JP2011038028A - Polyvinyl acetal-polyvinylpyrrolidone graft copolymer - Google Patents
Polyvinyl acetal-polyvinylpyrrolidone graft copolymer Download PDFInfo
- Publication number
- JP2011038028A JP2011038028A JP2009188392A JP2009188392A JP2011038028A JP 2011038028 A JP2011038028 A JP 2011038028A JP 2009188392 A JP2009188392 A JP 2009188392A JP 2009188392 A JP2009188392 A JP 2009188392A JP 2011038028 A JP2011038028 A JP 2011038028A
- Authority
- JP
- Japan
- Prior art keywords
- graft copolymer
- polyvinylpyrrolidone
- polyvinyl acetal
- segment
- mol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000001267 polyvinylpyrrolidone Substances 0.000 title claims abstract description 48
- 229920000036 polyvinylpyrrolidone Polymers 0.000 title claims abstract description 48
- 229920000578 graft copolymer Polymers 0.000 title claims abstract description 40
- 229920002554 vinyl polymer Polymers 0.000 title claims abstract description 33
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 46
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims abstract description 30
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 claims abstract description 30
- 238000006359 acetalization reaction Methods 0.000 claims abstract description 21
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical group C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002270 dispersing agent Substances 0.000 claims abstract description 13
- 229920001577 copolymer Polymers 0.000 claims abstract 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 19
- 229920002451 polyvinyl alcohol Polymers 0.000 description 19
- 229920000642 polymer Polymers 0.000 description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 239000000049 pigment Substances 0.000 description 12
- 239000006185 dispersion Substances 0.000 description 10
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000000975 dye Substances 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 4
- 150000001299 aldehydes Chemical class 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 3
- 229920006324 polyoxymethylene Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- AVTLBBWTUPQRAY-UHFFFAOYSA-N 2-(2-cyanobutan-2-yldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(CC)C#N AVTLBBWTUPQRAY-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-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
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000011354 acetal resin Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 239000005388 borosilicate glass Substances 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 235000010216 calcium carbonate Nutrition 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- GYHFUZHODSMOHU-UHFFFAOYSA-N nonanal Chemical compound CCCCCCCCC=O GYHFUZHODSMOHU-UHFFFAOYSA-N 0.000 description 2
- 239000012766 organic filler Substances 0.000 description 2
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N pentanal Chemical compound CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 235000014692 zinc oxide Nutrition 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- QLOKJRIVRGCVIM-UHFFFAOYSA-N 1-[(4-methylsulfanylphenyl)methyl]piperazine Chemical compound C1=CC(SC)=CC=C1CN1CCNCC1 QLOKJRIVRGCVIM-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- UNNGUFMVYQJGTD-UHFFFAOYSA-N 2-Ethylbutanal Chemical compound CCC(CC)C=O UNNGUFMVYQJGTD-UHFFFAOYSA-N 0.000 description 1
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- RJGDLRCDCYRQOQ-UHFFFAOYSA-N anthrone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3CC2=C1 RJGDLRCDCYRQOQ-UHFFFAOYSA-N 0.000 description 1
- 150000003934 aromatic aldehydes Chemical class 0.000 description 1
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- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
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- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
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- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- MYONAGGJKCJOBT-UHFFFAOYSA-N benzimidazol-2-one Chemical compound C1=CC=CC2=NC(=O)N=C21 MYONAGGJKCJOBT-UHFFFAOYSA-N 0.000 description 1
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- KSMVZQYAVGTKIV-UHFFFAOYSA-N decanal Chemical compound CCCCCCCCCC=O KSMVZQYAVGTKIV-UHFFFAOYSA-N 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
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- PPSZHCXTGRHULJ-UHFFFAOYSA-N dioxazine Chemical compound O1ON=CC=C1 PPSZHCXTGRHULJ-UHFFFAOYSA-N 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
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- -1 dosonite Substances 0.000 description 1
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- 238000011156 evaluation Methods 0.000 description 1
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
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- 238000004519 manufacturing process Methods 0.000 description 1
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
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- OBJNZHVOCNPSCS-UHFFFAOYSA-N naphtho[2,3-f]quinazoline Chemical compound C1=NC=C2C3=CC4=CC=CC=C4C=C3C=CC2=N1 OBJNZHVOCNPSCS-UHFFFAOYSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
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- 239000012860 organic pigment Substances 0.000 description 1
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- DGBWPZSGHAXYGK-UHFFFAOYSA-N perinone Chemical compound C12=NC3=CC=CC=C3N2C(=O)C2=CC=C3C4=C2C1=CC=C4C(=O)N1C2=CC=CC=C2N=C13 DGBWPZSGHAXYGK-UHFFFAOYSA-N 0.000 description 1
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- 239000001007 phthalocyanine dye Substances 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- GRLPQNLYRHEGIJ-UHFFFAOYSA-J potassium aluminium sulfate Chemical compound [Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRLPQNLYRHEGIJ-UHFFFAOYSA-J 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- BUKHSQBUKZIMLB-UHFFFAOYSA-L potassium;sodium;dichloride Chemical compound [Na+].[Cl-].[Cl-].[K+] BUKHSQBUKZIMLB-UHFFFAOYSA-L 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- LLBIOIRWAYBCKK-UHFFFAOYSA-N pyranthrene-8,16-dione Chemical compound C12=CC=CC=C2C(=O)C2=CC=C3C=C4C5=CC=CC=C5C(=O)C5=C4C4=C3C2=C1C=C4C=C5 LLBIOIRWAYBCKK-UHFFFAOYSA-N 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- FYNROBRQIVCIQF-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole-5,6-dione Chemical compound C1=CN=C2C(=O)C(=O)N=C21 FYNROBRQIVCIQF-UHFFFAOYSA-N 0.000 description 1
- IZMJMCDDWKSTTK-UHFFFAOYSA-N quinoline yellow Chemical compound C1=CC=CC2=NC(C3C(C4=CC=CC=C4C3=O)=O)=CC=C21 IZMJMCDDWKSTTK-UHFFFAOYSA-N 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229940100486 rice starch Drugs 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- JOUDBUYBGJYFFP-FOCLMDBBSA-N thioindigo Chemical compound S\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2S1 JOUDBUYBGJYFFP-FOCLMDBBSA-N 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 235000013337 tricalcium citrate Nutrition 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 235000013799 ultramarine blue Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- ZFZQOKHLXAVJIF-UHFFFAOYSA-N zinc;boric acid;dihydroxy(dioxido)silane Chemical compound [Zn+2].OB(O)O.O[Si](O)([O-])[O-] ZFZQOKHLXAVJIF-UHFFFAOYSA-N 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Abstract
Description
本発明は、ポリビニルアセタール・ポリビニルピロリドングラフト共重合体及びその用途に関する。 The present invention relates to a polyvinyl acetal / polyvinylpyrrolidone graft copolymer and use thereof.
ポリビニルアルコール・ポリビニルピロリドングラフト共重合体は、各種顔料等の微粒子に対して優れた分散効果を有することが見出され、低粘度、低チキソトロピック性で、塗膜の光沢にも優れるため、インキや塗料等の顔料分散体を得るための分散剤として好適に使用できることが開示されている（特許文献１）。 Polyvinyl alcohol / polyvinylpyrrolidone graft copolymer has been found to have an excellent dispersion effect on fine particles of various pigments, etc., has low viscosity, low thixotropic properties, and excellent gloss of the coating film. It is disclosed that it can be suitably used as a dispersant for obtaining pigment dispersions such as paints and paints (Patent Document 1).
しかし、上記ポリビニルアルコール・ポリビニルピロリドングラフト共重合体は、ポリビニルアルコールセグメントの影響により、例えば顔料の分散において、有機溶剤との相溶性が十分でない場合がある。 However, due to the influence of the polyvinyl alcohol segment, the polyvinyl alcohol / polyvinyl pyrrolidone graft copolymer may not be sufficiently compatible with an organic solvent in, for example, pigment dispersion.
従って、適用範囲がより広く、しかも分散性能がより向上した分散剤が求められている。 Therefore, there is a demand for a dispersant having a wider application range and further improved dispersion performance.
本発明は上記に鑑みてなされたものであり、ポリビニルアルコール・ポリビニルピロリドングラフト共重合体では十分な効果が得られない有機溶剤にも使用可能であり、分散性能がより向上した分散剤を提供することを目的とする。 The present invention has been made in view of the above, and can be used for an organic solvent in which a sufficient effect cannot be obtained with a polyvinyl alcohol / polyvinylpyrrolidone graft copolymer, and provides a dispersant having further improved dispersion performance. For the purpose.
本発明では、上記の課題を解決するために、ポリビニルアセタール・ポリビニルピロリドングラフト共重合体を用いるものとする。 In the present invention, a polyvinyl acetal / polyvinylpyrrolidone graft copolymer is used in order to solve the above problems.
上記ポリビニルアセタール・ポリビニルピロリドングラフト共重合体は、グラフト共重合体中のビニルピロリドン単位の割合が２〜９０モル％であり、ポリビニルピロリドンセグメントの重量平均分子量が１０００以上であり、かつポリビニルアセタールセグメントのアセタール化度が１０〜９０モル％であることが好ましい。 The polyvinyl acetal / polyvinyl pyrrolidone graft copolymer has a proportion of vinyl pyrrolidone units in the graft copolymer of 2 to 90 mol%, the polyvinyl pyrrolidone segment has a weight average molecular weight of 1000 or more, and the polyvinyl acetal segment The acetalization degree is preferably 10 to 90 mol%.
本発明の分散剤は、上記本発明のポリビニルアセタール・ポリビニルピロリドングラフト共重合体を含有してなるものとする。 The dispersant of the present invention contains the polyvinyl acetal / polyvinylpyrrolidone graft copolymer of the present invention.
本発明のポリビニルアセタールとポリビニルピロリドンとのグラフト共重合体は、適用範囲が広く分散性の良好な顔料等の分散剤として用いることができる。 The graft copolymer of polyvinyl acetal and polyvinyl pyrrolidone of the present invention can be used as a dispersant for pigments having a wide range of application and good dispersibility.
本発明のポリビニルアセタール・ポリビニルピロリドングラフト共重合体（以下、単に「グラフト共重合体」という場合もある）は、グラフト共重合物中のビニルピロリドン単位の割合が２〜９０モル％であるのが好ましい。ビニルピロリドン単位の割合がこの範囲から外れると、分散性が低下するなどの性能低下が見られる。 The polyvinyl acetal / polyvinylpyrrolidone graft copolymer of the present invention (hereinafter sometimes referred to simply as “graft copolymer”) has a vinyl pyrrolidone unit ratio of 2 to 90 mol% in the graft copolymer. preferable. When the ratio of the vinylpyrrolidone unit is out of this range, performance deterioration such as dispersibility is observed.
本発明のグラフト共重合体は、例えばエタノール等のポリビニルアルコール（ＰＶＡ）・ポリビニルピロリドングラフト共重合体が不溶な有機溶剤にも可溶であるため、分散剤等しての適用範囲がポリビニルアルコール・ポリビニルピロリドングラフト共重合体より広くなる。 The graft copolymer of the present invention is soluble in an organic solvent insoluble in, for example, polyvinyl alcohol (PVA) / polyvinylpyrrolidone graft copolymer such as ethanol. Wider than polyvinylpyrrolidone graft copolymer.
また、ポリビニルアセタール樹脂単独でも分散剤として使用されるが、その分散性能を十分に発揮させるには、通常はポリビニルアセタール樹脂の配合量をかなり多くする必要がある。しかし、多量に配合すると、得られるインクや塗料の粘度が上昇して塗布に支障が生じるという問題が生じる。これに対し本発明のグラフト共重合物によれば、少量でも十分な分散性能が得られ、これらの問題が解決される。 Further, although polyvinyl acetal resin alone is used as a dispersant, it is usually necessary to considerably increase the blending amount of polyvinyl acetal resin in order to fully exhibit its dispersion performance. However, when blended in a large amount, the viscosity of the resulting ink or paint increases, causing a problem that the coating is hindered. On the other hand, according to the graft copolymer of the present invention, sufficient dispersion performance can be obtained even with a small amount, and these problems are solved.
本発明のグラフト共重合体におけるポリビニルアセタールセグメントの重合度は１００〜３５００であることが好ましい。ポリビニルアセタールセグメントの重合度が１００未満となると、分散性が低下するなどの性能低下が見られ、重合度が３５００を超えると、ポリマー溶液の粘度が高くなり、扱いにくくなる。 The degree of polymerization of the polyvinyl acetal segment in the graft copolymer of the present invention is preferably 100 to 3500. When the degree of polymerization of the polyvinyl acetal segment is less than 100, performance degradation such as a decrease in dispersibility is observed. When the degree of polymerization exceeds 3,500, the viscosity of the polymer solution increases and it becomes difficult to handle.
また、アセタール化度は１０〜９０モル％が好ましい。アセタール化度が１０モル％未満では、ポリビニルアルコールの性質が現れ、有機溶剤との相溶性が低下するなどの性能低下が見られる。アセタール化度が９０モル％を超えるものは合成が困難である。 The degree of acetalization is preferably 10 to 90 mol%. When the degree of acetalization is less than 10 mol%, the properties of polyvinyl alcohol appear, and performance deterioration such as reduction in compatibility with organic solvents is observed. Those having a degree of acetalization exceeding 90 mol% are difficult to synthesize.
また、ポリビニルアセタールセグメントに対するアセチル基の割合が０．５〜３０モル％であることが好ましい。アセチル基の割合が３０モル％を超えると、分散性が低下するなどの性能低下が見られる。 Moreover, it is preferable that the ratio of the acetyl group with respect to a polyvinyl acetal segment is 0.5-30 mol%. When the ratio of acetyl groups exceeds 30 mol%, performance deterioration such as dispersibility is observed.
さらに、ポリビニルピロリドンセグメントの重量平均分子量は１，０００〜１，０００，０００であることが好ましい。ポリビニルピロリドンセグメントの当該重量平均分子量が１０００未満となると、分散性が低下するなどの性能低下が見られる。一方、１，０００，０００を超えると、ポリマー溶液の粘度が高くなり、扱いにくくなる。 Furthermore, it is preferable that the weight average molecular weight of a polyvinylpyrrolidone segment is 1,000-1,000,000. When the weight average molecular weight of the polyvinyl pyrrolidone segment is less than 1000, performance degradation such as dispersibility is observed. On the other hand, when it exceeds 1,000,000, the viscosity of the polymer solution becomes high and becomes difficult to handle.
本発明のグラフト共重合体の製法は特に限定されないが、ポリビニルアルコールにポリビニルピロリドンをグラフト化後アセタール化する方法、又はポリビニルアルコールをアセタール化後にポリビニルピロリドンをグラフト化する方法が用いられる。あるいはこれらと幹と枝が反転するように、ポリビニルピロリドンにポリビニルアルコールをグラフト化後アセタール化する方法、又はポリビニルアルコールをアセタール化後にポリビニルピロリドンにグラフト化する方法を用いることもできる。グラフト化、アセタール化は、公知の方法によって行うことができる。 Although the manufacturing method of the graft copolymer of this invention is not specifically limited, The method of grafting polyvinylpyrrolidone to polyvinyl alcohol, and acetalizing, or the method of grafting polyvinylpyrrolidone after acetalizing polyvinyl alcohol is used. Alternatively, a method of grafting polyvinyl alcohol onto polyvinyl pyrrolidone and then acetalizing it, or a method of grafting polyvinyl alcohol onto polyvinyl pyrrolidone after acetalization so that the trunk and branches are reversed can be used. Grafting and acetalization can be performed by a known method.
アセタール化に用いるアルデヒドは特に限定されず、例えば、アセトアルデヒド、ｎ−ブチルアルデヒド、プロピオンアルデヒド、ｉｓｏ−ブチルアルデヒド、ｎ−バレルアルデヒド、ｎ−ヘキシルアルデヒド、２−エチルブチルアルデヒド、ｎ−オクチルアルデヒド、ｎ−ノニルアルデヒド、ｎ−デシルアルデヒド等の脂肪族飽和アルデヒド類や、ベンズアルデヒド、シンナムアルデヒド等の芳香族アルデヒド等が挙げられる。これらの中でもアセタール化反応に優れるｎ−ブチルアルデヒドが好適に用いられる。上記アルデヒド類は単独で用いてもよく、２種類以上を併用してもよい。 The aldehyde used for acetalization is not particularly limited. For example, acetaldehyde, n-butyraldehyde, propionaldehyde, iso-butyraldehyde, n-valeraldehyde, n-hexylaldehyde, 2-ethylbutyraldehyde, n-octylaldehyde, n -Aliphatic saturated aldehydes such as nonyl aldehyde and n-decyl aldehyde, and aromatic aldehydes such as benzaldehyde and cinnamaldehyde. Among these, n-butyraldehyde excellent in acetalization reaction is preferably used. The aldehydes may be used alone or in combination of two or more.
本発明のグラフト共重合体を分散剤として使用するには、グラフト共重合体を顔料等の分散対象及び溶剤とともに混合すればよい。 In order to use the graft copolymer of the present invention as a dispersant, the graft copolymer may be mixed with a dispersion target such as a pigment and a solvent.
分散対象の例としては、一般に市販されている種々の顔料、フィラー、微粒子等を挙げることができる。 Examples of the dispersion target include various commercially available pigments, fillers, fine particles, and the like.
顔料の例としては、アゾ系、アンサンスロン系、アンスラピリミジン系、アントラキノン系、イソインドリノン系、イソインドリン系、インダンスロン系色素、キナクリドン系、キノフタロン系、ジオキサジン系、ジケトピロロピロール系、チオインジゴ系色素、ピランスロン系色素、フタロシアニン系、フラバンスロン系色素、ペリノン系色素、ペリレン系色素、ベンズイミダゾロン系などの有機顔料等、カーボンブラック、酸化チタン、黄鉛、カドミウムイエロー、カドミウムレッド、弁柄、鉄黒、亜鉛華、紺青、群青等の無機顔料等が挙げられる。 Examples of pigments include azo, anthrone, anthrapyrimidine, anthraquinone, isoindolinone, isoindoline, indanthrone, quinacridone, quinophthalone, dioxazine, diketopyrrolopyrrole, Organic pigments such as thioindigo dyes, pyranthrone dyes, phthalocyanine dyes, flavanthrone dyes, perinone dyes, perylene dyes, benzimidazolone dyes, carbon black, titanium oxide, yellow lead, cadmium yellow, cadmium red, valves Examples thereof include inorganic pigments such as patterns, iron black, zinc white, bitumen, ultramarine blue, and the like.
上記フィラーは、無機フィラー又は有機フィラーのいずれでもよい。無機フィラーとしては、例えば、タルク、クレー、二酸化ケイ素、ケイ藻土、カオリン、雲母、アスベスト、石膏、グラファイト、ガラスバルーン、ガラスビーズ、硫酸カルシウム、硫酸バリウム、硫酸アンモニウム、亜硫酸カルシウム、炭酸カルシウム、ウイスカー状炭酸カルシウム、炭酸マグネシウム、ドーソナイト、ドロマイト、チタン酸カリウム、カーボンブラック、ガラス繊維、アルミナ繊維、ボロン繊維、加工鉱物繊維、炭素繊維、炭素中空球、ベントナイト、モンモリロナイト、銅粉、硫酸ナトリウム、硫酸カリウム、硫酸亜鉛、硫酸銅、硫酸鉄、硫酸マグネシウム、硫酸アルミニウム、硫酸アルミニウムカリウム、硝酸アンモニウム、硝酸ナトリウム、硝酸カリウム、硝酸アルミニウム、塩化アンモニウム、塩化ナトリウム、塩化カリウム、塩化マグネシウム、塩化カルシウム、リン酸ナトリウム、クロム酸カリウム、クエン酸カルシウム等が挙げられる。有機フィラーとしては、例えば、澱粉、メラミン系樹脂、ポリメチル（メタ）アクリレート系樹脂、ポリスチレン系樹脂の他、ポリ乳酸、米澱粉等の生分解性樹脂等も挙げられる。 The filler may be either an inorganic filler or an organic filler. Examples of the inorganic filler include talc, clay, silicon dioxide, diatomaceous earth, kaolin, mica, asbestos, gypsum, graphite, glass balloon, glass beads, calcium sulfate, barium sulfate, ammonium sulfate, calcium sulfite, calcium carbonate, whisker Calcium carbonate, magnesium carbonate, dosonite, dolomite, potassium titanate, carbon black, glass fiber, alumina fiber, boron fiber, processed mineral fiber, carbon fiber, carbon hollow sphere, bentonite, montmorillonite, copper powder, sodium sulfate, potassium sulfate, Zinc sulfate, copper sulfate, iron sulfate, magnesium sulfate, aluminum sulfate, potassium aluminum sulfate, ammonium nitrate, sodium nitrate, potassium nitrate, aluminum nitrate, ammonium chloride, sodium chloride Potassium chloride, magnesium chloride, calcium chloride, sodium phosphate, potassium chromate, calcium citrate. Examples of the organic filler include starch, melamine resin, polymethyl (meth) acrylate resin, polystyrene resin, and biodegradable resins such as polylactic acid and rice starch.
上記微粒子としては、例えば、金粉、銀粉、銅粉、ニッケル粉、プラチナ粉、パラジウム粉等の金属粉、シリカ、アルミナ、ジルコニア、チタニア、酸化亜鉛、マグネシア、フェライト、ＩＴＯ等の金属酸化物粉、ソーダガラス、無アルカリガラス、硼珪酸鉛ガラス、硼珪酸ビスマス、硼珪酸亜鉛ガラス等のガラスフリット、窒化アルミ、窒化ケイ素、窒化ホウ素等の窒化物紛、蛍光体粉、シリコンカーバイド粉、チタン酸バリウム粉、カーボン粉等が挙げられる。 Examples of the fine particles include metal powders such as gold powder, silver powder, copper powder, nickel powder, platinum powder, and palladium powder, metal oxide powders such as silica, alumina, zirconia, titania, zinc oxide, magnesia, ferrite, and ITO, Glass frit such as soda glass, alkali-free glass, lead borosilicate glass, bismuth borosilicate, zinc borosilicate glass, nitride powder such as aluminum nitride, silicon nitride, boron nitride, phosphor powder, silicon carbide powder, barium titanate Examples thereof include powder and carbon powder.
さらに、分散の際に使用できる溶剤の例としては、シクロヘキサノン、エチルセロソルブアセテート、ブチルセロソルブアセテート、プロピレングリコールモノメチルエーテルアセテート、ジエチレングリコールジメチルエーテル、エチルベンゼン、エチレングリコールジエチルエーテル、トルエン、キシレン、エチルセロソルブ、メチル−ｎアミルケトン、プロピレングリコールモノメチルエーテル、トルエン、メチルエチルケトン、メチルイソブチルケトン、酢酸エチル、酢酸ブチル、ｎ−ヘキサン、メタノール、エタノール、イソプロピルアルコール、ブタノール、ジオキサン、ジメチルホルムアミド、ソルベッソ１００（エクソン化学株式会社製）、スワゾール１０００等が挙げられる。 Examples of solvents that can be used for dispersion include cyclohexanone, ethyl cellosolve acetate, butyl cellosolve acetate, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, ethylbenzene, ethylene glycol diethyl ether, toluene, xylene, ethyl cellosolve, and methyl-n amyl ketone. , Propylene glycol monomethyl ether, toluene, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, n-hexane, methanol, ethanol, isopropyl alcohol, butanol, dioxane, dimethylformamide, Solvesso 100 (manufactured by Exxon Chemical Co., Ltd.), Swazol 1000 Etc.
本発明のポリビニルアセタール・ポリビニルピロリドングラフト共重合体は、分散剤の他、接着剤、樹脂添加剤、防曇剤、合わせガラス中間膜、塗料、バインダー等に適用可能である。 The polyvinyl acetal / polyvinylpyrrolidone graft copolymer of the present invention is applicable to adhesives, resin additives, antifogging agents, laminated glass interlayers, paints, binders and the like in addition to dispersants.
以下、実施例により本発明をさらに具体的に説明するが、本発明は以下の実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example.
［実施例１］
（グラフト化）
純水８００ｇにポリビニルアルコール（重合度１７００、ケン化度９８〜９９ｍｏｌ％）１６０ｇを溶解させ、次いでビニルピロリドン４０ｇを添加、混合し、窒素パージにより脱酸素を行った。続いて、反応系を７０℃に温度調節した。これに２，２’−アゾビス（２−メチルブチロニトリル）１ｇをイソプロピルアルコールに溶解したものを添加し、重合を開始させた。重合中は温度を７０〜９０℃に維持し、３時間反応させ、ポリビニルアルコール・ポリビニルピロリドングラフト共重合体の２０％水溶液を得た。
[Example 1]
(Grafting)
160 g of polyvinyl alcohol (polymerization degree 1700, saponification degree 98 to 99 mol%) was dissolved in 800 g of pure water, then 40 g of vinylpyrrolidone was added and mixed, and deoxygenated by nitrogen purge. Subsequently, the temperature of the reaction system was adjusted to 70 ° C. A solution prepared by dissolving 1 g of 2,2′-azobis (2-methylbutyronitrile) in isopropyl alcohol was added thereto to initiate polymerization. During the polymerization, the temperature was maintained at 70 to 90 ° C. and reacted for 3 hours to obtain a 20% aqueous solution of polyvinyl alcohol / polyvinylpyrrolidone graft copolymer.
（アセタール化）
上記のポリマー水溶液に純水１６００ｇを加え、均一に撹拌した。この溶液を１５℃に温度調節し、３５重量％の塩酸１４５ｇとｎ−ブチルアルデヒド１１５ｇを加え、この温度を保持して反応させた。その後、反応系を６０℃で３時間保持して反応を完了させ、過剰の水で洗浄後、乾燥して白色粉末状のポリビニルアセタール・ポリビニルピロリドングラフト共重合体（重合物１）を得た。この重合物のポリビニルアセタールセグメントのアセタール化度は８０モル％、ポリビニルピロリドンセグメントの重量平均分子量は５００００、ビニルピロリドン単位の割合は６モル％であった。
(Acetalization)
1600 g of pure water was added to the above polymer aqueous solution and stirred uniformly. The temperature of this solution was adjusted to 15 ° C., 145 g of 35% by weight hydrochloric acid and 115 g of n-butyraldehyde were added, and this temperature was maintained and reacted. Thereafter, the reaction system was maintained at 60 ° C. for 3 hours to complete the reaction, washed with excess water, and dried to obtain a white powdery polyvinyl acetal / polyvinylpyrrolidone graft copolymer (polymer 1). The degree of acetalization of the polyvinyl acetal segment of this polymer was 80 mol%, the weight average molecular weight of the polyvinylpyrrolidone segment was 50000, and the proportion of vinylpyrrolidone units was 6 mol%.
［実施例２］
アセタール化においてｎ−ブチルアルデヒドの添加量を２０ｇとした以外は実施例１と同様に操作し重合物２を得た。この重合物のポリビニルアセタールセグメントのアセタール化度は１５モル％、ポリビニルピロリドンセグメントの重量平均分子量は５００００、ビニルピロリドン単位の割合は６モル％であった。
[Example 2]
A polymer 2 was obtained in the same manner as in Example 1 except that the amount of n-butyraldehyde added in the acetalization was 20 g. The degree of acetalization of the polyvinyl acetal segment of this polymer was 15 mol%, the weight average molecular weight of the polyvinylpyrrolidone segment was 50000, and the proportion of vinylpyrrolidone units was 6 mol%.
［実施例３］
グラフト化において２，２’−アゾビス（２−メチルブチロニトリル）の代わりに１重量％硫酸銅４０ｍｇ、２８重量％アンモニア水４ｇ及び３０重量％過酸化水素水３６ｇを添加し、重合を開始させた以外は実施例１と同様に操作し重合物３を得た。この重合物のポリビニルアセタールセグメントのアセタール化度は７８モル％、ポリビニルピロリドンセグメントの重量平均分子量は３０００、ビニルピロリドン単位の割合は７モル％であった。
[Example 3]
In the grafting, instead of 2,2′-azobis (2-methylbutyronitrile), 40 mg of 1 wt% copper sulfate, 4 g of 28 wt% aqueous ammonia and 36 g of 30 wt% aqueous hydrogen peroxide were added to initiate the polymerization. A polymer 3 was obtained in the same manner as in Example 1 except that. The degree of acetalization of the polyvinyl acetal segment of this polymer was 78 mol%, the weight average molecular weight of the polyvinylpyrrolidone segment was 3000, and the proportion of vinylpyrrolidone units was 7 mol%.
［比較例１］
実施例１のアセタール化前のポリビニルアルコール・ポリビニルピロリドングラフト共重合体の水溶液を加熱乾燥し、重合物４を得た。
[Comparative Example 1]
The aqueous solution of the polyvinyl alcohol / polyvinylpyrrolidone graft copolymer before acetalization in Example 1 was dried by heating to obtain a polymer 4.
［比較例２］
実施例１においてビニルピロリドンをグラフト化せず、ポリビニルアルコールのみをアセタール化してポリビニルアセタール（重合物５）を得た。
[Comparative Example 2]
In Example 1, vinyl pyrrolidone was not grafted, and only polyvinyl alcohol was acetalized to obtain polyvinyl acetal (polymer 5).
上記実施例及び比較例のポリマーの同定、アセタール化度の測定、グラフト共重合体中のビニルピロリドン単位の割合の測定、ポリビニルピロリドンセグメントの分子量は以下の方法により行った。また、得られた重合物の顔料分散性を以下の方法で評価した。 The identification of the polymers of the above Examples and Comparative Examples, the measurement of the degree of acetalization, the measurement of the proportion of vinylpyrrolidone units in the graft copolymer, and the molecular weight of the polyvinylpyrrolidone segment were carried out by the following methods. Moreover, the pigment dispersibility of the obtained polymer was evaluated by the following method.
〈ポリマーの同定〉
得られたポリマーを重水素化ジメチルスルホキシドを測定溶媒として１３Ｃ−ＮＭＲ測定し、ポリビニルアセタール由来のピークとポリビニルピロリドン由来のピークが観測されるのを確認した。ポリビニルピロリドンやポリビニルアルコール・ポリビニルピロリドングラフト共重合体はアセタール化工程の水洗で除去されることから、ポリビニルアセタール・ポリビニルピロリドングラフト共重合体が得られていることがわかる。
<Polymer identification>
The polymer obtained was subjected to 13C-NMR measurement using deuterated dimethyl sulfoxide as a measurement solvent, and it was confirmed that a peak derived from polyvinyl acetal and a peak derived from polyvinyl pyrrolidone were observed. Since polyvinyl pyrrolidone and polyvinyl alcohol / polyvinyl pyrrolidone graft copolymer are removed by washing with water in the acetalization step, it is understood that a polyvinyl acetal / polyvinyl pyrrolidone graft copolymer is obtained.
〈アセタール化度〉
定量モード１３Ｃ−ＮＭＲにおいて観測されたポリビニルアセタールの主鎖メチン炭素（６６〜７５ｐｐｍ）のピーク面積をＡ、アルデヒド由来メチン炭素（９４ｐｐｍ、１０１ｐｐｍ）のピーク面積をＢとし、次式により求めた；
アセタール化度（ｍｏｌ％）＝（Ｂ×２／Ａ）×１００
<Degree of acetalization>
The peak area of the main chain methine carbon (66 to 75 ppm) of polyvinyl acetal observed in quantitative mode 13C-NMR was defined as A, and the peak area of aldehyde-derived methine carbon (94 ppm, 101 ppm) was determined as B.
Degree of acetalization (mol%) = (B × 2 / A) × 100
〈グラフト共重合体中のビニルピロリドン単位の割合〉
定量モード１３Ｃ−ＮＭＲにおいて観測されたポリビニルアセタールの主鎖メチン炭素（６６〜７５ｐｐｍ）のピーク面積をＡ、ピロリドン由来メチレン炭素（１８ｐｐｍ）のピーク面積をＣとし、次式により求めた；
グラフト共重合体中のビニルピロリドン単位の割合（％）
＝｛Ｃ／（Ａ＋Ｃ）｝×１００
<Ratio of vinylpyrrolidone units in graft copolymer>
The peak area of the main chain methine carbon (66 to 75 ppm) of polyvinyl acetal observed in quantitative mode 13C-NMR was A, and the peak area of pyrrolidone-derived methylene carbon (18 ppm) was C.
Percentage of vinylpyrrolidone units in the graft copolymer (%)
= {C / (A + C)} × 100
〈ポリビニルピロリドンセグメントの分子量〉
グラフト化しているポリビニルピロリドンの分子量を直接測定することは困難であるため、グラフト化と同時に生成するポリビニルピロリドンホモポリマーの分子量を測定した。すなわちアセタール化前のポリビニルアルコール・ポリビニルピロリドングラフト共重合体水溶液をｔ−ブチルアルコールに添加すると、ポリビニルアルコール・ポリビニルピロリドングラフト共重合体は不溶化するが、ポリビニルピロリドンホモポリマーは溶解する。不溶物を除去し、ｔ−ブチルアルコールを留去してポリビニルピロリドンホモポリマーを得、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）により重量平均分子量を測定した。ＧＰＣによる分子量測定条件は以下の通りである。
<Molecular weight of polyvinylpyrrolidone segment>
Since it is difficult to directly measure the molecular weight of grafted polyvinylpyrrolidone, the molecular weight of the polyvinylpyrrolidone homopolymer formed simultaneously with grafting was measured. That is, when an aqueous polyvinyl alcohol / polyvinylpyrrolidone graft copolymer solution before acetalization is added to t-butyl alcohol, the polyvinyl alcohol / polyvinylpyrrolidone graft copolymer is insolubilized, but the polyvinylpyrrolidone homopolymer is dissolved. Insoluble matter was removed, t-butyl alcohol was distilled off to obtain a polyvinylpyrrolidone homopolymer, and the weight average molecular weight was measured by gel permeation chromatography (GPC). The molecular weight measurement conditions by GPC are as follows.
ＧＰＣ装置：ＨＬＣ−８０２０ ＲＩ検出（ＴＯＳＯＨ製）
カラム：TSK guard column PWXL, TSKgel G2500 PWXL, TSKgel G3000 PWXL, TSKgel G4000 PWXL, TSKgel G6000 PWXL（TOSOH製）
溶離液：０．０８Ｍ酢酸ナトリウム水溶液／アセトニトリル＝５０／５０vol%
流速：０．７ｍＬ／ｍｉｎ
温度：４０℃
GPC device: HLC-8020 RI detection (manufactured by TOSOH)
Column: TSK guard column PWXL, TSKgel G2500 PWXL, TSKgel G3000 PWXL, TSKgel G4000 PWXL, TSKgel G6000 PWXL (manufactured by TOSOH)
Eluent: 0.08M sodium acetate aqueous solution / acetonitrile = 50 / 50vol%
Flow rate: 0.7 mL / min
Temperature: 40 ° C
〈顔料分散性評価〉
上記の重合物１０ｇをエタノール１２０ｇに溶解し、これにフタロシアニンブルー（東洋インキ社製「ＬＩＯＮＯＬ ＢＬＵＥ ＦＧ−７３５１」）１５ｇ及びガラスビーズ（東芝バロティーニ社製「東芝ガラスビーズＧＢ５０３Ｍ」）５０ｇを加え、攪拌機で１時間攪拌してインクを作製した。４０℃で２週間保管した後、顔料分散性を目視にて観察し、以下の基準で評価した。結果を表１に示す。
良好……顔料の沈降や凝集がなく、均一な溶液である
不良……顔料の沈降や凝集が認められる
<Evaluation of pigment dispersibility>
10 g of the above polymer was dissolved in 120 g of ethanol, and 15 g of phthalocyanine blue (“LIONOL BLUE FG-7351” manufactured by Toyo Ink Co., Ltd.) and 50 g of glass beads (“Toshiba Glass Beads GB503M” manufactured by Toshiba Ballotini) were added to the agitator. The ink was prepared by stirring for 1 hour. After storage at 40 ° C. for 2 weeks, the pigment dispersibility was visually observed and evaluated according to the following criteria. The results are shown in Table 1.
Good …… There is no sedimentation or aggregation of the pigment, and it is a uniform solution. Bad …… Sedimentation or aggregation of the pigment is observed.
表１に示されたように、実施例１〜３のポリビニルアセタール・ポリビニルピロリドングラフト共重合体では良好な分散性が見られたのに対し、比較例１の重合体４（ポリビニルアルコール・ポリビニルピロリドングラフト共重合体）はエタノールに不溶であり、分散させることができなかった。比較例２の重合体５（ポリビニルアセタール）は不良の評価であったが、使用量を実施例の３倍量まで増量したときに、実施例と同程度の分散性が得られた。 As shown in Table 1, the polyvinyl acetal / polyvinylpyrrolidone graft copolymers of Examples 1 to 3 showed good dispersibility, whereas the polymer 4 of Comparative Example 1 (polyvinyl alcohol / polyvinylpyrrolidone). The graft copolymer) was insoluble in ethanol and could not be dispersed. The polymer 5 (polyvinyl acetal) of Comparative Example 2 was evaluated as poor, but when the amount used was increased to 3 times the amount, dispersibility comparable to that of the Example was obtained.
本発明のポリビニルアセタール・ポリビニルピロリドングラフト共重合体は、分散剤、接着剤等に適用可能である。 The polyvinyl acetal / polyvinylpyrrolidone graft copolymer of the present invention is applicable to a dispersant, an adhesive, and the like.
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| WO2013133013A1 (en) * | 2012-03-07 | 2013-09-12 | 第一工業製薬株式会社 | Dispersant including polyvinyl acetal-polyester graft copolymer, solid-particle dispersion using same, solid particle-containing composition and surface-treated solid particles |
| JP2014205137A (en) * | 2013-03-18 | 2014-10-30 | 第一工業製薬株式会社 | Dispersant and solid particle dispersion |
| US20150279505A1 (en) * | 2012-10-15 | 2015-10-01 | Dai Nippon Printing Co., Ltd. | Metal particle dispersion for electroconductive substrates, method for producing the same, and method for producing an electroconductive substrate |
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| WO2013133013A1 (en) * | 2012-03-07 | 2013-09-12 | 第一工業製薬株式会社 | Dispersant including polyvinyl acetal-polyester graft copolymer, solid-particle dispersion using same, solid particle-containing composition and surface-treated solid particles |
| JP2013185049A (en) * | 2012-03-07 | 2013-09-19 | Dai Ichi Kogyo Seiyaku Co Ltd | Dispersant including polyvinyl acetal-polyester graft copolymer, solid-particle dispersion using the same, solid particle-containing composition and surface-treated solid particle |
| TWI488689B (en) * | 2012-03-07 | 2015-06-21 | Dai Ichi Kogyo Seiyaku Co Ltd | A dispersant containing a polyvinyl acetal-polyester graft copolymer, a solid particle dispersion using the same, and a composition containing solid particles |
| US20150279505A1 (en) * | 2012-10-15 | 2015-10-01 | Dai Nippon Printing Co., Ltd. | Metal particle dispersion for electroconductive substrates, method for producing the same, and method for producing an electroconductive substrate |
| US9972413B2 (en) * | 2012-10-15 | 2018-05-15 | Dai Nippon Printing Co., Ltd. | Metal particle dispersion for electroconductive substrates, method for producing the same, and method for producing an electroconductive substrate |
| JP2014205137A (en) * | 2013-03-18 | 2014-10-30 | 第一工業製薬株式会社 | Dispersant and solid particle dispersion |
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