JP2023052330A - Polyvinyl alcohol-based resin, dispersing agent, and dispersing agent for suspension polymerization - Google Patents
Polyvinyl alcohol-based resin, dispersing agent, and dispersing agent for suspension polymerization Download PDFInfo
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- JP2023052330A JP2023052330A JP2023002514A JP2023002514A JP2023052330A JP 2023052330 A JP2023052330 A JP 2023052330A JP 2023002514 A JP2023002514 A JP 2023002514A JP 2023002514 A JP2023002514 A JP 2023002514A JP 2023052330 A JP2023052330 A JP 2023052330A
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- JP
- Japan
- Prior art keywords
- pva
- based resin
- polyvinyl alcohol
- absorbance
- resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229920005989 resin Polymers 0.000 title claims abstract description 151
- 239000011347 resin Substances 0.000 title claims abstract description 151
- 229920002451 polyvinyl alcohol Polymers 0.000 title claims abstract description 135
- 239000004372 Polyvinyl alcohol Substances 0.000 title claims abstract description 134
- 239000002270 dispersing agent Substances 0.000 title claims abstract description 32
- 238000010557 suspension polymerization reaction Methods 0.000 title claims abstract description 27
- 238000002835 absorbance Methods 0.000 claims abstract description 38
- 239000000843 powder Substances 0.000 claims abstract description 29
- 239000007864 aqueous solution Substances 0.000 claims abstract description 25
- 239000002245 particle Substances 0.000 claims abstract description 21
- 238000000862 absorption spectrum Methods 0.000 claims abstract description 15
- 238000007127 saponification reaction Methods 0.000 claims description 24
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 10
- 150000004679 hydroxides Chemical class 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 12
- 229920000915 polyvinyl chloride Polymers 0.000 abstract description 7
- 239000004800 polyvinyl chloride Substances 0.000 abstract description 7
- 239000000243 solution Substances 0.000 abstract description 4
- 239000000178 monomer Substances 0.000 description 34
- 238000006116 polymerization reaction Methods 0.000 description 27
- 238000000034 method Methods 0.000 description 25
- 229920001567 vinyl ester resin Polymers 0.000 description 22
- 238000010438 heat treatment Methods 0.000 description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- -1 poly(vinyl alcohol) Polymers 0.000 description 17
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 13
- 229920000642 polymer Polymers 0.000 description 13
- 238000004040 coloring Methods 0.000 description 12
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 11
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000000379 polymerizing effect Effects 0.000 description 6
- 239000003381 stabilizer Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000012986 chain transfer agent Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 239000000123 paper Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 150000002148 esters Chemical group 0.000 description 3
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 229940097364 magnesium acetate tetrahydrate Drugs 0.000 description 3
- XKPKPGCRSHFTKM-UHFFFAOYSA-L magnesium;diacetate;tetrahydrate Chemical compound O.O.O.O.[Mg+2].CC([O-])=O.CC([O-])=O XKPKPGCRSHFTKM-UHFFFAOYSA-L 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000004513 sizing Methods 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 2
- BCITXCOYSHAADW-UHFFFAOYSA-N 1-[2-(4-oxoheptoxymethyl)prop-2-enoxy]heptan-4-one Chemical compound C(CCC(=O)CCC)OCC(COCCCC(=O)CCC)=C BCITXCOYSHAADW-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-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
- 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 2
- FKAKGSJLTBVQOP-UHFFFAOYSA-N 2-(acetyloxymethyl)prop-2-enyl acetate Chemical compound CC(=O)OCC(=C)COC(C)=O FKAKGSJLTBVQOP-UHFFFAOYSA-N 0.000 description 2
- IGDCJKDZZUALAO-UHFFFAOYSA-N 2-prop-2-enoxypropane-1,3-diol Chemical compound OCC(CO)OCC=C IGDCJKDZZUALAO-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- DFINTYMPPWPMIF-UHFFFAOYSA-N CC(=O)OC(OC(C)=O)=CCO Chemical compound CC(=O)OC(OC(C)=O)=CCO DFINTYMPPWPMIF-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 2
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 2
- 239000001639 calcium acetate Substances 0.000 description 2
- 235000011092 calcium acetate Nutrition 0.000 description 2
- 229960005147 calcium acetate Drugs 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000008394 flocculating agent Substances 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- WGTGQGJDNAGBCC-UHFFFAOYSA-N hex-5-ene-1,2-diol Chemical compound OCC(O)CCC=C WGTGQGJDNAGBCC-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 2
- 229940069446 magnesium acetate Drugs 0.000 description 2
- 239000011654 magnesium acetate Substances 0.000 description 2
- 235000011285 magnesium acetate Nutrition 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- TUYPUNQWRBMHBZ-UHFFFAOYSA-N 1-methoxyethenyl acetate Chemical compound COC(=C)OC(C)=O TUYPUNQWRBMHBZ-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- JXPHLUCMHXXHEJ-UHFFFAOYSA-N 2-(aminomethyl)-4-bromoaniline Chemical compound NCC1=CC(Br)=CC=C1N JXPHLUCMHXXHEJ-UHFFFAOYSA-N 0.000 description 1
- DIBCJRYCOGXPAM-UHFFFAOYSA-N 2-(propanoyloxymethyl)prop-2-enyl propanoate Chemical compound CCC(=O)OCC(=C)COC(=O)CC DIBCJRYCOGXPAM-UHFFFAOYSA-N 0.000 description 1
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 1
- ZSPTYLOMNJNZNG-UHFFFAOYSA-N 3-Buten-1-ol Chemical compound OCCC=C ZSPTYLOMNJNZNG-UHFFFAOYSA-N 0.000 description 1
- BXAAQNFGSQKPDZ-UHFFFAOYSA-N 3-[1,2,2-tris(prop-2-enoxy)ethoxy]prop-1-ene Chemical compound C=CCOC(OCC=C)C(OCC=C)OCC=C BXAAQNFGSQKPDZ-UHFFFAOYSA-N 0.000 description 1
- LANDRZNMJOEVQO-UHFFFAOYSA-N 3-ethenoxypropane-1,2-diol Chemical compound OCC(O)COC=C LANDRZNMJOEVQO-UHFFFAOYSA-N 0.000 description 1
- KMPBSNWACXDMII-UHFFFAOYSA-N 3-methylpent-4-ene-1,2-diol Chemical compound C=CC(C)C(O)CO KMPBSNWACXDMII-UHFFFAOYSA-N 0.000 description 1
- UAIRLKNEZWEEJO-UHFFFAOYSA-N 3-prop-1-en-2-yloxypropane-1,2-diol Chemical compound CC(=C)OCC(O)CO UAIRLKNEZWEEJO-UHFFFAOYSA-N 0.000 description 1
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 1
- VXVUDUCBEZFQGY-UHFFFAOYSA-N 4,4-dimethylpentanenitrile Chemical compound CC(C)(C)CCC#N VXVUDUCBEZFQGY-UHFFFAOYSA-N 0.000 description 1
- BJWMSGRKJIOCNR-UHFFFAOYSA-N 4-ethenyl-1,3-dioxolan-2-one Chemical compound C=CC1COC(=O)O1 BJWMSGRKJIOCNR-UHFFFAOYSA-N 0.000 description 1
- SQXNZBLNWGWIHZ-UHFFFAOYSA-N 4-ethenyl-2,2-dimethyl-1,3-dioxolane Chemical class CC1(C)OCC(C=C)O1 SQXNZBLNWGWIHZ-UHFFFAOYSA-N 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical class C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BCZXFFBUYPCTSJ-UHFFFAOYSA-L Calcium propionate Chemical compound [Ca+2].CCC([O-])=O.CCC([O-])=O BCZXFFBUYPCTSJ-UHFFFAOYSA-L 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical group OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 239000004831 Hot glue Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- YSVZGWAJIHWNQK-UHFFFAOYSA-N [3-(hydroxymethyl)-2-bicyclo[2.2.1]heptanyl]methanol Chemical compound C1CC2C(CO)C(CO)C1C2 YSVZGWAJIHWNQK-UHFFFAOYSA-N 0.000 description 1
- RMKZLFMHXZAGTM-UHFFFAOYSA-N [dimethoxy(propyl)silyl]oxymethyl prop-2-enoate Chemical compound CCC[Si](OC)(OC)OCOC(=O)C=C RMKZLFMHXZAGTM-UHFFFAOYSA-N 0.000 description 1
- 238000006359 acetalization reaction Methods 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
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- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
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- 150000002009 diols Chemical class 0.000 description 1
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- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- NNBRCHPBPDRPIT-UHFFFAOYSA-N ethenyl(tripropoxy)silane Chemical compound CCCO[Si](OCCC)(OCCC)C=C NNBRCHPBPDRPIT-UHFFFAOYSA-N 0.000 description 1
- MBGQQKKTDDNCSG-UHFFFAOYSA-N ethenyl-diethoxy-methylsilane Chemical compound CCO[Si](C)(C=C)OCC MBGQQKKTDDNCSG-UHFFFAOYSA-N 0.000 description 1
- ZLNAFSPCNATQPQ-UHFFFAOYSA-N ethenyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C=C ZLNAFSPCNATQPQ-UHFFFAOYSA-N 0.000 description 1
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
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- 238000005187 foaming Methods 0.000 description 1
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- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
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- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- SNVLJLYUUXKWOJ-UHFFFAOYSA-N methylidenecarbene Chemical group C=[C] SNVLJLYUUXKWOJ-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
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- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- LQAVWYMTUMSFBE-UHFFFAOYSA-N pent-4-en-1-ol Chemical compound OCCCC=C LQAVWYMTUMSFBE-UHFFFAOYSA-N 0.000 description 1
- KCPNPXFJBCFNRU-UHFFFAOYSA-N pent-4-ene-1,2-diol Chemical compound OCC(O)CC=C KCPNPXFJBCFNRU-UHFFFAOYSA-N 0.000 description 1
- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical compound [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N penta-1,3-diene Chemical compound CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- MOVRCMBPGBESLI-UHFFFAOYSA-N prop-2-enoyloxysilicon Chemical compound [Si]OC(=O)C=C MOVRCMBPGBESLI-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- SGCFZHOZKKQIBU-UHFFFAOYSA-N tributoxy(ethenyl)silane Chemical compound CCCCO[Si](OCCCC)(OCCCC)C=C SGCFZHOZKKQIBU-UHFFFAOYSA-N 0.000 description 1
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F16/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F16/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an alcohol radical
- C08F16/04—Acyclic compounds
- C08F16/06—Polyvinyl alcohol ; Vinyl alcohol
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/20—Aqueous medium with the aid of macromolecular dispersing agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
本発明は、ポリビニルアルコール系樹脂に関し、更に詳しくは、ポリ塩化ビニル製造時にビニル系化合物を懸濁重合する際に用いる分散剤として好適なポリビニルアルコール系樹脂、分散剤及び懸濁重合用分散剤に関する。 TECHNICAL FIELD The present invention relates to a polyvinyl alcohol-based resin, and more particularly, to a polyvinyl alcohol-based resin suitable as a dispersant for suspension polymerization of a vinyl-based compound in the production of polyvinyl chloride, a dispersant, and a dispersant for suspension polymerization. .
ポリビニルアルコール系樹脂（以下、「ポリビニルアルコール」を「ＰＶＡ」と略記する場合がある。）は、酢酸ビニル等のビニルエステル系モノマーを重合した重合体をケン化することにより得られるものである。ＰＶＡ系樹脂は、通常熱処理することにより、脱水し、主鎖中に二重結合を有する構造をもつこととなり、かかる構造を有するＰＶＡ系樹脂は、ポリ塩化ビニル製造時の懸濁用分散安定剤、保水材等の用途に用いられている。また、ＰＶＡ系樹脂を用いてなるフィルムや繊維を熱処理することにより強度を向上させることができることも知られている。 Polyvinyl alcohol resin (hereinafter, "polyvinyl alcohol" may be abbreviated as "PVA") is obtained by saponifying a polymer obtained by polymerizing a vinyl ester monomer such as vinyl acetate. PVA-based resins are usually dehydrated by heat treatment, and have a structure having a double bond in the main chain. , water retention materials, etc. It is also known that the strength can be improved by heat-treating a film or fiber using a PVA-based resin.
上記ＰＶＡ系樹脂中の二重結合は、特に０．１重量％水溶液の紫外線吸収スペクトルにより確認することが出来る。２１５ｎｍ付近のピークは［－ＣＯ－ＣＨ＝ＣＨ－］の構造に帰属し、２８０ｎｍ付近のピークは［－ＣＯ－（ＣＨ＝ＣＨ）２－］の構造に帰属し、３２０ｎｍ付近のピークは［－ＣＯ－（ＣＨ＝ＣＨ）３－］の構造に帰属するものである。 The double bond in the PVA-based resin can be confirmed particularly by the ultraviolet absorption spectrum of a 0.1% by weight aqueous solution. The peak near 215 nm belongs to the [-CO-CH=CH-] structure, the peak near 280 nm belongs to the [-CO-(CH=CH) 2 -] structure, and the peak near 320 nm belongs to [- CO—(CH═CH) 3 —].
一方、ポリ塩化ビニルを製造する際の懸濁重合用分散剤としては、種々の熱処理ＰＶＡ系樹脂が検討されている。
例えば、分子内にカルボニル基を有し、かつ２～３価の金属の塩又は水酸化物を含有するポリビニルアルコール系樹脂が提案されている（例えば、特許文献１参照。）。また、濃度０．１重量％水溶液の紫外吸収スペクトルによる２８０ｎｍの吸光度（ａ）が０．１より大であり、同水溶液の紫外吸収スペクトルによる３２０ｎｍの吸光度（ｂ）が０．０３以上であり、吸光度（ｂ）／吸光度（ａ）が０．３未満であり、かつ残存酢酸基のブロックキャラクターが０．４以上であるＰＶＡ系重合体が提案されている（例えば、特許文献２参照。）。
On the other hand, various heat-treated PVA-based resins have been studied as dispersants for suspension polymerization in the production of polyvinyl chloride.
For example, a polyvinyl alcohol-based resin having a carbonyl group in the molecule and containing a salt or hydroxide of a divalent or trivalent metal has been proposed (see, for example, Patent Document 1). Further, the absorbance (a) at 280 nm according to the ultraviolet absorption spectrum of an aqueous solution with a concentration of 0.1% by weight is greater than 0.1, and the absorbance (b) at 320 nm according to the ultraviolet absorption spectrum of the same aqueous solution is 0.03 or more, A PVA-based polymer having an absorbance (b)/absorbance (a) ratio of less than 0.3 and a residual acetic acid block character of 0.4 or more has been proposed (see, for example, Patent Document 2).
しかし、特許文献１及び２に記載のＰＶＡ系樹脂を得るためには、約１５０℃で５～６時間熱処理を行なうことが必要であり、製造コストが高くなるという問題があった。また、製造工程において、酸素と接触する機会が多いため不溶解物が生じる可能性があるとともに、アセトキシ基等の残存脂肪酸エステル基のランダム性が上がらないという問題もあった。 However, in order to obtain the PVA-based resins described in Patent Documents 1 and 2, it is necessary to perform heat treatment at about 150° C. for 5 to 6 hours, which raises the problem of high production costs. In addition, in the manufacturing process, there is a possibility that insoluble matter is generated due to frequent contact with oxygen, and there is also the problem that the randomness of residual fatty acid ester groups such as acetoxy groups cannot be improved.
上記の課題を解決するために、例えば、特許文献３では、分子内にカルボニル基を有し、残存脂肪酸エステル基のブロックキャラクターが０．５以上であるポリビニルアルコール系樹脂であって、ポリビニルアルコール樹脂の０．１重量％水溶液の紫外線吸収スペクトルによる２１５ｎｍ、２８０ｎｍ、３２０ｎｍのそれぞれの吸光度が０．１以上であり、３２０ｎｍの吸光度／２８０ｎｍの吸光度の比が０．３以上であるＰＶＡ系樹脂が提案されている。 In order to solve the above problems, for example, in Patent Document 3, a polyvinyl alcohol resin having a carbonyl group in the molecule and a block character of the residual fatty acid ester group of 0.5 or more, which is a polyvinyl alcohol resin The absorbance at 215 nm, 280 nm, and 320 nm is 0.1 or more according to the ultraviolet absorption spectrum of a 0.1 wt% aqueous solution of PVA-based resin, and the ratio of absorbance at 320 nm/absorbance at 280 nm is 0.3 or more. It is
しかしながら、従来のＰＶＡ系樹脂は、得られた樹脂に着色が発生し、ひいてはポリ塩化ビニル製造時の懸濁重合用分散剤として用いた場合にポリ塩化ビニルに着色が発生するという問題が残るものであった。
近年の要求物性の高まりから、懸濁重合物（例えば、ポリ塩化ビニル）の着色を抑えるために、懸濁重合用分散剤として用いられるＰＶＡ系樹脂の着色を抑えることが求められている。
However, conventional PVA-based resins have the problem that the resulting resin is colored, and that polyvinyl chloride is colored when used as a dispersant for suspension polymerization in the production of polyvinyl chloride. Met.
Due to the increasing demand for physical properties in recent years, it is required to suppress the coloring of PVA-based resins used as dispersants for suspension polymerization in order to suppress the coloring of suspension polymers (eg, polyvinyl chloride).
そこで、本発明は、着色が抑えられたＰＶＡ系樹脂を提供すること、並びに該ＰＶＡ系樹脂を用いた分散剤及びポリ塩化ビニル製造時に用いる懸濁重合用分散剤を提供することを課題とする。 Accordingly, an object of the present invention is to provide a PVA-based resin in which coloring is suppressed, and to provide a dispersant using the PVA-based resin and a dispersant for suspension polymerization used in the production of polyvinyl chloride. .
本発明者らは上記課題を解決するために鋭意検討を重ねた結果、ＰＶＡ系樹脂の着色には樹脂中の微粉量が関係することを見出し、本発明を完成するに至った。 The present inventors have made intensive studies to solve the above problems, and as a result, have found that the coloring of PVA-based resins is related to the amount of fine powder in the resin, and have completed the present invention.
すなわち、本発明の要旨は、以下の（１）～（５）である。
（１）０．１重量％水溶液としたときの紫外線吸収スペクトルにおける３２０ｎｍの吸光度（Ｘ）が０．１以上であり、粒子径５００μｍ以下の微粉の含有量が６０重量％以下であるポリビニルアルコール系樹脂。
（２）０．１重量％水溶液としたときの紫外線吸収スペクトルにおける２８０ｎｍの吸光度（Ｙ）に対する３２０ｎｍの吸光度（Ｘ）の比（Ｘ／Ｙ）が０．３以上である、前記（１）に記載のポリビニルアルコール系樹脂。
（３）ケン化度が６０モル％以上である、前記（１）又は（２）に記載のポリビニルアルコール系樹脂。
（４）前記（１）～（３）のいずれか１つに記載のポリビニルアルコール系樹脂からなる分散剤。
（５）前記（１）～（３）のいずれか１つに記載のポリビニルアルコール系樹脂からなる懸濁重合用分散剤。
That is, the gist of the present invention is the following (1) to (5).
(1) A polyvinyl alcohol-based poly(vinyl alcohol) having an absorbance (X) of 0.1 or more at 320 nm in an ultraviolet absorption spectrum when made into a 0.1% by weight aqueous solution, and a content of fine powder having a particle diameter of 500 μm or less of 60% by weight or less. resin.
(2) The ratio (X/Y) of the absorbance (X) at 320 nm to the absorbance (Y) at 280 nm in the ultraviolet absorption spectrum when made into a 0.1 wt% aqueous solution is 0.3 or more, according to (1) The polyvinyl alcohol-based resin described.
(3) The polyvinyl alcohol resin according to (1) or (2) above, which has a degree of saponification of 60 mol % or more.
(4) A dispersant comprising the polyvinyl alcohol resin according to any one of (1) to (3) above.
(5) A dispersant for suspension polymerization comprising the polyvinyl alcohol-based resin according to any one of (1) to (3) above.
本発明によれば、着色の少ない外観良好なＰＶＡ系樹脂が得られる。よって、かかるＰＶＡ系樹脂を懸濁重合用分散剤として用いた場合に、得られる重合体の着色を抑えることができる。 According to the present invention, it is possible to obtain a PVA-based resin that is less colored and has a good appearance. Therefore, when such a PVA-based resin is used as a dispersant for suspension polymerization, coloring of the resulting polymer can be suppressed.
以下、本発明のポリビニルアルコール系樹脂について詳細に説明する。 The polyvinyl alcohol-based resin of the present invention will be described in detail below.
［ポリビニルアルコール系樹脂］
本発明のポリビニルアルコール系樹脂（ＰＶＡ系樹脂）は熱処理が施された熱処理タイプのＰＶＡ系樹脂であって、０．１重量％水溶液としたときの紫外線吸収スペクトルにおける３２０ｎｍの吸光度（Ｘ）が０．１以上であり、粒子径５００μｍ以下の微粉の含有量が６０重量％以下である。本発明者らの研究により、５００μｍ以下の微粉を成すＰＶＡ系樹脂は熱により着色しやすくなる傾向があることが明らかとなり、本発明のＰＶＡ系樹脂は、微粉の含有量を６０重量％以下に制御することによりその着色を抑制することができたものである。
[Polyvinyl alcohol resin]
The polyvinyl alcohol-based resin (PVA-based resin) of the present invention is a heat-treated PVA-based resin that has been subjected to heat treatment, and has an absorbance (X) of 0 at 320 nm in the ultraviolet absorption spectrum when made into a 0.1% by weight aqueous solution. .1 or more, and the content of fine powder having a particle diameter of 500 μm or less is 60% by weight or less. According to the studies of the present inventors, it has become clear that PVA-based resins that form fine powders of 500 μm or less tend to be easily colored by heat. It was possible to suppress the coloring by controlling.
一般的に、ＰＶＡ系樹脂は、ビニルエステル単独重合体、またはビニルエステルと他の単量体との共重合体を、アルカリ触媒等を用いてケン化して得られる樹脂である。本発明のＰＶＡ系樹脂は、このケン化により得られたＰＶＡ系樹脂を熱処理して、脱水又は脱酢酸反応を起こすことにより得られる。 In general, PVA-based resins are resins obtained by saponifying vinyl ester homopolymers or copolymers of vinyl esters and other monomers using an alkali catalyst or the like. The PVA-based resin of the present invention is obtained by heat-treating the PVA-based resin obtained by this saponification to cause dehydration or deacetic acid reaction.
本発明のＰＶＡ系樹脂のケン化度は、熱処理前のＰＶＡ系樹脂のケン化度と同じである。ケン化度（ＪＩＳ Ｋ ６７２６に準拠して測定。）は、６０モル％以上であることが好ましく、より好ましくは６５～９８モル％、更に好ましくは６７～９０モル％、特に好ましくは６９～８８モル％である。本発明のＰＶＡ系樹脂は、分子中に水酸基（親水性）の他に酢酸基（疎水基）が存在するため、界面活性能を有し、分散媒に対して均一に分散できる。ケン化度が低すぎると水分散性が低下する傾向があるため、ケン化度は６０モル％以上であることが好ましい。 The saponification degree of the PVA-based resin of the present invention is the same as the saponification degree of the PVA-based resin before the heat treatment. Saponification degree (measured according to JIS K 6726.) is preferably 60 mol% or more, more preferably 65 to 98 mol%, still more preferably 67 to 90 mol%, particularly preferably 69 to 88 in mol %. Since the PVA-based resin of the present invention has hydroxyl groups (hydrophilic) and acetic acid groups (hydrophobic groups) in its molecule, it has surface activity and can be uniformly dispersed in a dispersion medium. If the degree of saponification is too low, the water dispersibility tends to decrease, so the degree of saponification is preferably 60 mol % or more.
本発明のＰＶＡ系樹脂の平均重合度は、熱処理前のＰＶＡ系樹脂の平均重合度と同じである。平均重合度は、１００～４０００であることが好ましく、より好ましくは２００～３０００、特に好ましくは３００～１０００である。平均重合度が低すぎると、界面活性能が低くなる傾向があり、塩化ビニル懸濁重合用分散剤として用いる場合、懸濁重合時に凝集を起こしやすくなる。逆に平均重合度が高すぎると、ＰＶＡ系樹脂水溶液の粘度が上昇し、ハンドリング性が低下する。
なお、平均重合度はＪＩＳ Ｋ ６７２６に準拠して測定することができる。
The average degree of polymerization of the PVA-based resin of the present invention is the same as the average degree of polymerization of the PVA-based resin before heat treatment. The average degree of polymerization is preferably 100-4000, more preferably 200-3000, particularly preferably 300-1000. If the average degree of polymerization is too low, the surface activity tends to be low, and when used as a dispersant for vinyl chloride suspension polymerization, aggregation tends to occur during suspension polymerization. Conversely, if the average degree of polymerization is too high, the viscosity of the aqueous PVA-based resin solution will increase, resulting in poor handleability.
The average degree of polymerization can be measured according to JIS K6726.
本発明のＰＶＡ系樹脂を０．１重量％水溶液としたときの紫外線吸収スペクトルにおける３２０ｎｍの吸光度（Ｘ）は０．１以上である。ＰＶＡ系樹脂の０．１重量％水溶液の３２０ｎｍにおける紫外線吸光度が０．１未満であると、二重結合の生成が少ないため、界面活性能が低下する傾向がある。ＰＶＡ系樹脂の０．１重量％水溶液の３２０ｎｍにおける紫外線吸光度は、好ましくは０．２以上であり、上限は特に限定されないが、製造可能性の観点から１．５程度である。 The absorbance (X) at 320 nm in the ultraviolet absorption spectrum of a 0.1% by weight aqueous solution of the PVA-based resin of the present invention is 0.1 or more. If the UV absorbance at 320 nm of the 0.1% by weight aqueous solution of the PVA-based resin is less than 0.1, the formation of double bonds is small, and the surface activity tends to decrease. The ultraviolet absorbance at 320 nm of a 0.1% by weight aqueous solution of the PVA-based resin is preferably 0.2 or more, and although the upper limit is not particularly limited, it is about 1.5 from the viewpoint of manufacturability.
また、３２０ｎｍ以外のその他の波長における紫外線吸光度は、以下であることが好ましい。具体的には、２１５ｎｍにおける紫外線吸光度は０．１以上が好ましく、より好ましくは０．３以上であり、また上限は、２程度である。２８０ｎｍにおける紫外線吸光度は０．１以上が好ましく、より好ましくは０．３以上であり、また上限は、２程度である。これらの吸光度が低すぎると二重結合の生成が少ないため、界面活性能が低下する傾向があり、高すぎると製造可能性が低下する傾向がある。 Moreover, it is preferable that the ultraviolet absorbance at wavelengths other than 320 nm is as follows. Specifically, the ultraviolet absorbance at 215 nm is preferably 0.1 or more, more preferably 0.3 or more, and the upper limit is about 2. The ultraviolet absorbance at 280 nm is preferably 0.1 or more, more preferably 0.3 or more, and the upper limit is about 2. If these absorbances are too low, the formation of double bonds is small, so that the surface activity tends to decrease, and if it is too high, the manufacturability tends to decrease.
なお、紫外線吸収スペクトルの２１５ｎｍでの吸収は、ＰＶＡ系樹脂中の－ＣＯ－ＣＨ＝ＣＨ－の構造に帰属し、２８０ｎｍでの吸収は、ＰＶＡ系樹脂中の－ＣＯ－（ＣＨ＝ＣＨ）２－の構造に帰属し、３２０ｎｍでの吸収は、ＰＶＡ系樹脂中の－ＣＯ－（ＣＨ＝ＣＨ）３－の構造に帰属する。 The absorption at 215 nm of the ultraviolet absorption spectrum is attributed to the structure of -CO-CH=CH- in the PVA-based resin, and the absorption at 280 nm is -CO-(CH=CH) 2 in the PVA-based resin. -, and the absorption at 320 nm is attributed to the structure of -CO-(CH=CH) 3 - in the PVA-based resin.
また、本発明において、本発明のＰＶＡ系樹脂を０．１重量％水溶液としたときの紫外線吸収スペクトルにおける２８０ｎｍの吸光度（Ｙ）に対する３２０ｎｍの吸光度（Ｘ）の比（Ｘ／Ｙ：３２０ｎｍ／２８０ｎｍ）は、０．３以上であることが好ましく、より好ましくは０．４以上であり、更に好ましくは０．５以上である。前記吸光度比が小さすぎると、塩化ビニル懸濁重合用分散剤として用いた場合に、界面活性能が低くなり懸濁重合安定性が低下する傾向がある。また上限は特に限定されないが、生産性の観点から、３程度である。 In the present invention, the ratio of the absorbance (X) at 320 nm to the absorbance (Y) at 280 nm in the ultraviolet absorption spectrum when the PVA-based resin of the present invention is made into a 0.1% by weight aqueous solution (X/Y: 320 nm/280 nm ) is preferably 0.3 or more, more preferably 0.4 or more, and still more preferably 0.5 or more. If the absorbance ratio is too small, the surface activity tends to be low and the suspension polymerization stability tends to be low when used as a dispersant for vinyl chloride suspension polymerization. Although the upper limit is not particularly limited, it is about 3 from the viewpoint of productivity.
かかる吸光度は、紫外可視近赤外分光光度計（例えば、日本分光株式会社製「Ｖ－５６０」（商品名））を用いて、波長２１５ｎｍ、２８０ｎｍ、３２０ｎｍにおいて、ＰＶＡ系樹脂の０．１重量％水溶液の吸光度を測定することができる。なお、厚さ１ｃｍの試料容器（セル）を用いて、測定する。 Such absorbance is measured using an ultraviolet-visible-near-infrared spectrophotometer (for example, "V-560" (trade name) manufactured by JASCO Corporation) at wavelengths of 215 nm, 280 nm, and 320 nm. % aqueous solution can be measured. The measurement is performed using a sample container (cell) having a thickness of 1 cm.
本発明のＰＶＡ系樹脂は、粒子径５００μｍ以下の微粉の含有量が６０重量％以下であり、好ましくは５０重量％以下、更に好ましくは３５重量％以下、特に好ましくは２０重量％以下であり、粒子径５００μｍ以下の微粉が含まれていない（すなわち、０重量％である）ことが最も好ましい。５００μｍ以下の粒子径を有する微粉（樹脂粒子）の含有量が多すぎると、ＰＶＡ系樹脂が着色して、外観良好なＰＶＡ系樹脂が得られない傾向があり、ひいては、塩化ビニル懸濁重合用分散剤として用いた場合にも塩化ビニル樹脂が着色してしまう傾向がある。 In the PVA-based resin of the present invention, the content of fine powder having a particle size of 500 μm or less is 60% by weight or less, preferably 50% by weight or less, more preferably 35% by weight or less, and particularly preferably 20% by weight or less. Most preferably, it does not contain fine powder with a particle size of 500 μm or less (that is, it is 0% by weight). If the content of fine powder (resin particles) having a particle size of 500 μm or less is too high, the PVA resin tends to be colored and a PVA resin with a good appearance cannot be obtained. When used as a dispersant, the vinyl chloride resin tends to be colored.
なお、粒子径５００μｍ以下の微粉の含有量は、例えば、公称目開き５００μｍの篩（ＪＩＳ Ｚ８８０１－１：２０００「標準ふるい」）で篩分けして、ＰＶＡ系樹脂の全重量に対する篩を通過した微粉の割合を算出することにより求めることができる。 The content of fine powder with a particle size of 500 μm or less is, for example, sieved with a sieve with a nominal opening of 500 μm (JIS Z8801-1: 2000 “standard sieve”), and the total weight of the PVA-based resin is passed through the sieve. It can be obtained by calculating the proportion of fine powder.
本発明において、本発明のＰＶＡ系樹脂を１．０重量％水溶液としたときの該水溶液のイエローインデックス（ＹＩ）値は、３３以下であることが好ましく、より好ましくは３１以下、更に好ましくは３０以下、特に好ましくは２８以下である。ＹＩ値が小さいＰＶＡ系樹脂は着色が抑えられたＰＶＡ系樹脂である。下限値は０であることが好ましい。
なお、ＹＩ値の測定は、例えば、コニカミノルタ株式会社製の測色計「ＣＭ－３６００Ａ」（商品名）を用いて測定することができる。
In the present invention, when the PVA-based resin of the present invention is made into a 1.0% by weight aqueous solution, the yellow index (YI) value of the aqueous solution is preferably 33 or less, more preferably 31 or less, and still more preferably 30. 28 or less is particularly preferable. A PVA-based resin having a small YI value is a PVA-based resin in which coloring is suppressed. A lower limit of 0 is preferred.
The YI value can be measured using, for example, a colorimeter "CM-3600A" (trade name) manufactured by Konica Minolta, Inc.
本発明のＰＶＡ系樹脂のブロックキャラクター（ＰＶＡ系樹脂のビニルアルコール単位とビニルエステル単位のブロック性を表す指標）は０．５以上であることが好ましく、より好ましくは０．５５以上である。ブロックキャラクターが低すぎると、塩化ビニル等のビニル系化合物の懸濁重合時の発泡抑制効果が低くなる傾向がある。上限は特にはないが、ＰＶＡ系樹脂の製造可能性の点から０．９以下である。 The block character of the PVA-based resin of the present invention (an index representing the blocking properties of vinyl alcohol units and vinyl ester units of the PVA-based resin) is preferably 0.5 or more, more preferably 0.55 or more. If the block character is too low, the effect of inhibiting foaming during suspension polymerization of a vinyl compound such as vinyl chloride tends to be low. Although there is no particular upper limit, it is 0.9 or less from the viewpoint of the production possibility of the PVA-based resin.
なお、ブロックキャラクター（η）は以下のように測定できる。
ＰＶＡ系樹脂を１３Ｃ－ＮＭＲで測定し（内部標準物質として３－（トリメチルシリル）－２，２，３，３－ｄ４－プロピオン酸ナトリウム塩（３－（ｔｒｉｍｅｔｈｙｌｓｉｌｙｌ）ｐｒｏｐｉｏｎｉｃ－２，２，３，３－ｄ４ａｃｉｄ ｓｏｄｉｕｍ ｓａｌｔを使用）、３８～４９ｐｐｍの範囲に見られるメチレン炭素部分に基づき吸収〔（ＯＨ，ＯＨ）ｄｙａｄの吸収＝４３．５～４６ｐｐｍ、（ＯＨ，ＯＲ）ｄｙａｄの吸収＝４１～４３．５ｐｐｍ、（ＯＲ，ＯＲ）ｄｙａｄの吸収＝３８～４０．５ｐｐｍ、ただし、Ｒはアセチル基（ＣＨ３ＣＯ－）を表わす。〕の吸収強度比から求められるもので、より具体的には下記式より算出される値である。
〔η〕＝（ＯＨ，ＯＲ）／２（ＯＨ）（ＯＲ）
（ただし、（ＯＨ，ＯＲ）、（ＯＨ）、（ＯＲ）は、いずれもモル分率で計算するものとする。また、（ＯＨ）は１３Ｃ－ＮＭＲの積分比により算出されるケン化度（モル分率）で、（ＯＲ）はその時のアセトキシ基のモル分率を示す。）
The block character (η) can be measured as follows.
The PVA-based resin was measured by 13 C-NMR (3-(trimethylsilyl)-2,2,3,3-d 4 -propionic acid sodium salt (3-(trimethylsilyl) propionic-2,2,3 , using 3-d 4 acid sodium salt), absorption based on methylene carbon moieties found in the range of 38-49 ppm [(OH, OH) dyad absorption = 43.5-46 ppm, (OH, OR) dyad absorption = 41 to 43.5 ppm, (OR, OR) dyad absorption = 38 to 40.5 ppm, where R represents an acetyl group (CH 3 CO—). Specifically, it is a value calculated from the following formula.
[η]=(OH,OR)/2(OH)(OR)
(However, (OH, OR), (OH), and (OR) are all calculated as mole fractions. In addition, (OH) is the degree of saponification calculated by the integral ratio of 13 C-NMR (molar fraction), (OR) indicates the molar fraction of the acetoxy group at that time.)
本発明のＰＶＡ系樹脂には、２～３価の金属の塩及び水酸化物のうちの少なくとも１つを含有することが好ましい。２～３価の金属の塩及び水酸化物のうちの少なくとも１つを含有することで効率的に熱処理がかかる。 The PVA-based resin of the present invention preferably contains at least one of divalent to trivalent metal salts and hydroxides. By containing at least one of divalent to trivalent metal salts and hydroxides, efficient heat treatment is applied.
２～３価の金属としては、例えば、マグネシウム、カルシウム、亜鉛、アルミニウム等が挙げられる。
これら金属の塩又は水酸化物の具体例としては、例えば、酢酸マグネシウム４水和物、酢酸カルシウム、プロピオン酸カルシウム、酪酸マグネシウム、炭酸マグネシウム、水酸化マグネシウム、酢酸亜鉛、水酸化アルミニウム等が挙げられ、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。中でも、水及び／又はメタノール等に溶解して工業的に取り扱い易いという点で酢酸マグネシウム４水和物や酢酸カルシウムが好ましい。
Divalent to trivalent metals include, for example, magnesium, calcium, zinc and aluminum.
Specific examples of salts or hydroxides of these metals include magnesium acetate tetrahydrate, calcium acetate, calcium propionate, magnesium butyrate, magnesium carbonate, magnesium hydroxide, zinc acetate, and aluminum hydroxide. , may be used singly or in combination of two or more. Among them, magnesium acetate tetrahydrate and calcium acetate are preferable because they are dissolved in water and/or methanol and the like and are easy to handle industrially.
本発明のＰＶＡ系樹脂中の２～３価の金属の塩及び／又は水酸化物の含有量としては、ＰＶＡ系樹脂に対して３０～３００μｍｏｌ／ｇであることが好ましく、更に好ましくは４０～２００μｍｏｌ／ｇである。該含有量が少なすぎると、ビニレン基の生成量が低下し、逆に多すぎると、ＰＶＡ系樹脂の着色や分解が生じる傾向がある。 The content of divalent to trivalent metal salts and/or hydroxides in the PVA resin of the present invention is preferably 30 to 300 μmol/g, more preferably 40 to 300 μmol/g, relative to the PVA resin. 200 μmol/g. If the content is too small, the amount of vinylene groups produced will decrease, and if it is too large, the PVA resin tends to be colored or decomposed.
２～３価の金属の塩及び／又は水酸化物の含有方法は限定されず、上記の化合物をケン化前のペーストやケン化後のスラリー等に直接添加してもよいが、好ましくはメタノール、エタノール、プロパノール等のアルコール、又は水に溶解させて３～１５重量％程度の濃度の溶液状で、ケン化後のＰＶＡスラリーに添加し、ＰＶＡ系樹脂に分配させる方法が好ましい。 The method of containing the salt and / or hydroxide of divalent to trivalent metals is not limited, and the above compounds may be directly added to the paste before saponification or the slurry after saponification, but preferably methanol , ethanol, propanol, etc., or water to form a solution having a concentration of about 3 to 15% by weight, which is added to the PVA slurry after saponification and distributed to the PVA-based resin.
［ポリビニルアルコール系樹脂の製造方法］
本発明のＰＶＡ系樹脂は、上記したように、０．１重量％水溶液としたときの紫外線吸収スペクトルにおける３２０ｎｍの吸光度（Ｘ）が０．１以上である。３２０ｎｍにおける吸光度（Ｘ）を０．１以上にするためには、例えば、分子内にカルボニル基を有したＰＶＡ系樹脂に共役二重結合を導入した樹脂を用い、更にそれを熱処理し、脱水または脱酢酸反応を起こす方法が挙げられる。
[Method for producing polyvinyl alcohol-based resin]
As described above, the PVA-based resin of the present invention has an absorbance (X) of 0.1 or more at 320 nm in the ultraviolet absorption spectrum when it is made into a 0.1% by weight aqueous solution. In order to make the absorbance (X) at 320 nm 0.1 or more, for example, a resin obtained by introducing a conjugated double bond into a PVA resin having a carbonyl group in the molecule is used, and then heat-treated, dehydrated or A method of causing a deacetic acid reaction is mentioned.
まず、ＰＶＡ系樹脂の分子内にカルボニル基を導入する方法について説明する。かかる方法としては、例えば、以下の方法（ｉ）～（ｉｖ）が挙げられる。
（ｉ）ビニルエステル系単量体を重合し、得られた重合体をケン化し、得られたＰＶＡ系樹脂を過酸化水素等の酸化剤で酸化処理する方法
（ｉｉ）ビニルエステル系単量体の重合の際に、アルデヒド類やケトン類等のカルボニル基を含有する連鎖移動剤の共存下で重合を行い、得られた重合体をケン化する方法
（ｉｉｉ）１－メトキシ－ビニルアセテート等の共存下でビニルエステル系単量体を重合し、得られた重合体をケン化する方法
（ｉｖ）ビニルエステル系単量体の重合時にエアを吹き込んで重合し、得られた重合体をケン化する方法
中でも、工業的には、溶剤回収が容易であるという観点から上記（ｉｉ）の方法が好ましい。
First, a method for introducing a carbonyl group into the molecule of the PVA-based resin will be described. Such methods include, for example, the following methods (i) to (iv).
(i) A method of polymerizing a vinyl ester-based monomer, saponifying the obtained polymer, and oxidizing the obtained PVA-based resin with an oxidizing agent such as hydrogen peroxide (ii) Vinyl ester-based monomer (iii) a method of saponifying the resulting polymer by polymerizing in the presence of a chain transfer agent containing a carbonyl group such as aldehydes or ketones in the polymerization of (iii) 1-methoxy-vinyl acetate, etc. Method of polymerizing a vinyl ester-based monomer in the presence of a vinyl ester-based monomer and saponifying the obtained polymer (iv) Polymerizing the vinyl ester-based monomer by blowing air during polymerization, and saponifying the obtained polymer. Among them, industrially, the above method (ii) is preferable from the viewpoint of facilitating solvent recovery.
以下、上記（ｉｉ）の方法を例にとり、本発明のＰＶＡ系樹脂の製造方法を説明する。（ｉｉ）の方法では、本発明のＰＶＡ系樹脂は、以下のスキームにより示される方法により得られる。なお、スキーム中、Ａｃはアセチル基を示す。 Hereinafter, the method for producing the PVA-based resin of the present invention will be described by taking the above method (ii) as an example. In method (ii), the PVA-based resin of the present invention is obtained by the method shown in the scheme below. In the scheme, Ac represents an acetyl group.
出発原料であるビニルエステル系単量体としては、例えば、ギ酸ビニル、酢酸ビニル、プロピオン酸ビニル、酪酸ビニル、カプリン酸ビニル、ラウリン酸ビニル、パルミチン酸ビニル、ステアリン酸ビニルおよびその他の直鎖または分岐状の飽和脂肪酸ビニルエステル等が挙げられる。実用的観点から、酢酸ビニルが好ましく、通常、酢酸ビニルが単独でまたは酢酸ビニル以外の脂肪酸ビニルエステル化合物と組み合わせて使用される。 Vinyl ester monomers as starting materials include, for example, vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caprate, vinyl laurate, vinyl palmitate, vinyl stearate and other linear or branched saturated fatty acid vinyl ester and the like. From a practical point of view, vinyl acetate is preferred, and usually vinyl acetate is used alone or in combination with fatty acid vinyl ester compounds other than vinyl acetate.
ビニルエステル系単量体を重合するに当たっては特に制限はなく公知の重合方法が任意に用いられるが、通常、メタノール、エタノールあるいはイソプロピルアルコール等の炭素数１～３のアルコールを溶媒とする溶液重合が実施される。勿論、バルク重合、乳化重合、懸濁重合も可能である。
かかる溶液重合においてビニルエステル系単量体の仕込み方法は、分割仕込み、一括仕込み等任意の手段を用いてよい。重合反応は、アゾビスイソブチロニトリル、アセチルパーオキサイド、ベンゾイルパーオキサイド、ラウロイルパーオキサイド、アゾビスジメチルバレロニトリル、アゾビスメトキシバレロニトリル等の公知のラジカル重合触媒を用いて行われる。また、重合反応温度は４０℃～沸点程度の範囲から選択される。
There are no particular restrictions on the polymerization of the vinyl ester-based monomer, and any known polymerization method may be used. Usually, solution polymerization using an alcohol having 1 to 3 carbon atoms such as methanol, ethanol or isopropyl alcohol as a solvent is used. be implemented. Of course, bulk polymerization, emulsion polymerization and suspension polymerization are also possible.
In such solution polymerization, the vinyl ester monomer may be charged by any means such as divided charging and batch charging. The polymerization reaction is carried out using known radical polymerization catalysts such as azobisisobutyronitrile, acetyl peroxide, benzoyl peroxide, lauroyl peroxide, azobisdimethylvaleronitrile, azobismethoxyvaleronitrile and the like. Also, the polymerization reaction temperature is selected from the range of about 40° C. to the boiling point.
（ｉｉ）の方法に用いられる連鎖移動剤として、アルデヒド類には、例えば、アセトアルデヒド、プロピオンアルデヒド、ブチルアルデヒド、ベンズアルデヒド等が挙げられ、ケトン類としては、例えば、アセトン、メチルエチルケトン、ヘキサノン、シクロヘキサノン等が挙げられ、これらは１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。
中でも重合後の構造が最終生成物と類似する点で、アルデヒド類を用いることが好ましく、特にはアセトアルデヒドが好ましい。
Examples of chain transfer agents used in the method (ii) include aldehydes such as acetaldehyde, propionaldehyde, butyraldehyde, and benzaldehyde, and ketones such as acetone, methyl ethyl ketone, hexanone, and cyclohexanone. and these may be used singly or in combination of two or more.
Among them, aldehydes are preferred, and acetaldehyde is particularly preferred, because the structure after polymerization is similar to that of the final product.
連鎖移動剤の添加量は、添加する連鎖移動剤の連鎖移動定数や目的とするＰＶＡ系樹脂の重合度等により多少異なるが、通常、ビニルエステル系単量体に対して０.１～５重量％であることが好ましく、より好ましくは０.５～３重量％である。また、連鎖移動剤の仕込み方法は、初期の一括仕込みでもよく、また重合反応時に仕込んでもよい。連鎖移動剤を任意の方法で仕込むことにより、ＰＶＡ系樹脂の分子量分布のコントロールを行うことができる。 The amount of the chain transfer agent to be added varies somewhat depending on the chain transfer constant of the chain transfer agent to be added and the degree of polymerization of the target PVA-based resin, but is usually 0.1 to 5 weights relative to the vinyl ester-based monomer. %, more preferably 0.5 to 3% by weight. The method of charging the chain transfer agent may be batch charging at the initial stage or charging during the polymerization reaction. The molecular weight distribution of the PVA-based resin can be controlled by charging the chain transfer agent by any method.
ビニルエステル系単量体は単独で用いてもよいが、必要であればビニルエステル系単量体と重合可能な単量体を共重合した変性ＰＶＡ系樹脂を用いることもできる。かかる単量体としては、例えば、グリシジル（メタ）アクリレート、グリシジル（メタ）アリルエーテル、３，４－エポキシシクロヘキシル（メタ）アクリレート、アリルグリシジルエーテル等のビニル基とエポキシ基を有する単量体；トリアリルオキシエチレン、ジアリルマレアート、トリアリルシアヌレート、トリアリルイソシアヌレート、テトラアリルオキシエタン、ジアリルフタレート、トリアリルシアヌレート、トリアリルイソシアヌレート等のアリル基を２個以上有する単量体；酢酸アリル、アセト酢酸ビニルエステル、アセト酢酸アリルエステル、ジアセト酢酸アリルエステル等のアリルエステル系単量体；アセトアセトキシエチル（メタ）アクリレート、アセトアセトキシプロピル（メタ）アクリレート等のアセトアセトキシアルキル（メタ）アクリレート；アセトアセトキシエチルクロトナート、アセトアセトキシプロピルクロトナート等のアセトアセトキシアルキルクロトナート；２－シアノアセトアセトキシエチル（メタ）アクリレート；ジビニルベンゼン；エチレングリコールジ（メタ）アクリレート、１，２－プロピレングリコールジ（メタ）アクリレート、１，３－プロピレングリコールジ（メタ）アクリレート、１，４－ブタンジオールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート等のアルキレングリコール（メタ）アクリレート；トリメチロールプロパントリ（メタ）アクリレート；アリル（メタ）アクリレート；２－ヒドロキシエチル（メタ）アクリレート、ヒドロキシプロピル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート等のヒドロキシアルキル（メタ）アクリレート（アルキル部分がＣ１～Ｃ１０アルキル基であり、好ましくはＣ１～Ｃ６アルキル基）；（メタ）アクリロニトリル等のニトリル系単量体；スチレン、α－メチルスチレン等のスチレン系単量体；エチレン、プロピレン、１－ブテン、イソブテン等のオレフィン；塩化ビニル、塩化ビニリデン、フッ化ビニル、フッ化ビニリデン等のハロゲン化オレフィン；エチレンスルホン酸等のオレフィン系単量体；ブタジエン－１，３、２－メチルブタジエン、１，３又は２，３－ジメチルブタジエン－１，３、２－クロロブタジエン－１，３等のジエン系単量体；３－ブテン－１－オール、４－ペンテン－１－オール、５－ヘキセン－１，２－ジオール、グリセリンモノアリルエーテル等のヒドロキシ基含有α－オレフィン類、およびそのアシル化物等の誘導体；１，３－ジアセトキシ－２－メチレンプロパン、１，３－ジプロピオニルオキシ－２－メチレンプロパン、１，３－ジブチロニルオキシ－２－メチレンプロパン等のヒドロキシメチルビニリデンジアセテート類；イタコン酸、マレイン酸、アクリル酸等の不飽和酸類、その塩又はモノ若しくはジアルキルエステル；アクリロニトリル等のニトリル類、メタクリルアミド、ジアセトンアクリルアミド等のアミド類、エチレンスルホン酸、アリルスルホン酸、メタアリルスルホン酸、ＡＭＰＳ等のオレフィンスルホン酸あるいはその塩等の化合物、ビニルトリエトキシシラン、ビニルトリメトキシシラン、ビニルトリプロポキシシラン、ビニルトリブトキシシラン、ビニルメチルジメトキシシラン、ビニルメチルジエトキシシラン等のビニルアルキルジアルコキシシラン；γ－（メタ）アクリロキシプロピルトリメトキシシラン、γ－（メタ）アクリロキシプロピルトリエトキシシラン等のγ－（メタ）アクリロキシプロピルトリアルコキシシラン；γ－（メタ）アクリロキシプロピルメチルジメトキシシラン、γ－（メタ）アクリロキシプロピルメチルジエトキシシラン等のγ－（メタ）アクリロキシプロピルアルキルジアルコキシシラン；ビニルトリス（β－メトキシエトキシ）シラン、ヒドロキシメチルビニリデンジアセテートが挙げられる。ヒドロキシメチルビニリデンジアセテートの具体的な例としては、１，３－ジアセトキシ－２－メチレンプロパン、１，３－ジプロピオニルオキシ－２－メチレンプロパン、１，３－ジブチロニルオキシ－２－メチレンプロパン等が挙げられる。
また、３，４－ジヒドロキシ－１－ブテン、３，４－ジアシロキシ－１－ブテン、３－アシロキシ－４－ヒドロキシ－１－ブテン、４－アシロキシ－３－ヒドロキシ－１－ブテン、３，４－ジアシロキシ－２－メチル－１－ブテン、４，５－ジヒドロキシ－１－ペンテン、４，５－ジアシロキシ－１－ペンテン、４，５－ジヒドロキシ－３－メチル－１－ペンテン、４，５－ジアシロキシ－３－メチル－１－ペンテン、５，６－ジヒドロキシ－１－ヘキセン、５，６－ジアシロキシ－１－ヘキセン、グリセリンモノアリルエーテル、２，３－ジアセトキシ－１－アリルオキシプロパン、２－アセトキシ－１－アリルオキシ－３－ヒドロキシプロパン、３－アセトキシ－１－アリルオキシ－２－ヒドロキシプロパン、グリセリンモノビニルエーテル、グリセリンモノイソプロペニルエーテル、ビニルエチレンカーボネート、２，２－ジメチル－４－ビニル－１，３－ジオキソラン等のジオールを有する化合物等が挙げられる。これらの単量体は、単独で、又は２種以上を併用してもよい。
A vinyl ester-based monomer may be used alone, but if necessary, a modified PVA-based resin obtained by copolymerizing a vinyl ester-based monomer and a polymerizable monomer may also be used. Examples of such monomers include monomers having a vinyl group and an epoxy group, such as glycidyl (meth)acrylate, glycidyl (meth)allyl ether, 3,4-epoxycyclohexyl (meth)acrylate, and allyl glycidyl ether; Monomers having two or more allyl groups such as allyloxyethylene, diallyl maleate, triallyl cyanurate, triallyl isocyanurate, tetraallyloxyethane, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate; allyl acetate , acetoacetate vinyl ester, acetoacetate allyl ester, allyl ester monomers such as diacetoacetate allyl ester; acetoacetoxyalkyl (meth)acrylates such as acetoacetoxyethyl (meth)acrylate and acetoacetoxypropyl (meth)acrylate; Acetoxyethyl crotonate, acetoacetoxyalkyl crotonate such as acetoacetoxypropyl crotonate; 2-cyanoacetoacetoxyethyl (meth)acrylate; divinylbenzene; ethylene glycol di(meth)acrylate, 1,2-propylene glycol di(meth) Alkylene glycols such as acrylates, 1,3-propylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylate (meth) acrylate; trimethylolpropane tri (meth) acrylate; allyl (meth) acrylate; ) acrylate (alkyl moiety is a C1-C10 alkyl group, preferably a C1-C6 alkyl group); (meth) nitrile-based monomers such as acrylonitrile; styrene-based monomers such as α-methylstyrene; ethylene , propylene, 1-butene, olefins such as isobutene; halogenated olefins such as vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride; olefinic monomers such as ethylenesulfonic acid; butadiene-1,3,2- diene-based monomers such as methylbutadiene, 1,3 or 2,3-dimethylbutadiene-1,3,2-chlorobutadiene-1,3; 3-buten-1-ol, 4-penten-1-ol, hydroxy group-containing α-olefins such as 5-hexene-1,2-diol and glycerin monoallyl ether, and derivatives thereof such as acylated products; 1,3-diacetoxy-2-methylenepropane, 1,3-dipropionyloxy -hydroxymethylvinylidene diacetates such as 2-methylenepropane and 1,3-dibutyronyloxy-2-methylenepropane; unsaturated acids such as itaconic acid, maleic acid and acrylic acid, salts thereof, or mono- or dialkyl esters thereof; nitriles such as acrylonitrile; amides such as methacrylamide and diacetone acrylamide; vinylalkyldialkoxysilanes such as methoxysilane, vinyltripropoxysilane, vinyltributoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane; γ-(meth)acryloxypropyltrimethoxysilane, γ-(meth)acryloxy γ-(meth)acryloxypropyltrialkoxysilane such as propyltriethoxysilane; γ-(meth)acryloxysilane such as γ-(meth)acryloxypropylmethyldimethoxysilane and γ-(meth)acryloxypropylmethyldiethoxysilane; roxypropylalkyldialkoxysilane; vinyltris(β-methoxyethoxy)silane, hydroxymethylvinylidene diacetate. Specific examples of hydroxymethylvinylidene diacetate include 1,3-diacetoxy-2-methylenepropane, 1,3-dipropionyloxy-2-methylenepropane, 1,3-dibutyronyloxy-2-methylenepropane etc.
In addition, 3,4-dihydroxy-1-butene, 3,4-diacyloxy-1-butene, 3-acyloxy-4-hydroxy-1-butene, 4-acyloxy-3-hydroxy-1-butene, 3,4- diacyloxy-2-methyl-1-butene, 4,5-dihydroxy-1-pentene, 4,5-diacyloxy-1-pentene, 4,5-dihydroxy-3-methyl-1-pentene, 4,5-diacyloxy- 3-methyl-1-pentene, 5,6-dihydroxy-1-hexene, 5,6-diacyloxy-1-hexene, glycerin monoallyl ether, 2,3-diacetoxy-1-allyloxypropane, 2-acetoxy-1 - allyloxy-3-hydroxypropane, 3-acetoxy-1-allyloxy-2-hydroxypropane, glycerin monovinyl ether, glycerin monoisopropenyl ether, vinylethylene carbonate, 2,2-dimethyl-4-vinyl-1,3-dioxolane compounds having a diol such as These monomers may be used alone or in combination of two or more.
なお、「（メタ）アクリレート」とは「アクリレート及び／又はメタクリレート」を意味し、「（メタ）アリル」、「（メタ）アクリロ」についても同様である。 In addition, "(meth)acrylate" means "acrylate and/or methacrylate", and the same applies to "(meth)allyl" and "(meth)acrylo".
ビニルエステル系単量体と重合可能な単量体の含有量は、２０モル％以下であることが好ましく、１０モル％以下であることがより好ましい。 The content of the vinyl ester monomer and the polymerizable monomer is preferably 20 mol % or less, more preferably 10 mol % or less.
上記重合により得られたビニルエステル系重合体はケン化され、分子内にカルボニル基が導入される。
ケン化は公知の方法で行うことができ、通常、ビニルエステル系重合体をアルコールに溶解させ、アルカリ触媒又は酸触媒の存在下で行われる。アルコールとしては、例えば、メタノール、エタノール、ブタノール等の炭素数１～６のアルコールが挙げられる。
The vinyl ester polymer obtained by the above polymerization is saponified to introduce a carbonyl group into the molecule.
Saponification can be carried out by a known method, usually by dissolving a vinyl ester polymer in alcohol and carrying out in the presence of an alkali catalyst or an acid catalyst. Examples of alcohols include alcohols having 1 to 6 carbon atoms such as methanol, ethanol and butanol.
アルコール中のビニルエステル系重合体の濃度は、溶解率の観点から、２０～５０重量％の範囲から選ばれる。 The concentration of the vinyl ester polymer in alcohol is selected from the range of 20 to 50% by weight from the viewpoint of solubility.
アルカリ触媒としては、例えば、水酸化ナトリウム、水酸化カリウム、ナトリウムメチラート、ナトリウムエチラート、カリウムメチラート等のアルカリ金属の水酸化物やアルコラートの如きアルカリ触媒を用いることができる。酸触媒としては、例えば、塩酸、硫酸等の無機酸水溶液、ｐ－トルエンスルホン酸等の有機酸を用いることができる。かかる触媒の使用量はビニルエステル系単量体に対して１～１００ミリモル当量にすることが好ましく、より好ましくは１～４０ミリモル当量、更に好ましくは１～２０ミリモル当量である。触媒の使用量が少なすぎると、目的とするケン化度までケン化を進めることが困難となる傾向にあり、また触媒の使用量が多すぎてもケン化の反応性の向上は見られないため好ましくない。 Examples of alkali catalysts that can be used include hydroxides of alkali metals such as sodium hydroxide, potassium hydroxide, sodium methylate, sodium ethylate and potassium methylate, and alkali catalysts such as alcoholates. Examples of acid catalysts that can be used include aqueous solutions of inorganic acids such as hydrochloric acid and sulfuric acid, and organic acids such as p-toluenesulfonic acid. The amount of the catalyst to be used is preferably 1 to 100 millimole equivalents, more preferably 1 to 40 millimole equivalents, still more preferably 1 to 20 millimole equivalents, relative to the vinyl ester monomer. If the amount of catalyst used is too small, it tends to be difficult to proceed with saponification to the desired degree of saponification. I don't like it because
ケン化を行う際の反応温度は、特に制限はないが、通常、１０～７０℃が好ましく、より好ましくは２０～５０℃の範囲から選ぶのが望ましい。 The reaction temperature for saponification is not particularly limited, but it is usually preferably 10 to 70°C, more preferably 20 to 50°C.
ケン化を行う際の反応時間は、ケン化の処理方法により適宜調整されればよく、例えば、バッチケン化で行われる場合、ケン化反応は通常２～３時間にわたって行なわれる。 The reaction time for saponification may be appropriately adjusted according to the saponification treatment method. For example, in the case of batch saponification, the saponification reaction is usually carried out for 2 to 3 hours.
本発明では、得られたＰＶＡ系樹脂を後変性させることにより変性ＰＶＡ系樹脂を製造してもよい。変性ＰＶＡ系樹脂を製造する方法としては、例えば、ＰＶＡ系樹脂をアセト酢酸エステル化、アセタール化、ウレタン化、エーテル化、グラフト化、リン酸エステル化、オキシアルキレン化する方法等が挙げられる。 In the present invention, the modified PVA-based resin may be produced by post-modifying the obtained PVA-based resin. Examples of the method for producing the modified PVA-based resin include methods of acetoacetic esterification, acetalization, urethanization, etherification, grafting, phosphate esterification, and oxyalkylenation of the PVA-based resin.
得られたＰＶＡ系樹脂は、熱処理することにより、脱水または脱酢酸反応が起き、共役二重結合が生成し、本発明のＰＶＡ系樹脂が得られる。 By heat-treating the obtained PVA-based resin, a dehydration or deacetic acid reaction occurs, conjugated double bonds are generated, and the PVA-based resin of the present invention is obtained.
熱処理の温度は、通常、１２０～１８０℃の範囲で行うことが好ましく、より好ましくは１４０～１５５℃である。かかる熱処理の温度が低すぎると、所望のビニレン基量（二重結合）が得難くなる傾向があり、逆に高すぎると、熱処理による分解が生じやすくなる傾向がある。 The heat treatment temperature is generally preferably in the range of 120 to 180°C, more preferably 140 to 155°C. If the heat treatment temperature is too low, it tends to be difficult to obtain the desired amount of vinylene groups (double bonds).
熱処理の時間は、通常、０．５～５時間であることが好ましく、より好ましくは１．５～４時間である。かかる熱処理の時間が短すぎると、ビニレン基の生成量が低下する傾向があり、逆に長すぎると、ＰＶＡ系樹脂の着色の原因や水に対する不溶解分生成の原因となる傾向がある。 The heat treatment time is generally preferably 0.5 to 5 hours, more preferably 1.5 to 4 hours. If the heat treatment time is too short, the amount of vinylene groups produced tends to decrease.
熱処理は、いかなる装置を用いてもよく、例えば、ナウターミキサー、コニカルドライヤー等の内容物を加熱しながら撹拌する撹拌装置を用いて行うことができる。 Any device may be used for the heat treatment, and for example, a stirrer that stirs the contents while heating, such as a Nauta mixer or a conical dryer, can be used.
また、熱処理は、酸素濃度が２０容量％以下の酸素雰囲気下で行うのが好ましく、３～１２容量％の酸素雰囲気下で行うのがより好ましい。該酸素濃度が高すぎると、ＰＶＡ系樹脂の着色が生じたり、また不溶化の原因となる傾向がある。 The heat treatment is preferably performed in an oxygen atmosphere with an oxygen concentration of 20% by volume or less, more preferably in an oxygen atmosphere with an oxygen concentration of 3 to 12% by volume. If the oxygen concentration is too high, the PVA resin tends to be colored or become insoluble.
かかる熱処理においては、公知の方法で得られたＰＶＡ系樹脂に上記に示した金属塩を含有させたものを用いることができるが、良好な界面活性能を得るために十分な量のビニレン基を生成せしめるためには、熱処理前のＰＶＡ系樹脂のカルボニル基の含有量は、０．０３～２．５モル％、更には０．０５～２モル％であることが好ましい。 In such a heat treatment, a PVA-based resin obtained by a known method containing the metal salt shown above can be used. For this purpose, the carbonyl group content of the PVA-based resin before heat treatment is preferably 0.03 to 2.5 mol %, more preferably 0.05 to 2 mol %.
上記のようにして得られた熱処理後のＰＶＡ系樹脂は、粒子径５００μｍ以下の微粉が６０重量％以下で含有されるように微粉の含有量を調整する。熱処理後のＰＶＡ系樹脂中の５００μｍ以下の微粉の含有量は、５０重量％以下であることが好ましく、より好ましくは３５重量％以下、特に好ましくは２０重量％以下であり、粒子径５００μｍ以下の微粉が全く含有しない（すなわち、０重量％である）ことが最も好ましい。ＰＶＡ系樹脂は粒子径が小さいほど熱処理により着色が強くなる傾向があるため、粒子径５００μｍ以下の微粉の含有量を６０重量％以下とすることにより、ＰＶＡ系樹脂の着色を抑制することができる。 The fine powder content of the heat-treated PVA-based resin obtained as described above is adjusted so that fine powder having a particle diameter of 500 μm or less is contained in an amount of 60% by weight or less. The content of fine powder of 500 μm or less in the PVA-based resin after heat treatment is preferably 50% by weight or less, more preferably 35% by weight or less, and particularly preferably 20% by weight or less, and has a particle diameter of 500 μm or less. Most preferably, it contains no fines (ie, 0% by weight). Since the smaller the particle size of the PVA-based resin, the more intensely the PVA-based resin tends to be colored by heat treatment, the coloring of the PVA-based resin can be suppressed by setting the content of the fine powder having a particle size of 500 μm or less to 60% by weight or less. .
粒子径５００μｍ以下の微粉の含有量を調整するには、例えば、公称目開き５００μｍの篩（ＪＩＳ Ｚ８８０１－１：２０００「標準ふるい」）で篩分けする方法、ケン化や乾燥等撹拌する工程において、撹拌動力を小さくしたり、撹拌時間を短くする方法等が挙げられる。 In order to adjust the content of fine powder with a particle size of 500 μm or less, for example, a method of sieving with a sieve with a nominal opening of 500 μm (JIS Z8801-1: 2000 “standard sieve”), saponification, drying, etc. In the process of stirring , a method of reducing the stirring power, a method of shortening the stirring time, and the like.
［用途］
上記のようにして得られた本発明のＰＶＡ系樹脂は、着色が抑えられているので色相に優れ、様々な用途に好適に使用することができる。本発明のＰＶＡ系樹脂の用途としては、例えば、以下が挙げられる。
（１）成形物関係：繊維、フィルム、シート、パイプ、チューブ、防漏膜、暫定皮膜、ケミカルレース用、水溶性繊維等。
（２）接着剤関係：木材、紙、アルミ箔、プラスチック等の接着剤、粘着剤、再湿剤、不織布用バインダー、石膏ボードや繊維板等の各種建材用バインダー、各種粉体造粒用バインダー、セメントやモルタル用添加剤、ホットメルト型接着剤、感圧接着剤、アニオン性塗料の固着剤等。
（３）被覆剤関係：紙のクリアーコーティング剤、紙の顔料コーティング剤、紙の内添サイズ剤、繊維製品用サイズ剤、経糸糊剤、繊維加工剤、皮革仕上げ剤、塗料、防曇剤、金属腐食防止剤、亜鉛メッキ用光沢剤、帯電防止剤、導電剤、暫定塗料等。
（４）疎水性樹脂用ブレンド剤関係：疎水性樹脂の帯電防止剤、および親水性付与剤、複合繊維、フィルムその他成形物用添加剤等。
（５）分散剤関係：感熱発色層用塗工液の顕色剤用分散剤、塗料、墨汁、水性カラー、接着剤等の顔料分散安定剤、塩化ビニル、塩化ビニリデン、スチレン、（メタ）アクリレート、酢酸ビニル等の各種ビニル化合物の懸濁重合用分散安定剤等。
（６）乳化分散安定剤関係：各種アクリルモノマー、エチレン性不飽和化合物、ブタジエン性化合物の乳化重合用乳化剤、ポリオレフィン、ポリエステル樹脂等疎水性樹脂、エポキシ樹脂、パラフィン、ビチューメン等の後乳化剤等。
（７）増粘剤関係：各種水溶液やエマルジョンや石油掘削流体の増粘剤等。
（８）凝集剤関係：水中懸濁物及び溶存物の凝集剤、パルプ、スラリーの濾水性等。
（９）交換樹脂等関係：イオン交換樹脂、キレート交換樹脂、イオン交換膜等。
（１０）その他：土壌改良剤、感光剤、感光性レジスト樹脂等。
上記の中でも特に、本発明のＰＶＡ系樹脂は、酢酸ビニルや塩化ビニル等の各種ビニル化合物の懸濁重合用分散安定剤に有用であり、特に塩化ビニル系化合物の懸濁重合用分散安定剤として有用である。
[Use]
Since the PVA-based resin of the present invention obtained as described above has suppressed coloring, it is excellent in hue and can be suitably used for various purposes. Applications of the PVA-based resin of the present invention include, for example, the following.
(1) Molded products: fibers, films, sheets, pipes, tubes, leak-proof membranes, temporary membranes, chemical laces, water-soluble fibers, and the like.
(2) Adhesives: Adhesives for wood, paper, aluminum foil, plastics, adhesives, rewetting agents, binders for non-woven fabrics, binders for various building materials such as gypsum boards and fiberboards, binders for various powder granulation , additives for cement and mortar, hot-melt adhesives, pressure-sensitive adhesives, fixing agents for anionic paints, etc.
(3) Coating agents: clear coating agents for paper, pigment coating agents for paper, internal sizing agents for paper, sizing agents for textile products, warp sizing agents, fiber processing agents, leather finishing agents, paints, anti-fogging agents, Metal corrosion inhibitor, brightener for zinc plating, antistatic agent, conductive agent, temporary paint, etc.
(4) Blending agents for hydrophobic resins: Antistatic agents for hydrophobic resins, hydrophilicity-imparting agents, composite fibers, films and other molding additives, and the like.
(5) Dispersants: Dispersants for color developers of thermosensitive coloring layer coating liquids, paints, India ink, aqueous colors, pigment dispersion stabilizers for adhesives, etc., vinyl chloride, vinylidene chloride, styrene, (meth)acrylates , a dispersion stabilizer for suspension polymerization of various vinyl compounds such as vinyl acetate.
(6) Emulsion dispersion stabilizers: various acrylic monomers, ethylenically unsaturated compounds, emulsifiers for emulsion polymerization of butadiene compounds, hydrophobic resins such as polyolefin and polyester resins, post-emulsifiers such as epoxy resins, paraffin and bitumen.
(7) Thickening agents: Thickening agents for various aqueous solutions, emulsions, and oil drilling fluids.
(8) Flocculants: Flocculants for suspended and dissolved substances in water, freeness of pulp and slurry, and the like.
(9) Exchange resins, etc.: ion exchange resins, chelate exchange resins, ion exchange membranes, and the like.
(10) Others: soil improvers, photosensitizers, photosensitive resist resins, and the like.
Among the above, the PVA-based resin of the present invention is particularly useful as a dispersion stabilizer for suspension polymerization of various vinyl compounds such as vinyl acetate and vinyl chloride, and particularly as a dispersion stabilizer for suspension polymerization of vinyl chloride-based compounds. Useful.
［分散剤］
本発明のＰＶＡ系樹脂を分散剤として使用する場合、被分散体としては、例えば、重合性モノマー、粉体などが挙げられるが、特に重合性モノマーを分散し、懸濁重合用の分散剤として用いることが好ましい。
懸濁重合の対象となる重合性モノマーとしては、例えば、塩化ビニル、ハロゲン化ビニリデン、ビニルエーテル、酢酸ビニル、安息香酸ビニル、アクリル酸、メタクリル酸、マレイン酸又はその無水物やエチレン、プロピレン、スチレン等が挙げられる。中でも、塩化ビニル単独重合又は塩化ビニルと共重合可能なモノマーとの共重合に好適に用いられる。
[Dispersant]
When the PVA-based resin of the present invention is used as a dispersant, examples of the substance to be dispersed include polymerizable monomers and powders. It is preferable to use
Examples of polymerizable monomers subject to suspension polymerization include vinyl chloride, vinylidene halide, vinyl ether, vinyl acetate, vinyl benzoate, acrylic acid, methacrylic acid, maleic acid or their anhydrides, ethylene, propylene, styrene, and the like. is mentioned. Among others, it is preferably used for homopolymerization of vinyl chloride or copolymerization of vinyl chloride with a monomer that can be copolymerized.
［懸濁重合用分散剤］
本発明のＰＶＡ系樹脂を懸濁重合用分散剤として使用する場合について以下に詳述する。
本発明のＰＶＡ系樹脂の使用量は懸濁重合させる単量体に応じて適宜調整すればよいが、例えば、塩化ビニル系単量体の懸濁重合に使用する場合は、通常、塩化ビニル系単量体１００重量部に対して５重量部以下で用いることが好ましく、０．０１～１重量部がより好ましく、さらに好ましくは０．０２～０．２重量部である。かかる使用量が多すぎると分散剤として作用しないＰＶＡ系樹脂が増加する傾向がある。
[Dispersant for suspension polymerization]
The use of the PVA-based resin of the present invention as a dispersant for suspension polymerization will be described in detail below.
The amount of the PVA-based resin of the present invention used may be appropriately adjusted according to the monomer to be suspension-polymerized. It is preferably used in an amount of 5 parts by weight or less, more preferably 0.01 to 1 part by weight, still more preferably 0.02 to 0.2 parts by weight, based on 100 parts by weight of the monomer. If the amount used is too large, the amount of PVA-based resin that does not act as a dispersant tends to increase.
懸濁重合する際には、通常、水又は加熱水媒体に本発明のＰＶＡ系樹脂を分散剤として添加し、塩化ビニル系単量体を分散させて油溶性触媒の存在下で重合を行う。 For suspension polymerization, the PVA-based resin of the present invention is usually added to water or a heated aqueous medium as a dispersant, the vinyl chloride-based monomer is dispersed, and the polymerization is carried out in the presence of an oil-soluble catalyst.
ＰＶＡ系樹脂の添加方法としては、粉末のまま、水又は、アルコール、ケトン、エステル等の有機溶媒又は、これら有機溶媒と水との混合溶媒に溶かした溶液、上記の溶媒に分散させた分散液の状態で添加する。
添加のタイミングとしては、重合の初期に一括添加しても、又重合の途中で分割して添加してもよい。
As a method for adding the PVA-based resin, the powder is dissolved in water, an organic solvent such as alcohol, ketone, ester, etc., or a mixed solvent of these organic solvents and water, or a dispersion liquid dispersed in the above solvent. Add in the state of
As for the timing of addition, it may be added all at once at the beginning of the polymerization, or may be added in portions during the polymerization.
その他添加剤としては、公知の安定剤、例えば高分子物質を併用することも可能である。高分子物質としては、本発明のＰＶＡ系樹脂以外のＰＶＡ系樹脂が挙げられる。ＰＶＡ系樹脂としては、未変性のＰＶＡや、上述の変性ＰＶＡ系樹脂等が挙げられる。 As other additives, known stabilizers such as polymeric substances can be used in combination. Examples of polymeric substances include PVA-based resins other than the PVA-based resin of the present invention. Examples of PVA-based resins include unmodified PVA and modified PVA-based resins described above.
重合助剤としては、各種界面活性剤あるいは無機分散剤等が挙げられ、本発明のＰＶＡ系樹脂を重合助剤として使用することも可能である。 Examples of the polymerization aid include various surfactants, inorganic dispersants, and the like, and it is also possible to use the PVA-based resin of the present invention as the polymerization aid.
重合触媒は油溶性の触媒であればいずれでもよく、例えば、ベンゾイルパーオキサイド、ラウロイルパーオキサイド、ジイソプロピルパーオキシジカーボネート、α，α’－アゾビスイソブチロニトリル、α，α’－アゾビス－２，４－ジメチル－バレロニトリル、アセチルシクロヘキシルスルホニルパーオキサイドあるいはこれらの混合物が使用される。 The polymerization catalyst may be any oil-soluble catalyst, such as benzoyl peroxide, lauroyl peroxide, diisopropyl peroxydicarbonate, α,α'-azobisisobutyronitrile, α,α'-azobis-2. ,4-dimethyl-valeronitrile, acetylcyclohexylsulfonyl peroxide or mixtures thereof are used.
以下、本発明を実施例により更に詳細に説明するが、本発明はその要旨を超えない限り以下の実施例に限定されるものではない。なお、「部」、「％」等は重量基準である。 EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. "Parts", "%" and the like are based on weight.
（実施例１）
＜ＰＶＡ系樹脂の製造＞
酢酸ビニル１００部、アセトアルデヒド１．２部、メタノール４．７部及び酢酸ビニルに対して０．００９２％のアセチルパーオキサイド（ＡＰＯ）を重合缶に仕込み、窒素で置換した。その後、加熱して沸点下で重合を開始させ、反応時間約５．７時間後に重合率９１．８％に達した時点で重合を停止した。次いで未重合の酢酸ビニルを除去し、得られた重合体を水酸化ナトリウムで常法によりケン化して樹脂分１２％のＰＶＡ系樹脂（重合度７７０、ケン化度７１．７モル％、カルボニル基量０．１６モル％）のケン化スラリー（酢酸メチル／メタノール＝８／２（重量比）の溶媒）を調製した。
次に上記で調製したＰＶＡ系樹脂に金属化合物として酢酸マグネシウム４水和物の１０％メタノール溶液をＰＶＡ系樹脂１ｋｇに対して３５０ｇの割合で添加し、２５℃で１時間撹拌した。その後、ヌッチェで振り切りを行って、酢酸マグネシウム１７７μｍｏｌ／ｇを含有したＰＶＡ系樹脂を得た。
次いで、熱処理缶内で、窒素雰囲気下、１１０℃において２時間乾燥させた後、窒素：空気＝１：１（容積比）のガスを１００Ｌ／ｈｒの速度で熱処理缶内に流し込んで、酸素濃度を１０％に保ちつつ１４５℃で３時間熱処理を行った。熱処理後のＰＶＡ系樹脂の特性は以下の通りであった。
平均重合度；６５０（ＪＩＳＫ ６７２６に準拠して測定）、ケン化度；７２.０モル％（ＪＩＳ ６７２６に準拠して測定））、酢酸マグネシウム含有量；１７７μｍｏｌ／ｇ（含有マグネシウム量より算出）
(Example 1)
<Production of PVA-based resin>
100 parts of vinyl acetate, 1.2 parts of acetaldehyde, 4.7 parts of methanol, and 0.0092% of acetyl peroxide (APO) relative to vinyl acetate were charged into a polymerization vessel and purged with nitrogen. Thereafter, the mixture was heated to initiate polymerization below the boiling point, and the polymerization was stopped when the polymerization rate reached 91.8% after about 5.7 hours of reaction time. Next, unpolymerized vinyl acetate is removed, and the resulting polymer is saponified with sodium hydroxide by a conventional method to obtain a PVA resin with a resin content of 12% (polymerization degree 770, saponification degree 71.7 mol%, carbonyl group A saponification slurry (methyl acetate/methanol = 8/2 (weight ratio) solvent) was prepared with an amount of 0.16 mol%).
Next, 350 g of a 10% methanol solution of magnesium acetate tetrahydrate as a metal compound was added to the PVA-based resin prepared above per 1 kg of the PVA-based resin, and the mixture was stirred at 25° C. for 1 hour. Thereafter, the mixture was shaken off with a Nutsche to obtain a PVA-based resin containing 177 μmol/g of magnesium acetate.
Next, in the heat treatment can, after drying at 110 ° C. for 2 hours under a nitrogen atmosphere, a gas of nitrogen: air = 1: 1 (volume ratio) was flowed into the heat treatment can at a rate of 100 L / hr to increase the oxygen concentration. was maintained at 10%, heat treatment was performed at 145° C. for 3 hours. The properties of the PVA-based resin after heat treatment were as follows.
Average degree of polymerization: 650 (measured according to JISK 6726) Saponification degree: 72.0 mol% (measured according to JIS 6726) Magnesium acetate content: 177 µmol/g (calculated from the amount of magnesium contained)
＜微粉回収工程＞
続いて、得られたＰＶＡ系樹脂を３０メッシュの篩（目開き：５００μｍ）を用いてふるい分けし、粒子径５００μｍ以下の微粉（樹脂粒子）を除き、粒子径が５００μｍより大きい粒子径のみのＰＶＡ系樹脂Ａ（微粉量０重量％）を得た。
<Fine powder recovery process>
Subsequently, the obtained PVA-based resin is sieved using a 30-mesh sieve (opening: 500 μm) to remove fine powder (resin particles) having a particle size of 500 μm or less, and only PVA having a particle size larger than 500 μm. A system resin A (fine powder amount: 0% by weight) was obtained.
＜評価１：紫外線吸光度の測定＞
ＰＶＡ系樹脂Ａの０．１％水溶液を作製した。紫外可視近赤外分光光度計（日本分光株式会社製「Ｖ－５６０」（商品名））を用いて、波長２１５ｎｍ、２８０ｎｍ、３２０ｎｍにおける、ＰＶＡ系樹脂Ａの０．１％水溶液の吸光度を測定した。なお、厚さ１ｃｍの試料容器（セル）を用いた。
また、２８０ｎｍの吸光度（Ｙ）に対する３２０ｎｍの吸光度（Ｘ）の比（Ｘ／Ｙ）を算出した。
結果を表１に示す。
<Evaluation 1: Measurement of UV absorbance>
A 0.1% aqueous solution of PVA-based resin A was prepared. Measure the absorbance of a 0.1% aqueous solution of PVA-based resin A at wavelengths of 215 nm, 280 nm, and 320 nm using an ultraviolet-visible near-infrared spectrophotometer (“V-560” (trade name) manufactured by JASCO Corporation). bottom. A sample container (cell) having a thickness of 1 cm was used.
Also, the ratio (X/Y) of the absorbance (X) at 320 nm to the absorbance (Y) at 280 nm was calculated.
Table 1 shows the results.
＜評価２：イエローインデックス（ＹＩ）値の測定＞
ＰＶＡ系樹脂Ａの１．０％水溶液を作製した。かかる水溶液のＹＩ値をコニカミノルタ株式会社製測色計「ＣＭ－３６００Ａ」（商品名）を用いて測定した。
結果を表１に示す。
<Evaluation 2: Measurement of yellow index (YI) value>
A 1.0% aqueous solution of PVA-based resin A was prepared. The YI value of the aqueous solution was measured using a colorimeter "CM-3600A" (trade name) manufactured by Konica Minolta, Inc.
Table 1 shows the results.
（実施例２）
実施例１で得られたＰＶＡ系樹脂Ａに対し、実施例１の回収工程で回収された粒子径５００μｍ以下の微粉を、その含有量が樹脂全体中で３１％となるように混合し、ＰＶＡ系樹脂Ｂ（微粉量３１重量％）を得た。
得られたＰＶＡ系樹脂Ｂについて、実施例１と同様に、各波長における紫外線吸光度、Ｘ／Ｙ値、ＹＩ値を測定した。結果を表１に示す。
(Example 2)
The PVA-based resin A obtained in Example 1 was mixed with the fine powder having a particle size of 500 μm or less recovered in the recovery step of Example 1 so that the content thereof was 31% in the entire resin, and PVA was obtained. A system resin B (fine powder amount: 31% by weight) was obtained.
As in Example 1, the obtained PVA-based resin B was measured for ultraviolet absorbance, X/Y value, and YI value at each wavelength. Table 1 shows the results.
（実施例３）
実施例１で得られたＰＶＡ系樹脂Ａに対し、実施例１の回収工程で回収された粒子径５００μｍ以下の微粉を、その含有量が樹脂全体中で５７％となるように混合し、ＰＶＡ系樹脂Ｃ（微粉量５７重量％）を得た。
得られたＰＶＡ系樹脂Ｃについて、実施例１と同様に、各波長における紫外線吸光度、Ｘ／Ｙ値、ＹＩ値を測定した。結果を表１に示す。
(Example 3)
The PVA-based resin A obtained in Example 1 was mixed with fine powder having a particle size of 500 μm or less recovered in the recovery step of Example 1 so that the content thereof was 57% in the entire resin, and PVA was obtained. A system resin C (fine powder amount: 57% by weight) was obtained.
As in Example 1, the obtained PVA-based resin C was measured for ultraviolet absorbance, X/Y value, and YI value at each wavelength. Table 1 shows the results.
（比較例１）
実施例１において、微粉回収工程を行わなかった以外は実施例１と同様に行い、ＰＶＡ系樹脂Ｄを得た。粒子径５００μｍ以下の微粉の含有量は７８重量％であった。
得られたＰＶＡ系樹脂Ｄについて、実施例１と同様に、各波長における紫外線吸光度、Ｘ／Ｙ値、ＹＩ値を測定した。結果を表１に示す。
(Comparative example 1)
A PVA-based resin D was obtained in the same manner as in Example 1, except that the fine powder recovery step was not performed. The content of fine powder having a particle size of 500 μm or less was 78% by weight.
As in Example 1, the obtained PVA-based resin D was measured for ultraviolet absorbance, X/Y value, and YI value at each wavelength. Table 1 shows the results.
表１の結果より、実施例１～３は、比較例１に比べてＹＩ値が小さく、着色が抑えられていることがわかった。特に粒子径５００μｍ以下の微粉の含有量が少ないほど、ＰＶＡ系樹脂の着色は小さくなることがわかった。
そして、ＰＶＡ系樹脂の０．１重量％水溶液における紫外線吸収スペクトルによる２８０ｎｍの吸光度（Ｙ）に対する３２０ｎｍの吸光度（Ｘ）の比は、実施例１～３のいずれも高く、懸濁重合用分散剤として用いた場合に、懸濁重合安定性が良好に保たれることが示唆された。
From the results in Table 1, it was found that Examples 1 to 3 had smaller YI values than Comparative Example 1, and that coloring was suppressed. In particular, it was found that the smaller the content of fine powder having a particle size of 500 μm or less, the smaller the coloring of the PVA-based resin.
Then, the ratio of the absorbance (X) at 320 nm to the absorbance (Y) at 280 nm in the ultraviolet absorption spectrum of a 0.1% by weight aqueous solution of the PVA-based resin is high in all of Examples 1 to 3, and the dispersant for suspension polymerization It was suggested that suspension polymerization stability was maintained well when used as
本発明を詳細にまた特定の実施形態を参照して説明したが、本発明の精神と範囲を逸脱することなく様々な変更や修正を加えることができることは当業者にとって明らかである。本出願は、２０１６年１２月２１日出願の日本特許出願（特願２０１６－２４７６８６）に基づくものであり、その内容はここに参照として取り込まれる。 Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. This application is based on a Japanese patent application (Japanese Patent Application No. 2016-247686) filed on December 21, 2016, the contents of which are incorporated herein by reference.
本発明のＰＶＡ系樹脂は、二重結合を有し、更に着色が小さいため、各種分散剤として用いた場合に、得られる重合体の着色も抑制できる。特に、塩化ビニル系モノマーの懸濁重合用分散剤として有用である。 Since the PVA-based resin of the present invention has a double bond and is less colored, when it is used as various dispersants, the resulting polymer can be prevented from being colored. In particular, it is useful as a dispersant for suspension polymerization of vinyl chloride monomers.
Claims (7)
Ｘ）が０．１以上であり、粒子径５００μｍ以下の微粉の含有量が３５重量％以下である
ポリビニルアルコール系樹脂。 Absorbance at 320 nm in the ultraviolet absorption spectrum when it is made into a 0.1 wt% aqueous solution (
A polyvinyl alcohol resin in which X) is 0.1 or more and the content of fine powder having a particle diameter of 500 μm or less is 35% by weight or less.
Ｙ）に対する３２０ｎｍの吸光度（Ｘ）の比（Ｘ／Ｙ）が０．３以上である、請求項１記
載のポリビニルアルコール系樹脂。 Absorbance at 280 nm in the ultraviolet absorption spectrum when 0.1% by weight aqueous solution (
2. The polyvinyl alcohol resin according to claim 1, wherein the ratio (X/Y) of absorbance (X) at 320 nm to Y) is 0.3 or more.
。 3. The polyvinyl alcohol resin according to claim 1, wherein the degree of saponification is 60 mol % or more.
いずれか１項に記載のポリビニルアルコール系樹脂。 The polyvinyl alcohol resin according to any one of claims 1 to 3, which contains at least one of divalent to trivalent metal salts and hydroxides.
ルコール系樹脂に対して３０～３００μｍｏｌ／ｇである、請求項４記載のポリビニルア
ルコール系樹脂。 5. The polyvinyl alcohol resin according to claim 4, wherein the content of at least one of the divalent to trivalent metal salts and hydroxides is 30 to 300 μmol/g relative to the polyvinyl alcohol resin.
分散剤。 A dispersant for suspension polymerization comprising the polyvinyl alcohol-based resin according to any one of claims 1 to 5.
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| JP2016247686 | 2016-12-21 | ||
| JP2016247686 | 2016-12-21 | ||
| PCT/JP2017/046047 WO2018117246A1 (en) | 2016-12-21 | 2017-12-21 | Polyvinyl alcohol-based resin, dispersing agent, and dispersing agent for suspension polymerization |
| JP2017567273A JPWO2018117246A1 (en) | 2016-12-21 | 2017-12-21 | Polyvinyl alcohol resin, dispersant, and dispersant for suspension polymerization |
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| US20220056169A1 (en) * | 2018-12-27 | 2022-02-24 | Sekisui Chemical Co., Ltd. | Vinyl alcohol polymer and method for producing vinyl alcohol polymer |
| WO2021006234A1 (en) * | 2019-07-08 | 2021-01-14 | 株式会社クラレ | Water-based adhesive for paper straw, and paper straw in which same is used |
| CN114341302B (en) * | 2019-07-08 | 2023-10-20 | 株式会社可乐丽 | Aqueous emulsion and adhesive using same |
| US20220259467A1 (en) * | 2019-07-08 | 2022-08-18 | Kuraray Co., Ltd. | Water-based adhesive for paper straw, and paper straw in which same is used |
| EP4091704A4 (en) * | 2020-01-16 | 2023-06-07 | Mitsubishi Chemical Corporation | Polyvinyl alcohol resin, production method for polyvinyl alcohol resin, dispersant, and suspension polymerization dispersant |
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| JPS582962B2 (en) * | 1974-10-16 | 1983-01-19 | 株式会社クラレ | Manufacturing method of vinyl chloride resin |
| JPS61108602A (en) * | 1984-11-02 | 1986-05-27 | Nippon Synthetic Chem Ind Co Ltd:The | Dispersion stabilizer for suspension polymerization of vinyl compound |
| JP3540863B2 (en) * | 1995-04-03 | 2004-07-07 | 日本合成化学工業株式会社 | Dispersion stabilizer for suspension polymerization of vinyl compounds |
| FR2733756B1 (en) * | 1995-05-05 | 1997-08-01 | Rhone Poulenc Chimie | PROCESS FOR THE PURIFICATION OF POLYVINYL ALCOHOL |
| JP4223192B2 (en) * | 1998-10-07 | 2009-02-12 | 株式会社クラレ | Multilayer structure and manufacturing method thereof |
| JP2000265026A (en) * | 1999-03-18 | 2000-09-26 | Nippon Synthetic Chem Ind Co Ltd:The | Polyvinyl alcohol powder of excellent solubility |
| ATE386750T1 (en) * | 2002-12-11 | 2008-03-15 | Kuraray Co | DISPERSION STABILIZER FOR THE SUSPENSION POLYMERIZATION OF A VINYL COMPOUND AND METHOD FOR THE PRODUCTION THEREOF |
| JP2004189889A (en) * | 2002-12-11 | 2004-07-08 | Kuraray Co Ltd | Dispersion stabilizer for suspension polymerization of vinyl compound |
| TWI256954B (en) * | 2003-01-30 | 2006-06-21 | Nippon Synthetic Chem Ind | Dispersing agent comprising vinyl alcohol polymer having conjugated double bonds in its molecule |
| EP2058342B1 (en) * | 2006-08-01 | 2011-05-11 | The Nippon Synthetic Chemical Industry Co., Ltd. | Dispersion stabilizer for suspension polymerization of vinyl-based compound |
| DE102007033970A1 (en) * | 2007-07-19 | 2009-01-22 | Kuraray Europe Gmbh | Use of tempered polyvinyl alcohols as stabilizer additive of PVC |
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| CN112920293A (en) * | 2015-03-05 | 2021-06-08 | 积水精细化工美国有限公司 | PVOH dispersants for VCM polymerization |
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