixing order.
本発明の消泡剤は、発泡成分及び懸濁粒子を含む発泡性分散液体（特に塩化ビニル系樹脂スラリー）に対しても優れた消泡性を発揮する。
したがって、本発明の消泡剤は、塩化ビニル系樹脂の製造方法（上記の消泡剤の存在下で単量体を重合させて塩化ビニル系樹脂スラリーを得る重合工程を含む方法；上記の消泡剤の存在下で塩化ビニル系樹脂スラリーから残留モノマーを回収及び／又は除去する脱モノマー工程を含む方法）においても優れた消泡性を発揮する。
The defoaming agent of the present invention also exhibits excellent defoaming properties against a foaming dispersion liquid (particularly a vinyl chloride resin slurry) containing a foaming component and suspended particles.
Therefore, the defoaming agent of the present invention is a method for producing a vinyl chloride resin (a method including a polymerization step of polymerizing a monomer in the presence of the above defoaming agent to obtain a vinyl chloride resin slurry; the above defoaming agent. It also exhibits excellent defoaming properties (a method including a demonomerization step of recovering and / or removing residual monomers from a vinyl chloride resin slurry in the presence of a foaming agent).
本発明の消泡剤は、いずれのタイミングで添加してもよく、添加に際しては消泡剤を適当な希釈溶媒（たとえば水）で希釈してもよい。 The defoaming agent of the present invention may be added at any timing, and the defoaming agent may be diluted with an appropriate diluting solvent (for example, water) at the time of addition.
塩化ビニル系樹脂としては、塩化ビニル及び塩化ビニルと共重合可能なモノマーの重合物であり、塩化ビニルと共重合可能なモノマーとしては、塩化ビニリデン、酢酸ビニル、（メタ）アクリル酸エステル、エチレン、プロピレン、アルキルビニルエーテル、無水マレイン酸、アクリロニトリル及びスチレン等が含まれる。 The vinyl chloride resin is a polymer of vinyl chloride and a monomer copolymerizable with vinyl chloride, and the monomer copolymerizable with vinyl chloride includes vinylidene chloride, vinyl acetate, (meth) acrylic acid ester, ethylene, and the like. Includes propylene, alkyl vinyl ether, maleic anhydride, acrylonitrile, styrene and the like.
（メタ）アクリル酸エステルとしては、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ヒドロキシエチル等が含まれる。 Examples of the (meth) acrylic acid ester include methyl (meth) acrylate, ethyl (meth) acrylate, hydroxyethyl (meth) acrylate and the like.
消泡剤の使用量は発泡状態等に応じて適宜決定できるが、塩化ビニル系樹脂の重量に基づいて、０．００１〜０．１重量％程度である。 The amount of the defoaming agent used can be appropriately determined depending on the foaming state and the like, but is about 0.001 to 0.1% by weight based on the weight of the vinyl chloride resin.
塩化ビニル系樹脂スラリーの濃度、樹脂粒子径、重合工程の条件、脱モノマー工程の条件等の詳細については、通常の条件、範囲がそのまま適用できる。 As for the details such as the concentration of the vinyl chloride resin slurry, the resin particle size, the conditions of the polymerization step, and the conditions of the demonomerization step, the usual conditions and ranges can be applied as they are.
以下、特記しない限り「部」は重量部を意味する。 Hereinafter, unless otherwise specified, "part" means a part by weight.
ポリエーテル化合物（Ａ）として、以下のポリエーテル化合物（ａ１）〜（ａ４）を使用した。
ポリエーテル化合物（ａ１）：ｎ−ブタノールのプロピレンオキシド（４モル）付加物
ポリエーテル化合物（ａ２）：ｎ−ブタノールのプロピレンオキシド（１６モル）付加物
ポリエーテル化合物（ａ３）：ｎ−ブタノールのプロピレンオキシド（２５モル）付加物
ポリエーテル化合物（ａ４）：ｎ−ブタノールのプロピレンオキシド（４０モル）付加物
The following polyether compounds (a1) to (a4) were used as the polyether compound (A).
Polyether compound (a1): Propylene oxide (4 mol) adduct of n-butanol Polyether compound (a2): Propylene oxide (16 mol) adduct of n-butanol Polyether compound (a3): Propylene oxide of n-butanol Oxide (25 mol) Additives Polyether compound (a4): Propylene oxide (40 mol) adduct of n-butanol
ポリエーテル化合物（Ｂ）として、以下のポリエーテル化合物（ｂ１）〜（ｂ３）を使用した。
ポリエーテル化合物（ｂ１）：ポリプロピレンオキシド（数平均分子量９５０（ｍ＝１６））
ポリエーテル化合物（ｂ２）：、ポリプロピレンオキシド（数平均分子量２０００（ｍ＝３４））
ポリエーテル化合物（ｂ３）：ポリプロピレンオキシド（数平均分子量４０００（ｍ＝６９））
As the polyether compound (B), the following polyether compounds (b1) to (b3) were used.
Polyether compound (b1): polypropylene oxide (number average molecular weight 950 (m = 16))
Polyether compound (b2) :, polypropylene oxide (number average molecular weight 2000 (m = 34))
Polyether compound (b3): polypropylene oxide (number average molecular weight 4000 (m = 69))
ポリエーテル化合物（Ｃ）として、以下のポリエーテル化合物（ｃ１）〜（ｃ４）を使用した。
ポリエーテル化合物（ｃ１）：グリセリンのプロピレンオキシド（２１モル）エチレンオキシド（９モル）付加物（ｑ＝７；ｐ＝３）
ポリエーテル化合物（ｃ２）：グリセリンのプロピレンオキシド（４０モル）エチレンオキシド（１４モル）付加物（ｑ＝１３、１４；ｐ＝４、５）
ポリエーテル化合物（ｃ３）：トリメチロールプロパンのプロピレンオキシド（６８モル）エチレンオキシド（２１モル）（ｑ＝２２、２３；ｐ＝７）
ポリエーテル化合物（ｃ４）：ジグリセリンのプロピレンオキシド（４８モル）エチレンオキシド（１６モル）（ｑ＝１２；ｐ＝４）
The following polyether compounds (c1) to (c4) were used as the polyether compound (C).
Polyether compound (c1): Propylene oxide (21 mol) ethylene oxide (9 mol) adduct of glycerin (q = 7; p = 3)
Polyether compound (c2): Propylene oxide (40 mol) ethylene oxide (14 mol) adduct of glycerin (q = 13, 14; p = 4, 5)
Polyether compound (c3): Propylene oxide (68 mol) of trimethylolpropane (21 mol) Ethylene oxide (21 mol) (q = 22, 23; p = 7)
Polyether compound (c4): Propylene oxide (48 mol) of diglycerin Ethylene oxide (16 mol) (q = 12; p = 4)
疎水性シリカ（Ｄ）として、以下の疎水性シリカ（ｄ１）〜（ｄ３）を使用した。
疎水性シリカ（ｄ１）：ＡＥＲＯＳＩＬ Ｒ９７２（日本アエロジル株式会社）
疎水性シリカ（ｄ２）：ＳＩＰＥＲＮＡＴ Ｄ１０（エボニックジャパン株式会社）
疎水性シリカ（ｄ３）：Ｎｉｐｓｉｌ ＳＳ−１００（東ソー・シリカ株式会社）
The following hydrophobic silicas (d1) to (d3) were used as the hydrophobic silica (D).
Hydrophobic silica (d1): AEROSIL R972 (Japan Aerosil Co., Ltd.)
Hydrophobic silica (d2): SIPERANT D10 (Evonik Japan Co., Ltd.)
Hydrophobic silica (d3): Nipponsil SS-100 (Tosoh Silica Co., Ltd.)
基油（Ｅ）として、以下の基油（ｅ１）〜（ｅ２）を使用した。
基油（ｅ１）：鉱物油（コスモＳＰ−１０、コスモ石油株式会社）
基油（ｅ２）：鉱物油（コスモＳＣ−２２、コスモ石油株式会社）
The following base oils (e1) to (e2) were used as the base oil (E).
Base oil (e1): Mineral oil (Cosmo SP-10, Cosmo Oil Co., Ltd.)
Base oil (e2): Mineral oil (Cosmo SC-22, Cosmo Oil Co., Ltd.)
水（Ｆ）として、以下の基油（ｆ１）を使用した。
水（ｆ１）：脱イオン水
The following base oil (f1) was used as water (F).
Water (f1): Deionized water
＜製造例１＞
攪拌の可能な容器内で、基油（ｅ１）８７０部及び疎水性シリカ（ｄ２）１３０部を６０分間攪拌混合し、ゴーリンホモジナイザーを用いて３５００ｐｓｉ（２４．１ＭＰａ）にて均質化処理して、疎水性シリカ基油分散液（１）を得た。
<Manufacturing example 1>
In a stirable container, 870 parts of the base oil (e1) and 130 parts of the hydrophobic silica (d2) were stirred and mixed for 60 minutes, homogenized at 3500 psi (24.1 MPa) using a gorin homogenizer, and treated. A hydrophobic silica base oil dispersion (1) was obtained.
＜製造例２＞
攪拌の可能な容器内で、基油（ｅ２）９００部及び疎水性シリカ（ｄ３）１００部を６０分間攪拌混合し、ゴーリンホモジナイザーを用いて３５００ｐｓｉ（２４．１ＭＰａ）にて均質化処理して、疎水性シリカ分散液（２）を得た。
<Manufacturing example 2>
In a stirable container, 900 parts of base oil (e2) and 100 parts of hydrophobic silica (d3) were stirred and mixed for 60 minutes, homogenized at 3500 psi (24.1 MPa) using a gorin homogenizer, and treated. A hydrophobic silica dispersion (2) was obtained.
＜実施例１＞
攪拌の可能な容器内で、ポリエーテル化合物（ａ１）１００部、ポリエーテル化合物（ｂ３）３００部、ポリエーテル化合物（ｃ３）６００部及び水（ｆ１）６０部を均一混合して、本発明の消泡剤（１）を得た。
<Example 1>
In a container capable of stirring, 100 parts of the polyether compound (a1), 300 parts of the polyether compound (b3), 600 parts of the polyether compound (c3) and 60 parts of water (f1) are uniformly mixed to obtain the present invention. An antifoaming agent (1) was obtained.
＜実施例２＞
攪拌の可能な容器内で、ポリエーテル化合物（ａ２）４０部、ポリエーテル化合物（ｂ２）５００部、ポリエーテル化合物（ｃ２）４６０部及び疎水性シリカ（ｄ１）３０部を均一混合して、本発明の消泡剤（２）を得た。
<Example 2>
40 parts of the polyether compound (a2), 500 parts of the polyether compound (b2), 460 parts of the polyether compound (c2) and 30 parts of the hydrophobic silica (d1) are uniformly mixed in a stirable container. The antifoaming agent (2) of the present invention was obtained.
＜実施例３＞
攪拌の可能な容器内で、ポリエーテル化合物（ａ３）１２０部、ポリエーテル化合物（ｂ１）２００部、ポリエーテル化合物（ｂ２）２００部、ポリエーテル化合物（ｃ１）２００部、ポリエーテル化合物（ｃ３）２８０部、疎水性シリカ（ｄ１）７部及び水（ｆ１）２０部を均一混合して、本発明の消泡剤（３）を得た。
<Example 3>
In a stirable container, 120 parts of polyether compound (a3), 200 parts of polyether compound (b1), 200 parts of polyether compound (b2), 200 parts of polyether compound (c1), polyether compound (c3) 280 parts, 7 parts of hydrophobic silica (d1) and 20 parts of water (f1) were uniformly mixed to obtain the defoaming agent (3) of the present invention.
＜実施例４＞
攪拌の可能な容器内で、ポリエーテル化合物（ａ４）４０部、ポリエーテル化合物（ｂ２）３００部、ポリエーテル化合物（ｃ２）６００部、ポリエーテル化合物（ｃ４）６０部、疎水性シリカ基油分散液（１）２３０部を均一混合して、本発明の消泡剤（４）を得た。
<Example 4>
40 parts of the polyether compound (a4), 300 parts of the polyether compound (b2), 600 parts of the polyether compound (c2), 60 parts of the polyether compound (c4), and a hydrophobic silica base oil dispersion in a stirable container. 230 parts of the liquid (1) were uniformly mixed to obtain the defoaming agent (4) of the present invention.
＜実施例５＞
攪拌の可能な容器内で、ポリエーテル化合物（ａ２）６０部、ポリエーテル化合物（ｂ３）４００部、ポリエーテル化合物（ｃ１）５４０部、疎水性シリカ（ｄ１）１０部及び疎水性シリカ基油分散液（２）５５５部を均一混合して、本発明の消泡剤（５）を得た。
<Example 5>
Dispersion of 60 parts of the polyether compound (a2), 400 parts of the polyether compound (b3), 540 parts of the polyether compound (c1), 10 parts of the hydrophobic silica (d1) and the hydrophobic silica base oil in a stirable container. 555 parts of the liquid (2) was uniformly mixed to obtain the defoaming agent (5) of the present invention.
＜実施例６＞
攪拌の可能な容器内で、ポリエーテル化合物（ａ１）７０部、ポリエーテル化合物（ｂ２）４００部、ポリエーテル化合物（ｃ２）５３０部、疎水性シリカ基油分散液（１）２５０部及び疎水性シリカ分散液（２）１５０部を均一混合して、本発明の消泡剤（６）を得た。
<Example 6>
In a stirable container, 70 parts of the polyether compound (a1), 400 parts of the polyether compound (b2), 530 parts of the polyether compound (c2), 250 parts of the hydrophobic silica base oil dispersion (1) and hydrophobicity. 150 parts of the silica dispersion (2) was uniformly mixed to obtain the defoaming agent (6) of the present invention.
＜実施例７＞
攪拌の可能な容器内で、ポリエーテル化合物（ａ２）１００部、ポリエーテル化合物（ｂ２）２００部、ポリエーテル化合物（ｂ３）２００部、ポリエーテル化合物（ｃ１）１００部、ポリエーテル化合物（ｃ２）４００部及び疎水性シリカ（ｄ２）７０部を均一混合して、本発明の消泡剤（７）を得た。
<Example 7>
In a stirable container, 100 parts of the polyether compound (a2), 200 parts of the polyether compound (b2), 200 parts of the polyether compound (b3), 100 parts of the polyether compound (c1), and the polyether compound (c2). 400 parts and 70 parts of hydrophobic silica (d2) were uniformly mixed to obtain the defoaming agent (7) of the present invention.
＜比較例１＞
特許文献１の実施例２の記載に準拠して、炭化水素油（ピュアスピンＧ、流動点−１０℃、コスモ石油ルブリカンツ株式会社）９５部及び疎水性シリカ（Ｎｉｐｓｉｌ ＳＳ−５０、体積平均粒子径１μｍ、東ソー・シリカ株式会社）５部からなる疎水性シリカ分散液６０部と、ブタノールのプロピレンオキシド（４０モル）付加体（ニューポールＬＢ−１７１５、三洋化成工業株式会社）３０部と、ポリオキシエチレン（重合度：６０）ソルビトールテトラオレイン酸エステル（レオドール４６０Ｖ、ＨＬＢ＝１３、８、花王株式会社）１０部とを均一混合して、比較用の消泡剤（Ｈ１）とした。
<Comparative example 1>
In accordance with the description of Example 2 of Patent Document 1, 95 parts of hydrocarbon oil (Pure Spin G, flow point -10 ° C, Cosmo Petroleum Lubricants Co., Ltd.) and hydrophobic silica (Nipsil SS-50, volume average particle size) 1 μm, Toso Silica Co., Ltd.) 60 parts of hydrophobic silica dispersion, butanol propylene oxide (40 mol) adduct (New Pole LB-1715, Sanyo Kasei Kogyo Co., Ltd.) 30 parts, and polyoxy Ethylene (degree of polymerization: 60) sorbitol tetraoleic acid ester (Leodor 460V, HLB = 13, 8, Kao Co., Ltd.) was uniformly mixed with 10 parts to prepare a defoaming agent (H1) for comparison.
＜比較例２＞
ケン化度８０モル％、平均重合度２５００の部分ケン化ポリ酢酸ビニル（ＰＶＡ）（特許文献３の実施例１で使用した発泡防止成分）の１重量％水溶液を比較用の消泡剤（Ｈ２）とした。
<Comparative example 2>
A defoaming agent (H2) for comparison with a 1% by weight aqueous solution of partially saponified polyvinyl acetate (PVA) (anti-foaming component used in Example 1 of Patent Document 3) having a saponification degree of 80 mol% and an average degree of polymerization of 2500. ).
＜比較例３＞
特許文献２に記載されたようなジメチルポリシロキサンからなるシリコーン系消泡剤を比較用の消泡剤（Ｈ３）とした。
<Comparative example 3>
A silicone-based defoaming agent composed of dimethylpolysiloxane as described in Patent Document 2 was used as a comparative defoaming agent (H3).
消泡剤（１）〜（７）及び（Ｈ１）〜（Ｈ３）を用いて、以下のようにして消泡性を評価し、評価結果を表１及び２に示した。 Using the antifoaming agents (1) to (7) and (H1) to (H3), the antifoaming property was evaluated as follows, and the evaluation results are shown in Tables 1 and 2.
＜塩化ビニル重合用水相に対する消泡性の評価＞
１．試験用水溶液の調製
ポリビニルアルコール（１）［ゴーセノールＧＨ−２０（けん化度８８モル％）、日本合成化学工業株式会社、「ゴーセノール」は同社の登録商標である。以下、同様である］５部、ポリビニルアルコール（２）［ゴーセノールＬＷ−２００（けん化度５０モル％）２部、ポリビニルアルコール（３）［クラレポバールＬ−１０（けん化度７２モル％）］３部及び水９９９０部を均一に混合してポリビニルアルコールを溶解させ、試験用水溶液を得た。
<Evaluation of defoaming property for aqueous phase for vinyl chloride polymerization>
1. 1. Preparation of test aqueous solution Polyvinyl alcohol (1) [Gosenol GH-20 (saponification degree 88 mol%), Nippon Synthetic Chemical Industry Co., Ltd., "Gosenol" are registered trademarks of the same company. The same applies hereinafter] 5 parts, polyvinyl alcohol (2) [Gosenol LW-200 (saponification degree 50 mol%) 2 parts, polyvinyl alcohol (3) [Kuraray Poval L-10 (saponification degree 72 mol%)] 3 parts And 9990 parts of water were uniformly mixed to dissolve polyvinyl alcohol to obtain a test aqueous solution.
２．消泡試験液の調製
試験用水溶液１００部を５５℃まで加熱し、消泡剤を０．００２部を加えて混合し、消泡試験液を得た。
消泡剤を加えないこと以外、上記と同様にして、消泡試験液(ブランク)も調製した。
2. 2. Preparation of Defoaming Test Solution 100 parts of the test aqueous solution was heated to 55 ° C., 0.002 part of the defoaming agent was added and mixed to obtain a defoaming test solution.
A defoaming test solution (blank) was also prepared in the same manner as above, except that no defoaming agent was added.
３．消泡性試験
温度調節可能であり、底部に直径３ｃｍの攪拌翼を有するガラス製シリンダー（内径４ｃｍ、高さ２５ｃｍ）を５５℃に温度調節して、このガラス製シリンダーに、５５℃に温度調節した消泡試験液５０ｍｌを入れ、４０００ｒｐｍで攪拌翼を５分間回転させて消泡試験液を泡立て、攪拌翼の停止直後の泡面高さを読み取った。数値の小さい方が消泡性が高いことを意味し好ましい。
3. 3. Defoaming test The temperature of a glass cylinder (inner diameter 4 cm, height 25 cm) that is adjustable and has a stirring blade with a diameter of 3 cm at the bottom is adjusted to 55 ° C, and the temperature of this glass cylinder is adjusted to 55 ° C. 50 ml of the defoaming test solution was added, and the stirring blade was rotated at 4000 rpm for 5 minutes to whisk the defoaming test solution, and the height of the foam surface immediately after the stirring blade was stopped was read. The smaller the value, the higher the defoaming property, which is preferable.
＜塩化ビニル樹脂スラリーに対する消泡性の評価＞
１．試験用スラリーの調製
水６００部及び塩化ビニル樹脂粒子（カネビニールＳ−１００８、株式会社カネカ、「カネビニール」は同社の登録商標である。）４００部を均一混合して試験用スラリーを得た。
<Evaluation of defoaming property for vinyl chloride resin slurry>
1. 1. Preparation of test slurry 600 parts of water and 400 parts of vinyl chloride resin particles (Kaneka S-1008, Kaneka Corporation, "Kaneka" is a registered trademark of the same company) were uniformly mixed to obtain a test slurry. ..
２．消泡試験液の調製
試験用スラリー１０００部を６０℃まで加熱し、消泡剤を０．１２部を加えて混合し、消泡試験液を得た。
消泡剤を加えないこと以外、上記と同様にして、消泡試験液(ブランク)も調製した。
2. 2. Preparation of Defoaming Test Solution 1000 parts of the test slurry was heated to 60 ° C., 0.12 parts of the defoaming agent was added and mixed to obtain a defoaming test solution.
A defoaming test solution (blank) was also prepared in the same manner as above, except that no defoaming agent was added.
３．消泡性試験
１００ｍＬのガラス製メスシリンダーを６０℃に温度調節しながら、このガラス製メスシリンダーに、６０℃に温度調節した消泡試験液４０ｇを入れ、デフューザーストーンをガラス製メスシリンダーの底部まで挿入し３００ｍｌ／分で窒素ガスをバブリングすることによって消泡試験液を泡立てて、変化する泡及び発泡液の容量（ｍｌ）を試験開始１５秒後、１分後及び１０分後に読み取った。数値の小さい方が消泡性が高いことを意味し好ましい。
3. 3. Defoaming test While adjusting the temperature of a 100 mL glass graduated cylinder to 60 ° C, put 40 g of the defoaming test solution whose temperature has been adjusted to 60 ° C into this glass graduated cylinder, and apply the diffuser stone to the bottom of the glass graduated cylinder. The defoaming test solution was whipped by inserting and bubbling nitrogen gas at 300 ml / min, and the changing foam and volume (ml) of the foaming solution were read 15 seconds, 1 minute and 10 minutes after the start of the test. The smaller the value, the higher the defoaming property, which is preferable.
本発明の消泡剤は、比較用の消泡剤に比べて、塩化ビニル重合用水相及び塩化ビニル樹脂スラリーのいずれにおいても優れた消泡性を発揮した。一方、比較用の消泡剤（Ｈ２）は塩化ビニル重合用水相に対してブランクよりも消泡性が悪かったが、塩化ビニル樹脂スラリーに対しては良好な消泡性を示した。 The defoaming agent of the present invention exhibited excellent defoaming properties in both the aqueous phase for vinyl chloride polymerization and the vinyl chloride resin slurry as compared with the defoaming agent for comparison. On the other hand, the comparative defoaming agent (H2) had a worse defoaming property than the blank with respect to the aqueous phase for vinyl chloride polymerization, but showed good defoaming property with respect to the vinyl chloride resin slurry.
塩化ビニル系樹脂の製造の際、消泡剤が残留し、得られる塩化ビニル系樹脂の物性に影響することがあるが、上記の消泡剤を用いて塩化ビニル系樹脂を製造すると、消泡性に優れるので、より少ない消泡剤で塩化ビニル系樹脂を製造でき、塩化ビニル系樹脂の物性への影響を低減できる（塩化ビニル系樹脂の物性が優れる）と共に、塩化ビニル系樹脂を効率的に生産できる（生産性に優れる）。 During the production of the vinyl chloride resin, the defoaming agent may remain and affect the physical properties of the obtained vinyl chloride resin. However, when the vinyl chloride resin is produced using the above defoaming agent, the defoaming agent is used. Since it has excellent properties, vinyl chloride-based resin can be produced with less defoaming agent, the influence on the physical properties of vinyl chloride-based resin can be reduced (the physical properties of vinyl chloride-based resin are excellent), and vinyl chloride-based resin is efficient. Can be produced (excellent in productivity).
本発明の消泡剤は、塩化ビニル系樹脂スラリー用消泡剤として好適であり、塩化ビニル系樹脂スラリーを得る重合工程、塩化ビニル系樹脂スラリーから残留モノマーを回収及び／又は除去する脱モノマー工程を含む塩化ビニル系樹脂の製造方法に最適である。 The defoaming agent of the present invention is suitable as a defoaming agent for vinyl chloride resin slurry, and is a polymerization step for obtaining a vinyl chloride resin slurry and a demonomerization step for recovering and / or removing residual monomer from the vinyl chloride resin slurry. It is most suitable for the method for producing a vinyl chloride resin containing.
Claims (5)
ポリエーテル化合物（Ａ）、ポリエーテル化合物（Ｂ）及びポリエーテル化合物（Ｃ）の重量に基づいて、ポリエーテル化合物（Ａ）の含有量が１〜１５重量％、ポリエーテル化合物（Ｂ）の含有量が２０〜５９重量％、ポリエーテル化合物（Ｃ）の含有量が４０〜７９重量％であることを特徴とする消泡剤。
Ｒ１Ｏ-（ＰＯ）ｎ-Ｈ （１）
ＨＯ-（ＰＯ）ｍ-Ｈ （２）
Ｒ２-｛（ＰＯ）ｑ-（ＥＯ）ｐ-Ｈ｝ｓ （３）
Ｒ１は炭素数１〜４のアルキル基、Ｒ２は炭素数３〜６のｓ価アルコールの反応残基、ＰＯはオキシプロピレン基、ＥＯはオキシエチレン基を表し、ｎは１〜５０の整数、ｍは３〜１００の整数、ｑは１〜３０の整数、ｐは１〜１０の整数であり、ｓは３または４の整数でｓ個の｛（ＰＯ）ｍ-（ＥＯ）ｐ-Ｈ｝はそれぞれ同じでも異なっていてもよい。 Contains the polyether compound (A) represented by the general formula (1), the polyether compound (B) represented by the general formula (2), and the polyether compound (C) represented by the general formula (3). ,
Based on the weights of the polyether compound (A), the polyether compound (B) and the polyether compound (C), the content of the polyether compound (A) is 1 to 15% by weight, and the content of the polyether compound (B) is contained. A defoaming agent characterized in that the amount is 20 to 59% by weight and the content of the polyether compound (C) is 40 to 79% by weight.
R 1 O- (PO) n -H (1)
HO- (PO) m -H (2)
R 2 -{(PO) q- (EO) p -H} s (3)
R 1 is an alkyl group having 1 to 4 carbon atoms, R 2 is a reaction residue of an s-valent alcohol having 3 to 6 carbon atoms, PO is an oxypropylene group, EO is an oxyethylene group, and n is an integer of 1 to 50. , M is an integer of 3 to 100, q is an integer of 1 to 30, p is an integer of 1 to 10, and s is an integer of 3 or 4 and s {(PO) m- (EO) p -H. } May be the same or different.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1991000763A1 (en) * | 1989-07-12 | 1991-01-24 | Rhone-Poulenc Surfactants And Specialties, L.P. | Low viscosity defoaming/antifoaming formulations |
| JP2010162429A (en) * | 2009-01-13 | 2010-07-29 | San Nopco Ltd | Antifoaming agent |
| JP2019025447A (en) * | 2017-08-02 | 2019-02-21 | サンノプコ株式会社 | Defoaming agent for vinyl chloride resin slurry and method for producing vinyl chloride resin |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1991000763A1 (en) * | 1989-07-12 | 1991-01-24 | Rhone-Poulenc Surfactants And Specialties, L.P. | Low viscosity defoaming/antifoaming formulations |
| JP2010162429A (en) * | 2009-01-13 | 2010-07-29 | San Nopco Ltd | Antifoaming agent |
| JP2019025447A (en) * | 2017-08-02 | 2019-02-21 | サンノプコ株式会社 | Defoaming agent for vinyl chloride resin slurry and method for producing vinyl chloride resin |
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