CN114940820A - Aqueous resin composition, and aqueous surface treatment agent and article using same - Google Patents
Aqueous resin composition, and aqueous surface treatment agent and article using same Download PDFInfo
- Publication number
- CN114940820A CN114940820A CN202210137880.1A CN202210137880A CN114940820A CN 114940820 A CN114940820 A CN 114940820A CN 202210137880 A CN202210137880 A CN 202210137880A CN 114940820 A CN114940820 A CN 114940820A
- Authority
- CN
- China
- Prior art keywords
- resin composition
- aqueous resin
- aqueous
- viscosity
- acid
- 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
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- 239000011342 resin composition Substances 0.000 title claims abstract description 91
- 239000012756 surface treatment agent Substances 0.000 title claims abstract description 10
- 239000011248 coating agent Substances 0.000 claims abstract description 52
- 239000004814 polyurethane Substances 0.000 claims abstract description 50
- 229920002635 polyurethane Polymers 0.000 claims abstract description 50
- 238000000576 coating method Methods 0.000 claims abstract description 47
- 239000000654 additive Substances 0.000 claims abstract description 13
- 230000000996 additive effect Effects 0.000 claims abstract description 12
- 239000002736 nonionic surfactant Substances 0.000 claims description 19
- 239000004034 viscosity adjusting agent Substances 0.000 claims description 14
- 239000006224 matting agent Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 12
- 150000001875 compounds Chemical class 0.000 description 37
- 239000000049 pigment Substances 0.000 description 34
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 30
- 150000003077 polyols Chemical class 0.000 description 27
- -1 polypropylene Polymers 0.000 description 26
- 239000000463 material Substances 0.000 description 25
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 21
- 229920005862 polyol Polymers 0.000 description 19
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 16
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 15
- 239000001993 wax Substances 0.000 description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- 239000002270 dispersing agent Substances 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- 239000003431 cross linking reagent Substances 0.000 description 11
- 239000005056 polyisocyanate Substances 0.000 description 11
- 229920001228 polyisocyanate Polymers 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 11
- 229920000098 polyolefin Polymers 0.000 description 11
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 10
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 10
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 10
- 239000000377 silicon dioxide Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 8
- 229910000271 hectorite Inorganic materials 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 125000003277 amino group Chemical group 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 229920000768 polyamine Polymers 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 229920002397 thermoplastic olefin Polymers 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 5
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 5
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 5
- 239000011324 bead Substances 0.000 description 5
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 229920005906 polyester polyol Polymers 0.000 description 5
- 229920005749 polyurethane resin Polymers 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 4
- 239000004970 Chain extender Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 125000002947 alkylene group Chemical group 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
- 239000010985 leather Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000005457 optimization Methods 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 239000004417 polycarbonate Substances 0.000 description 4
- 229920000515 polycarbonate Polymers 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 125000000542 sulfonic acid group Chemical group 0.000 description 4
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 4
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 3
- 229940035437 1,3-propanediol Drugs 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 3
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- 235000010216 calcium carbonate Nutrition 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 238000007756 gravure coating Methods 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 3
- 239000001095 magnesium carbonate Substances 0.000 description 3
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 3
- 239000010445 mica Substances 0.000 description 3
- 229910052618 mica group Inorganic materials 0.000 description 3
- 239000011325 microbead Substances 0.000 description 3
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000600 sorbitol Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 239000002562 thickening agent Substances 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
- 229940043375 1,5-pentanediol Drugs 0.000 description 2
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 2
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 2
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 2
- IAXFZZHBFXRZMT-UHFFFAOYSA-N 2-[3-(2-hydroxyethoxy)phenoxy]ethanol Chemical compound OCCOC1=CC=CC(OCCO)=C1 IAXFZZHBFXRZMT-UHFFFAOYSA-N 0.000 description 2
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 2
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 description 2
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000004606 Fillers/Extenders Substances 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
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- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- 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 2
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- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 2
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- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
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- 239000006096 absorbing agent Substances 0.000 description 2
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- 235000011037 adipic acid Nutrition 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 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
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 2
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- 235000019437 butane-1,3-diol Nutrition 0.000 description 2
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- PMMYEEVYMWASQN-IMJSIDKUSA-N cis-4-Hydroxy-L-proline Chemical compound O[C@@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-IMJSIDKUSA-N 0.000 description 2
- 239000008199 coating composition Substances 0.000 description 2
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- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 2
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- 238000013461 design Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
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- 239000006185 dispersion Substances 0.000 description 2
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- 239000003822 epoxy resin Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- MNUOZFHYBCRUOD-UHFFFAOYSA-N hydroxyphthalic acid Natural products OC(=O)C1=CC=CC(O)=C1C(O)=O MNUOZFHYBCRUOD-UHFFFAOYSA-N 0.000 description 2
- 239000012770 industrial material Substances 0.000 description 2
- 239000001023 inorganic pigment Substances 0.000 description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 239000002648 laminated material Substances 0.000 description 2
- 239000002649 leather substitute Substances 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
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- 239000000499 gel Substances 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229930185053 grandol Natural products 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000001056 green pigment Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- HNDVDQJCIGZPNO-UHFFFAOYSA-N histidine Natural products OC(=O)C(N)CC1=CN=CN1 HNDVDQJCIGZPNO-UHFFFAOYSA-N 0.000 description 1
- 235000014304 histidine Nutrition 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000001034 iron oxide pigment Substances 0.000 description 1
- LDHBWEYLDHLIBQ-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide;hydrate Chemical compound O.[OH-].[O-2].[Fe+3] LDHBWEYLDHLIBQ-UHFFFAOYSA-M 0.000 description 1
- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- GKQPCPXONLDCMU-CCEZHUSRSA-N lacidipine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C1=CC=CC=C1\C=C\C(=O)OC(C)(C)C GKQPCPXONLDCMU-CCEZHUSRSA-N 0.000 description 1
- 229940094522 laponite Drugs 0.000 description 1
- MOUPNEIJQCETIW-UHFFFAOYSA-N lead chromate Chemical compound [Pb+2].[O-][Cr]([O-])(=O)=O MOUPNEIJQCETIW-UHFFFAOYSA-N 0.000 description 1
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- XCOBTUNSZUJCDH-UHFFFAOYSA-B lithium magnesium sodium silicate Chemical compound [Li+].[Li+].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Na+].[Na+].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3 XCOBTUNSZUJCDH-UHFFFAOYSA-B 0.000 description 1
- 235000010187 litholrubine BK Nutrition 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 1
- 239000000983 mordant dye Substances 0.000 description 1
- 238000010137 moulding (plastic) Methods 0.000 description 1
- SCZVXVGZMZRGRU-UHFFFAOYSA-N n'-ethylethane-1,2-diamine Chemical compound CCNCCN SCZVXVGZMZRGRU-UHFFFAOYSA-N 0.000 description 1
- QHJABUZHRJTCAR-UHFFFAOYSA-N n'-methylpropane-1,3-diamine Chemical compound CNCCCN QHJABUZHRJTCAR-UHFFFAOYSA-N 0.000 description 1
- YNTOKMNHRPSGFU-UHFFFAOYSA-N n-Propyl carbamate Chemical compound CCCOC(N)=O YNTOKMNHRPSGFU-UHFFFAOYSA-N 0.000 description 1
- ABMFBCRYHDZLRD-UHFFFAOYSA-N naphthalene-1,4-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1 ABMFBCRYHDZLRD-UHFFFAOYSA-N 0.000 description 1
- VAWFFNJAPKXVPH-UHFFFAOYSA-N naphthalene-1,6-dicarboxylic acid Chemical compound OC(=O)C1=CC=CC2=CC(C(=O)O)=CC=C21 VAWFFNJAPKXVPH-UHFFFAOYSA-N 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 235000012736 patent blue V Nutrition 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- LGYJSPMYALQHBL-UHFFFAOYSA-N pentanedihydrazide Chemical compound NNC(=O)CCCC(=O)NN LGYJSPMYALQHBL-UHFFFAOYSA-N 0.000 description 1
- 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
- 150000002978 peroxides Chemical class 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229940044654 phenolsulfonic acid Drugs 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920006295 polythiol Polymers 0.000 description 1
- 229920003009 polyurethane dispersion Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 229940088417 precipitated calcium carbonate Drugs 0.000 description 1
- UWHMFGKZAYHMDJ-UHFFFAOYSA-N propane-1,2,3-trithiol Chemical compound SCC(S)CS UWHMFGKZAYHMDJ-UHFFFAOYSA-N 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000001054 red pigment Substances 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000010356 sorbitol Nutrition 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229950000244 sulfanilic acid Drugs 0.000 description 1
- QXKXDIKCIPXUPL-UHFFFAOYSA-N sulfanylidenemercury Chemical compound [Hg]=S QXKXDIKCIPXUPL-UHFFFAOYSA-N 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000010998 test method Methods 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
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 239000000984 vat dye Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- NDKWCCLKSWNDBG-UHFFFAOYSA-N zinc;dioxido(dioxo)chromium Chemical compound [Zn+2].[O-][Cr]([O-])(=O)=O NDKWCCLKSWNDBG-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/06—Polyurethanes from polyesters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/06—Polyurethanes from polyesters
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2211/00—Specially adapted uses
- D06N2211/12—Decorative or sun protection articles
- D06N2211/28—Artificial leather
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Textile Engineering (AREA)
- Wood Science & Technology (AREA)
- Dispersion Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyurethanes Or Polyureas (AREA)
- Paints Or Removers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides an aqueous resin composition which can be used for evaluating the coating quality with high efficiency, thereby improving the coating efficiency and improving the coating quality, and an aqueous surface treatment agent and an article using the aqueous resin composition. The aqueous resin composition is an aqueous resin composition containing aqueous polyurethane (A), a matte agent (B) and an additive (C), and has a shear rate of 1000s at a temperature of 30 DEG C ‑1 The shear viscosity of the aqueous resin composition is not less than 0.3 pas and not more than 3.0 pasIn the range of 3000s as shear rate at a temperature of 30 DEG C ‑1 Shear viscosity and drawing speed 3000s ‑1 The ratio of the elongational viscosity (t) to the elongational viscosity (t) of the aqueous resin composition is in the range of 3.0 to 8.0.
Description
Technical Field
The present invention relates to an aqueous resin composition, and an aqueous surface treatment agent and an article using the same.
Background
Synthetic leathers such as polyurethane leathers, polyvinyl chloride leathers, and TPO (thermoplastic olefin, thermoplastic olefin resin) leathers are used in various fields such as clothing, bags, shoes, and industrial materials as substitutes for natural leathers or as leather materials having excellent durability over natural leathers. In particular, synthetic leathers used for industrial materials such as vehicle interior materials and interior materials are required to have excellent durability and abrasion resistance. In order to meet such demands, various efforts are being made.
For example, there are a method of forming a skin layer from a silicone-modified polycarbonate polyurethane resin; a method for applying a coating agent comprising an aqueous polyurethane resin, a crosslinking agent, a silicone compound and a filler to the surface of leather. In the above method, the abrasion resistance can be improved by lowering the friction coefficient of the polyurethane resin layer as the surface of the synthetic leather.
In recent years, from the viewpoint of environmental problems, it has been desired to replace conventional solvent-based coating agents with aqueous coating agents for industrial products. However, the aqueous material tends to have inferior coating quality due to the influence of wettability and viscosity as compared with the solvent-based material. In particular, in gravure coating, when an aqueous material and a solvent material are compared, a significant difference in surface smoothness is observed.
As a conventional aqueous material, for example, there is disclosed an aqueous matte coating agent in which 50 to 300 parts by weight of fine particles having an average particle diameter of 0.1 to 3.0 μm, which are at least 1 kind of crosslinked spherical organic resin selected from acrylic resin, polyurethane resin, urea resin, silicone resin, epoxy resin, melamine resin, polypropylene resin, polyethylene resin, nylon resin, and fluororesin, are blended with respect to 100 parts by weight of a solid content of an aqueous polyurethane resin (patent document 1).
As another conventional aqueous material, an aqueous resin composition containing an aqueous polyurethane (a) obtained by reacting a polyol (a1) and a polyisocyanate (a2), an acid-modified non-chlorinated polyolefin (B), a matte agent (C), and a crosslinking agent (D) has been proposed, and the mass ratio [ (a)/(B) ] of the aqueous polyurethane (a) to the acid-modified non-chlorinated polyolefin (B) is in the range of 55/45 to 98/2 (patent document 2).
In addition, in order to improve wettability which affects coating quality, an example of using a nonionic surfactant as a constituent component of an aqueous surface treatment agent for synthetic leather has been proposed (patent document 3).
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2007-262248
Patent document 2: japanese patent laid-open publication No. 2016-084400
Patent document 3: japanese patent No. 6207304
Disclosure of Invention
Problems to be solved by the invention
However, none of the patent documents 1 to 3 disclose the adjustment of the viscosity of the aqueous resin composition, and there is a limit to the improvement of the coating quality of the aqueous resin composition.
In order to obtain an appropriate viscosity of the aqueous resin composition, it is actually necessary to adjust the type and amount of the viscosity modifier (thickener) while checking the surface state after coating using a gravure coater, and the optimization efficiency of the coatability is poor. Specifically, it is necessary to repeat a coating test on a sample of an aqueous resin composition which is subjected to a coating design based on a viscosity (a measured value obtained by a B-type viscometer or a jenn cup viscometer) close to that of a coating material for which the coating property is confirmed, and to prepare a viscosity having a good coating quality based on the result. Therefore, it is necessary to provide the aqueous resin composition to a customer who is a paint manufacturer, and to perform trial production using a real machine to obtain a result of feedback, and the cooperation of the customer is indispensable. In addition, the viscosity adjustment work in the actual machine trial test is very complicated, and the test time is long, so that the efficiency is poor. Moreover, each time the mixture ratio is changed and the coating equipment is changed, the same inspection needs to be carried out, and the improvement needs to consume time.
The present invention has been made in view of the above circumstances, and an object thereof is to provide an aqueous resin composition capable of improving coating optimization efficiency by efficiently evaluating coating quality and improving coating quality, and an aqueous surface treatment agent and an article using the aqueous resin composition.
Means for solving the problems
As a result of extensive and intensive studies, the present inventors have found that by adjusting the shear viscosity and the trouton ratio of an aqueous resin composition as a blend to within a predetermined range, the viscosity adjustment at the time of coating trial production as in the conventional blend designed according to the viscosity standard is not or hardly required, the number of trials is reduced, the coating quality can be evaluated efficiently, and the efficiency of product development can be improved by improving the efficiency of coating property optimization. Further, it has been found that the conventional blend may have a change in quality due to a viscosity modifier used for viscosity adjustment at the time of coating, water, or the like, and that in the present invention, since viscosity adjustment at the time of coating is not required, good coating quality can be stably obtained.
That is, the present invention provides the following configuration.
[1]An aqueous resin composition comprising an aqueous polyurethane (A), a matting agent (B) and an additive (C), and having a shear rate of 1000s at a temperature of 30 ℃ and a shear rate of 1000s -1 The shear viscosity of the aqueous resin composition is in the range of 0.3 pas to 3.0 pas, and the shear rate is 3000s at a temperature of 30 DEG C -1 Shear viscosity and drawing speed at 3000s -1 The ratio of the elongational viscosities of the aqueous resin compositions is in the range of 3.0 to 8.0 inclusive.
[2] The aqueous resin composition according to the above [1], wherein the shear viscosity is not less than 0.3 pas and not more than 1.0 pas.
[3] The aqueous resin composition according to the above [1], wherein the extensional viscosity is 1.0 pas to 10.0 pas.
[4] The aqueous resin composition according to any one of the above [1] to [3], wherein the content of the aqueous polyurethane (A) is 3.0 mass% or more and 50.0 mass% or less, assuming that the total amount of the aqueous resin composition is 100 mass%.
[5] The aqueous resin composition according to any one of the above [1] to [4], wherein the additive (C) contains a viscosity modifier of a nonionic surfactant.
[6] An aqueous surface treatment agent comprising the aqueous resin composition according to any one of the above [1] to [5 ].
[7] An article having a coating film of the aqueous resin composition according to any one of the above [1] to [5 ].
Effects of the invention
According to the present invention, the coating quality can be efficiently evaluated, the efficiency of coating optimization can be improved, and the coating quality can be improved.
Detailed Description
The embodiments of the present invention are described in detail below.
[ aqueous resin composition ]
The aqueous resin composition of the present invention is an aqueous resin composition comprising an aqueous polyurethane (A), a matting agent (B) and an additive (C), and has a shear rate of 1000s at a temperature of 30 ℃ and a shear rate of 1000s -1 (1/sec) has a shear viscosity of 0.3 pas-3.0 pas-3 and a shear rate of 3000s at a temperature of 30 DEG C -1 Shear viscosity and drawing speed at 3000s -1 The ratio of the elongational viscosities of the two resins, that is, the trouton ratio (i.e., elongational viscosity/shear viscosity) of the aqueous resin composition, is in the range of 3.0 to 8.0.
[ shear viscosity of aqueous resin composition ]
In the present embodiment, the shear rate is 1000s at a temperature of 30 ℃ C -1 The shear viscosity of the aqueous resin composition at that time is 0.3 pas to 3.0 pas, preferably 0.3 pas to 1.0 pas, and more preferably 0.3 pas to 0.5 pas. If the shear viscosity of the aqueous resin composition is in the range of 0.3 pas to 3.0 pas, the viscosity is not less thanWhen a predetermined shear force is applied, the viscosity of the aqueous resin composition is easily adjusted, and good coating quality is easily obtained without adjusting the viscosity by a viscosity adjusting agent or the like at the time of coating, and the coating efficiency can be improved. Further, the coating composition can exhibit low viscosity at the time of coating at a high shear rate such as roll coating or gravure coating, and the coating quality can be improved.
[ Trouton ratio of aqueous resin composition ]
The "Teluton ratio" in the present embodiment is a temperature of 30 ℃ and a drawing speed of 3000s -1 The elongational viscosity at that time was 30 ℃ at a shear rate of 3000s -1 Ratio of shear viscosity (extensional viscosity/shear viscosity).
In the present embodiment, the aqueous resin composition under the above conditions has a trouton ratio of 3.0 to 8.0, preferably 3.5 to 7.5, and more preferably 3.5 to 5.5. If the trouton ratio of the aqueous resin composition is in the range of 3.0 to 8.0, the fluidity of the aqueous resin composition can be maintained, the elongation of the aqueous resin composition becomes good, and the coating efficiency can be improved. In particular, when the aqueous resin composition is coated, it can exhibit a viscosity that facilitates coating when a roll coater or a gravure roll coater is used.
The trouton ratio of the aqueous resin composition can be controlled by adjusting the ratio of the low-viscosity material and the high-viscosity material contained in the aqueous resin composition to adjust the extensional viscosity and/or the shear viscosity. For example, the trouton ratio of the aqueous resin composition can be controlled by adjusting the mixing ratio of the aqueous polyurethane in the aqueous resin composition to adjust the extensional viscosity and/or the shear viscosity. Further, the extensional viscosity and/or the shear viscosity can be controlled by adjusting the ratio of the low-viscosity material and the high-viscosity material contained in the materials (polyol (a1), polyisocyanate (a2)) used in the aqueous polyurethane (a).
The viscosity of the aqueous polyurethane (a) used in the aqueous resin composition can be grasped by those skilled in the art. Further, a person skilled in the art can obtain an aqueous resin composition having a shear viscosity and a trouton ratio within desired ranges based on a known technique within a range of ordinary experiments by appropriately adjusting the mixing ratio of the aqueous polyurethane (a) in the aqueous resin composition. Further, as described above, the shear viscosity and the trouton ratio of the aqueous polyurethane (a) which is a reaction product of the polyol (a1) and the polyisocyanate (a2) can be obtained by those skilled in the art by adjusting the kind, the blending ratio, and the like of the polyol (a1) and the polyisocyanate (a 2).
(aqueous polyurethane (A))
The aqueous polyurethane (a) is a compound obtained by reacting a polyol (a1) with a polyisocyanate (a 2). As the aqueous polyurethane (A), a compound obtained by reacting a compound (a-1) having an active hydrogen group, a compound (a-2) having at least one active hydrogen group and a hydrophilic group, and a compound (a-3) having an isocyanate group is preferable.
The content of the aqueous polyurethane (a) is preferably 3.0 mass% or more and 50.0 mass% or less, more preferably 4.0 mass% or more and 30.0 mass% or less, and further preferably 5.0 mass% or more and 20.0 mass% or less, assuming that the total amount of the aqueous resin composition is 100 mass%. The content of the aqueous polyurethane (a) is a value in terms of solid content relative to the entire aqueous resin composition. When the content of the aqueous polyurethane (a) is 3.0 mass% or more and 50.0 mass% or less, a suitable aqueous resin composition can be obtained as an aqueous coating agent used for gravure coating or the like.
The aqueous polyurethane (A) is preferably an aqueous polyurethane obtained by reacting a compound (a-1) having an active hydrogen group, a compound (a-2) having at least one active hydrogen group and a hydrophilic group, and a compound (a-3) having an isocyanate group.
Examples of the active hydrogen group of the compound (a-1) include a hydroxyl group, a phenolic hydroxyl group, an amino group, and a mercapto group. Among them, hydroxyl group, carboxyl group and amino group are preferable. Further, the above-mentioned compound (a-1) preferably has 2 or more of these active hydrogen groups in 1 molecule.
Examples of the compound (a-1) include relatively low molecular weight polyols such as ethylene glycol, propylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 3-methyl-1, 5-pentanediol, 1, 6-hexanediol, neopentyl glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, bishydroxyethoxybenzene, 1, 4-cyclohexanediol, 1, 4-cyclohexanedimethanol, bisphenol a, hydrogenated bisphenol a, hydroquinone, and alkylene oxide adducts thereof, glycerin, trimethylolethane, trimethylolpropane, sorbitol, pentaerythritol, and the like.
Examples of the compound (a-1) other than the above include polyester polyol, polyether polyol, polycarbonate polyol, polyacetal polyol, polyacrylate polyol, polyesteramide polyol, polythioether polyol, polyolefin polyol, and polyamine. These compounds (a-1) may be used alone or in combination of 2 or more.
The polyester polyol can be obtained by a dehydration condensation reaction of a diol compound, a dicarboxylic acid compound, a hydroxycarboxylic acid compound, or the like, a ring-opening polymerization reaction of a cyclic ester compound such as e-caprolactone, or the like, and copolymerization of a polyester obtained by these reactions. Examples of the diol compound which is a raw material of the polyester polyol include ethylene glycol, propylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 3-methyl-1, 5-pentanediol, 1, 6-hexanediol, neopentyl glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, bishydroxyethoxybenzene, 1, 4-cyclohexanediol, 1, 4-cyclohexanedimethanol, bisphenol a, hydrogenated bisphenol a, hydroquinone, and alkylene oxide adducts thereof.
Examples of the dicarboxylic acid compound to be used as a raw material of the polyester polyol include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic acid, fumaric acid, 1, 3-cyclopentanedicarboxylic acid, 1, 4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, 1, 4-naphthalenedicarboxylic acid, 2, 5-naphthalenedicarboxylic acid, 2, 6-naphthalenedicarboxylic acid, biphenyldicarboxylic acid, and 1, 2-bis (phenoxy) ethane-p, p' -dicarboxylic acid.
Examples of the hydroxycarboxylic acid compound to be used as a raw material of the polyester polyol include p-hydroxybenzoic acid and p- (2-hydroxyethoxy) benzoic acid.
Examples of the polyether polyol include those obtained by addition polymerization of a cyclic ether compound having 2 or more active hydrogen groups such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, 1, 3-butanediol, 1, 4-butanediol, 1, 6-hexanediol, neopentyl glycol, glycerol, trimethylolethane, trimethylolpropane, sorbitol, sucrose, aconite sugar, trimellitic acid, phosphoric acid, ethylenediamine, diethylenetriamine, triisopropanolamine, pyrogallol, dihydroxybenzoic acid, hydroxyphthalic acid, 1,2, 3-propanetrithiol, etc., with ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, cyclohexene, etc., or a product obtained by ring-opening polymerization of the cyclic ether compound using a cationic catalyst, a protonic acid, a Lewis acid, or the like as a catalyst.
The polycarbonate polyol is obtained by reacting a diol compound such as 1, 4-butanediol, 1, 6-hexanediol, or diethylene glycol with diphenyl carbonate and phosgene.
Examples of the polyamine include ethylenediamine, 1, 6-hexamethylenediamine, piperazine, isophoronediamine, 4' -dicyclohexylmethanediamine, 3' -dimethyl-4, 4' -dicyclohexylmethanediamine, 1, 4-cyclohexanediamine, 1, 2-propanediamine, diethylenetriamine, triethylenetetramine, and hydrazine.
The compound (a-2) is a compound having at least one active hydrogen group and a hydrophilic group, and examples thereof include a compound having at least one active hydrogen group and having a carboxyl group, a sulfonic acid group, or a salt thereof as a hydrophilic group, and a compound having a nonionic hydrophilic group having a repeating unit of an alkylene oxide. These compounds (a-2) may be used alone, or 2 or more of them may be used in combination.
Examples of the compound having a carboxyl group as the hydrophilic group include compounds having a carboxyl group and a hydroxyl group or an amino group, such as 2, 2-dimethylolpropionic acid, 2-dimethylolbutyric acid, 2-dimethylolvaleric acid, dioxymaleic acid, 2, 6-dioxybenzoic acid, 3, 4-diaminobenzoic acid, succinic acid, adipic acid, maleic acid, phthalic acid, alanine, aminobutyric acid, aminocaproic acid, glycine, glutamic acid, aspartic acid, and histidine, and dicarboxylic acid compounds.
Examples of the compound having a sulfonic acid group as the hydrophilic group include compounds having a sulfonic acid group and a hydroxyl group, a carboxyl group or an amino group, and disulfonic acid compounds, such as 2-oxyethanesulfonic acid, phenolsulfonic acid, sulfobenzoic acid, sulfosuccinic acid, 5-sulfoisophthalic acid, sulfanilic acid, 1, 3-phenylenediamine-4, 6-disulfonic acid, and 2, 4-diaminotoluene-5-sulfonic acid.
Further, examples of the compound having a nonionic hydrophilic group as the hydrophilic group include polyethylene glycol, polypropylene glycol, a copolymer of ethylene oxide and propylene oxide, a copolymer of ethylene oxide and polybutylene oxide, and a copolymer of ethylene oxide and another alkylene oxide.
Examples of the compound (a-3) having an isocyanate group include 2, 4-tolylene diisocyanate, 2, 6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4-diphenylmethane diisocyanate, 2,4' -diphenylmethane diisocyanate, 2-diphenylmethane diisocyanate, 3-dimethyl-4, 4-biphenyl diisocyanate, 3-dimethoxy-4, 4' -biphenyl diisocyanate, 3' -dichloro-4, 4-biphenyl diisocyanate, 1, 5-naphthalene diisocyanate, 1, 5-tetrahydronaphthalene diisocyanate, tetramethylene diisocyanate, 1, 6-hexamethylene diisocyanate, dodecamethylene diisocyanate, and mixtures thereof, Polyisocyanates such as trimethylhexamethylene diisocyanate, 1, 3-cyclohexane diisocyanate, 1, 4-cyclohexane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, hydrogenated xylylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, 4-dicyclohexylmethane diisocyanate, 3-dimethyl-4, 4-dicyclohexylmethane diisocyanate, and the like. These isocyanate group-containing compounds may be used alone, or 2 or more of them may be used in combination.
Among the compounds (a-3) having an isocyanate group, 2, 4-tolylene diisocyanate and 2, 6-tolylene diisocyanate are preferable because the raw material cost can be reduced, and 1, 6-hexamethylene diisocyanate, isophorone diisocyanate and 4, 4-dicyclohexylmethane diisocyanate are preferable because the light resistance and heat resistance can be improved.
Examples of the method for producing the aqueous polyurethane (a) by reacting the polyol (a1) with the polyisocyanate (a2) include: a method in which a compound (a-1) having an active hydrogen group, a compound (a-2) having at least one active hydrogen group and a hydrophilic group, and a compound (a-3) having an isocyanate group are added in an appropriate order and mixed without a solvent or in the presence of an organic solvent, and the reaction is carried out at a reaction temperature in the range of about 25 ℃ to 150 ℃.
The reaction of the polyol (a1) and the polyisocyanate (a2) is preferably carried out, for example, in such a manner that the equivalent ratio of the isocyanate group of the polyisocyanate (a2) to the hydroxyl group of the polyol (a1) is 0.8 to 2.5, more preferably 0.9 to 1.5.
In the aqueous polyurethane (a), when the compound (a-2) having at least one active hydrogen group and a hydrophilic group has an acid group such as a carboxyl group or a sulfonic acid group as a hydrophilic group, the acid group is preferably neutralized. The neutralization may be carried out by adding a basic compound to the reactants after the polyol (a1) is reacted with the polyisocyanate (a 2). Typical examples of the basic compound include tertiary amines such as trimethylamine, triethylamine and tri-n-butylamine; and inorganic alkaline substances such as lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium chloride, and potassium chloride.
In addition, a chain extender may be used as necessary in the production of the aqueous polyurethane (a).
Examples of the chain extender include polyamines, hydrazine compounds, and other compounds having active hydrogen atoms. These chain extenders may be used alone, or 2 or more of them may be used in combination.
Among them, the aqueous polyurethane (a) obtained by hydrazine extension using a hydrazine compound is preferable because of improved adhesion to the plastic substrate.
Examples of the polyamine include diamines such as ethylenediamine, 1, 2-propylenediamine, 1, 6-hexamethylenediamine, piperazine, 2, 5-dimethylpiperazine, isophoronediamine, 4' -dicyclohexylmethanediamine, 3' -dimethyl-4, 4' -dicyclohexylmethanediamine and 1, 4-cyclohexanediamine, and N-hydroxymethylaminoethylamine, N-hydroxyethylaminoethylamine, N-hydroxypropylaminopropylamine, N-ethylaminoethylamine, N-methylaminopropylamine, diethylenetriamine, dipropylenetriamine and triethylenetetramine. Among these, ethylenediamine is preferred.
Examples of the hydrazine compound include hydrazine, N' -dimethylhydrazine, 1, 6-hexamethylenedihydrazine, succinic dihydrazide, adipic dihydrazide, glutaric dihydrazide, sebacic dihydrazide, isophthalic dihydrazide, β -semicarbazide propionic acid hydrazide, 3-semicarbazide propyl carbamate, semicarbazide-3-semicarbazide methyl-3, 5, 5-trimethylcyclohexane, and the like. Of these, hydrazine is preferred.
Examples of the other active hydrogen-containing compounds include glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1, 3-propanediol, 1, 3-butanediol, 1, 4-butanediol, hexamethylene glycol, sucrose, methylene glycol, glycerin, and sorbitol; phenols such as bisphenol a, 4' -dihydroxybiphenyl, 4' -dihydroxydiphenyl ether, 4' -dihydroxydiphenyl sulfone, hydrogenated bisphenol a and hydroquinone, and water.
When a polyamine is used as the chain extender, the equivalent ratio [ amino group/isocyanate group ] of the amino group and the isocyanate group of the polyamine is preferably 1.2 or less, and more preferably in the range of 0.3 to 1.
Examples of the organic solvent that can be used in the production of the aqueous polyurethane (a) include ketone solvents such as acetone and methyl ethyl ketone; ether solvents such as tetrahydrofuran and dioxane; acetate solvents such as ethyl acetate and butyl acetate; nitrile solvents such as acetonitrile; amide solvents such as dimethylformamide and N-methylpyrrolidone, and the like. These organic solvents may be used alone, or 2 or more of them may be used in combination.
In addition, in order to achieve safety and reduce the load on the environment, the organic solvent may be partially or completely removed by, for example, distillation under reduced pressure during or after the production of the aqueous polyurethane (a).
The aqueous polyurethane (a) obtained by the above method is preferably a compound having a mass average molecular weight of 5,000 to 500,000, more preferably a compound having a mass average molecular weight of 5,000 to 200,000, and even more preferably a compound having a mass average molecular weight of 20,000 to 100,000, from the viewpoint of achieving durability.
The mass average molecular weight (in terms of polyethylene) measurement by GPC (gel permeation chromatography) in the present invention was performed under the following conditions using the system HLC8220 manufactured by tokyo corporation.
Separating the column: 4 TSK gel GMHHR-N manufactured by Tosoh corporation
Column temperature: 40 deg.C
A flowing layer: tetrahydrofuran manufactured by Wako pure chemical industries Ltd
Flow rate: 1.0 ml/min
Sample concentration: 0.4% by mass
Sample injection amount: 100 microliter
A detector: differential refractometer
When the mass average molecular weight is 5,000 or more, not only the durability is improved, but also various problems due to drying failure tend to be less likely to occur, and when the molecular weight is 500,000 or less, problems such as a decrease in coatability are less likely to occur, and therefore, the use is preferable.
(matte finishing agent (B))
Examples of the matte agent (B) include silica particles, organic microbeads, calcium carbonate, magnesium carbonate, barium carbonate, talc, aluminum hydroxide, calcium sulfate, kaolin, mica, asbestos, mica, calcium silicate, and aluminum silicate.
Examples of the silica particles include dry silica and wet silica. From the viewpoint of light resistance and abrasion resistance, wet silica such as silica gel can be used. From the viewpoint of high scattering effect and wide adjustment range of the gloss value, dry silica may be used. In addition, from the viewpoint of easy dispersion in the composition, dry silica surface-modified with an organic compound may also be used. The average particle diameter of these silica particles is preferably in the range of 2 μm to 14 μm, and more preferably in the range of 3 μm to 12 μm.
Examples of the organic beads include acrylic beads, urethane beads, silicon beads, and olefin beads.
The matte agent (B) may contain 1 or 2 or more of the above materials. For example, the matte agent (B) may contain wet silica and organic microbeads.
(additive (C))
The aqueous resin composition of the present invention may contain an additive (C) in addition to the above components. The additive (C) may be contained in the aqueous polyurethane (A) or may be contained in the aqueous resin composition.
Examples of additives (C) include: leveling agent; inorganic fine particles such as colloidal silica and alumina sol; polymethyl methacrylate-based organic fine particles; defoaming agents (antifoaming agents), anti-sagging agents, wetting dispersants, viscosity modifiers, ultraviolet absorbers, metal deactivators, peroxide decomposers, flame retardants, reinforcing agents, plasticizers, lubricants, rust inhibitors, fluorescent brighteners, inorganic heat ray absorbers, flameproofing agents, antistatic agents, dehydrating agents, and the like. The additive (C) may contain 1 or 2 or more of the above components. Further, the above components constituting the additive (C) may be composed of 1 or 2 or more kinds of materials.
When the additive (C) contains a viscosity modifier, the content of the viscosity modifier is preferably in the range of 0.3 to 3.5% by mass, more preferably in the range of 0.5 to 2.0% by mass, and still more preferably in the range of 1.0 to 1.8% by mass, based on 100% by mass of the total amount of the aqueous resin composition. The content of the viscosity modifier is a value in terms of solid content relative to the entire aqueous resin composition. When the content of the viscosity modifier is 0.3% by mass or less, the desired viscoelastic properties are not easily obtained. Further, if the content is 3.5% by mass or more, the coating film properties such as water resistance and light resistance as a coating composition are deteriorated.
The viscosity modifier is not particularly limited, and is preferably a nonionic surfactant such as a polymer type special nonionic surfactant. The viscosity modifier may contain 1 or 2 or more of nonionic surfactants.
(crosslinking agent (D))
The aqueous resin composition of the present invention may further contain a crosslinking agent (D). The crosslinking agent (D) may be contained in the aqueous polyurethane (A) or may be contained in the aqueous resin composition.
Examples of the crosslinking agent (D) include urea resin crosslinking agents such as oxazoline, carbodiimide, polyisocyanate, blocked isocyanate, epoxy resin, polysiloxane, aziridine, and alkylated melamine, and hydrazide crosslinking agents. Among these, carbodiimide can be used from the viewpoint of crosslinking performance and safety. The crosslinking agent (D) may contain 1 or 2 or more of the above components.
The content of the crosslinking agent (D) is preferably in the range of 0.2 to 12.0 mass%, more preferably in the range of 0.4 to 8.0 mass%, from the viewpoint of the coating film strength, assuming that the total amount of the aqueous resin composition is 100 mass%. The content of the crosslinking agent (D) is a value in terms of solid content relative to the entire aqueous resin composition.
(wax (E))
The aqueous resin composition of the present embodiment may further contain a wax (E) as necessary.
The wax (E) is not particularly limited, and examples thereof include polyolefin waxes. Among the polyolefin waxes, those having a melting range of 140 to 180 ℃ are preferable, those having a melting range of 145 to 175 ℃ are more preferable, and those having a melting range of 150 to 170 ℃ are even more preferable, from the viewpoint of preventing the coating film from leaving traces (solvent marks) even when it comes into contact with a solvent such as alcohol and improving the solvent resistance. Examples of such polyolefin waxes include polyethylene wax and polypropylene wax. The polyolefin wax may contain 1 or 2 or more of the above materials. When 2 or more kinds of polyolefin waxes are used in combination, the melting range is the melting range of the mixture. The melting range was measured according to JIS test method K0064-1992.
Among the polyolefin waxes, polypropylene waxes are preferable because solvent marks can be reduced. In addition, the content of the polyolefin wax is preferably in the range of 0.5 to 10 mass%, more preferably in the range of 1.0 to 8.0 mass%, from the viewpoint of improving the solvent mark reducing effect and the strength of the coating film, when the total amount of the aqueous resin composition is 100 mass%. The content of the polyolefin wax is a value in terms of solid content relative to the entire aqueous resin composition.
(pigment)
The aqueous resin composition of the present embodiment may be used in combination with a pigment as necessary. The pigment may be contained in the aqueous polyurethane (a) or may be contained in the aqueous resin composition.
The pigment is not particularly limited, and various pigments can be used. Examples of the pigment include organic pigments such as extender pigments, white pigments, black pigments, gray pigments, red pigments, brown pigments, green pigments, blue pigments, metal powder pigments, luminescent pigments, pearl pigments, and the like, inorganic pigments, plastic pigments, and the like described in "stock of paint" 1970 edition (edited by japan paint association).
Examples of the organic pigment include various insoluble azo pigments such as benzidine yellow, hansa yellow and lake Red 4R, soluble azo pigments such as lake Red C, carmine 6B and purplish Red 10, various (copper) phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green, various basic dye lakes such as rhodamine lake and methyl violet lake, various mordant dye pigments such as quinoline lake and fast sky blue, various vat dye pigments such as anthraquinone pigment, thioindigo pigment and perinone pigment, various quinacridone pigments such as quinacridone Red (cinqua Red) B, various dioxazine pigments such as dioxazine violet, various condensed azo pigments such as phthalein (ChromoPhthal), and aniline black.
Examples of the inorganic pigment include various chromates such as chrome yellow, zinc chromate, and molybdate orange; various ferrocyanides such as ultramarine blue, various metal oxides such as titanium oxide, zinc oxide, Mapico Yellow, iron oxide, red iron oxide, chromium oxide green, and zirconium oxide, various sulfides or selenides such as cadmium Yellow, cadmium red, and mercury sulfide, various sulfates such as barium sulfate and lead sulfate, various silicates such as calcium silicate and ultramarine blue, various carbonates such as calcium carbonate and magnesium carbonate, various phosphates such as cobalt violet and manganese violet, various metal powder pigments such as aluminum powder, gold powder, silver powder, copper powder, bronze powder, and brass powder, flake pigments of these metals, mica flake pigments in the form of a coated metal oxide, metal pigments such as mica-like iron oxide pigments, pearl pigments, graphite, and carbon black.
Examples of the extender pigment include precipitated barium sulfate, chalk (chalk), precipitated calcium carbonate, calcium hydrogen carbonate, calcite, alumina white, silica, hydrated fine silica (white carbon), ultrafine anhydrous silica (aerosil), silica sand (silica sand), talc, precipitated magnesium carbonate, bentonite, clay, kaolin, and ochre.
Examples of the plastic pigment include "GRANDOL PP-1000" and "PP-2000S" manufactured by DIC.
As the pigment, from the viewpoint of excellent durability, weather resistance and design properties, it is more preferable to use an inorganic acid compound such as titanium oxide or zinc oxide as a white pigment, or carbon black as a black pigment.
The aqueous surface treatment agent according to the present embodiment contains the aqueous resin composition. The aqueous surface treatment agent is typically used for the surface of an article described later.
Further, the article according to the present embodiment has a coating film of the aqueous resin composition of the present invention. Examples of the articles include housings of household appliances (refrigerators, washing machines, air conditioners, televisions, etc.), housings of electronic devices (computers, mobile phones, smart phones, etc.), materials of musical instruments (pianos, electronic organs, electronic musical instruments, etc.), interior materials of automobiles or railway vehicles (instrument panels, door trims, ceilings, car covers, etc.), plastic moldings such as building materials or furniture materials (wall papers, decorative sheets for plywood, decorative sheets for steel sheets, leather for attaching chairs, etc.), packaging materials (packaging films, etc.), wooden materials (plywood, laminated materials, single-layer laminated materials, etc.), and ceramic materials (interior tiles, bricks, etc.). Examples thereof include materials for sporting goods (e.g., ski, archery, golf, tennis, etc.), materials for footwear (e.g., upper materials, sole, core materials, heel surface, insole, etc., of shoes), and metal materials (e.g., iron, copper, zinc, aluminum, etc.). Among these articles, the aqueous resin composition of the present invention can be suitably used for plastic molded articles, and is preferably used for TPO leather and TPO sheets in the plastic molded articles.
Examples
The present invention will be described in more detail with reference to examples. The present invention is not limited to the following examples. In the following examples, "part" and "%" are based on mass unless otherwise specified.
Production example 1
Into a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen gas blowing tube were charged 500 parts by mass of a polycarbonate diol (weight average molecular weight: 1,000) as a1, 6-hexanediol base, 34 parts by mass of 2, 2-dimethylolpropionic acid and 355 parts by mass of methyl ethyl ketone under a nitrogen gas flow, and the mixture was uniformly mixed. Then, after 295 parts by mass of 4, 4-dicyclohexylmethane diisocyanate was added, 0.1 part by mass of dibutyltin dilaurate was added, and the reaction was carried out at 70 ℃ for about 4 hours, thereby obtaining a methyl ethyl ketone solution of a urethane prepolymer having an isocyanate group at a molecular end (NCO% in terms of solid content: 3.8% by mass).
To the methyl ethyl ketone solution of the urethane prepolymer obtained above was added 25 parts by mass of triethylamine, and after the carboxyl groups in the urethane prepolymer were neutralized, 1,555 parts by mass of ion-exchanged water was added. Then, 23 parts by mass of ethylenediamine was added to the reaction solution to carry out a reaction. After the reaction, methyl ethyl ketone was distilled off under reduced pressure to obtain an aqueous polyurethane PUD-1 (nonvolatile content: 35 mass%).
(example 1)
Aqueous polyurethane PUD-1, propylene glycol, a polysiloxane leveling agent (BYK-342, manufactured by BYK), silica gel (NIPGEL AZ-200, manufactured by Tosoh corporation), crosslinked urethane microbeads (Art Pearl C-800T, manufactured by Yokoku corporation), a high molecular type special nonionic surfactant (ADEKA NOL UH-420, manufactured by ADEKA corporation, 30% of active ingredient), a foam breaker (SN Deformer 777, manufactured by Santanopoco corporation) and water were mixed in the proportions shown in Table 1, and the aqueous resin composition was obtained by mixing them uniformly.
(example 2)
An aqueous resin composition was obtained in the same manner as in example 1, except that the amount of the polymer type special nonionic surfactant was increased.
(example 3)
An aqueous resin composition was obtained in the same manner as in example 1, except that propylene glycol as a water-soluble solvent was not used.
(example 4)
An aqueous resin composition was obtained in the same manner as in example 1, except that a different polymer type special nonionic surfactant (ADEKA NOL UH-450VF, effective component 30%) was used and the amount of the surfactant was reduced.
(example 5)
An aqueous resin composition was obtained in the same manner as in example 4, except that a urethane-modified polyether viscosity modifier (Sn Thickener-612NC, 45% as an active ingredient, manufactured by Santa Nuo Co., Ltd.) was used instead of the polymer type special nonionic surfactant.
Comparative examples 1 and 2
An aqueous resin composition was obtained in the same manner as in example 1, except that the amount of the polymer type special nonionic surfactant was decreased and the viscosity was further decreased by heating at 50 ℃ for 30 days.
Comparative example 2
An aqueous resin composition was obtained in the same manner as in example 1, except that the amount of the polymer type special nonionic surfactant to be added was decreased.
Comparative example 3
An aqueous resin composition was obtained in the same manner as in example 1, except that layered hectorite (LAPONITE (registered trademark) RD, manufactured by BYK corporation, having a water content of less than 10%) was used in place of the polymer type special nonionic surfactant and the amount of the layered hectorite was reduced.
Comparative example 4
An aqueous resin composition was obtained in the same manner as in comparative example 3, except that the amount of the layered hectorite was further reduced.
Comparative example 5
An aqueous resin composition was obtained in the same manner as in comparative example 4, except that an alkali-soluble thickener (vocoact VE, 29% active ingredient, manufactured by DIC corporation) was used instead of the layered hectorite.
The aqueous polyurethane and aqueous resin compositions used in examples 1 to 5 and comparative examples 1 to 5 were measured and evaluated by the following methods.
(measurement of shear viscosity and calculation of the Trouton ratio)
For examples 1 to 5 and comparative examples 1 to 5, the shear rate was measured at 30 ℃ for 1000s by the following methods -1 The shear viscosity and the elongation rate of the aqueous polyurethane at 30 ℃ for 3000s -1 The elongational viscosity of the aqueous polyurethane in the above case was determined as the trouton ratio (elongational viscosity/shear viscosity).
The extensional viscosity was measured according to the capillary rheometer evaluation method described in JIS-7199(ISO 11443, ASTM D3835).
Specifically, a double capillary type apparatus (RHEOGRAPH 20, product of Gottfert) was used. The polyurethane dispersant (aqueous polyurethane) was measured at a measurement temperature of 30 ℃ using a capillary die having a length of 10mm and a diameter of 0.5mm, and a capillary die having a length of 0.25mm and a diameter of 0.5 mm.
Then, the shear rate is 300-300000 s -1 The apparent shear viscosity (pressure) measured below, corrected using Bagley to remove pressure loss, gives the true shear viscosity of the polyurethane dispersant (aqueous polyurethane). From the obtained true shear viscosity and pressure loss, the elongational viscosity corresponding to the elongation rate was obtained using the Cogswell formula. From shear rate 3000s -1 True shear viscosity and drawing speed at 3000s -1 The elongational viscosity in the above case was determined as the trouton ratio (elongational viscosity/shear rate).
The temperature is 30 ℃ and the shearing speed is 1000s -1 Shear viscosity and temperature at 30 deg.CShear rate 3000s -1 The values of the elongational viscosity and the trouton ratio are shown in table 1.
For reference, the viscosities of the aqueous resin compositions of examples 1 to 5 and comparative examples 1 to 5 were measured using a B-type VISCOMETER (VISCOMETER TVB-22, manufactured by tokyo industries, inc.) with a rotor No.2 at a rotation speed of 30rpm, and the measured values are shown in tables 1 to 2.
(coatability)
The aqueous resin compositions obtained in examples 1 to 5 and comparative examples 1 to 5 were coated on a TPO sheet (thickness: 0.4mm) by using a gravure roll coater (#100 gravure, coating speed: 10 m/min), and then dried at 120 ℃ for 1 minute to obtain samples for evaluation.
The coating quality as the appearance was good "when there were no irregularities or few irregularities in the coating film, slight poor" Δ "when irregularities such as a slash or an orange peel were observed in the observation direction, and poor" x "when irregularities such as a slash or an orange peel were clearly observed.
The results of measurement and evaluation by the above-described methods are shown in tables 1 to 2.
[ Table 1]
[ Table 2]
As is clear from the results in Table 1, in example 1, the temperature was 30 ℃ and the shear rate was 1000 seconds -1 When the shear viscosity of the polyurethane dispersant is 0.37 pas and the trouton ratio is 3.5, the coating property is good.
In example 2, it is found that when the amount of the polymer type special nonionic surfactant is larger than that in example 1, the temperature is 30 ℃ and the shear rate is 1000s -1 The shear viscosity of the polyurethane dispersant was 0.46 pas and the Trouton ratio was 5.3, and the coating was conductedThe assembly performance is good.
Example 3 shows that the temperature was 30 ℃ and the shear rate was 1000 seconds without using propylene glycol as a water-soluble solvent -1 The shear viscosity of the polyurethane dispersant was 0.35 pas, the Trouton ratio was 5.5, and the coatability was good.
Example 4 shows that when a polymer type special nonionic surfactant different from that used in example 1 was used and the amount of the surfactant added was reduced, the temperature was 30 ℃ and the shear rate was 1000 seconds -1 The shear viscosity of the polyurethane dispersant was 0.37 pas, the Trouton ratio was 7.3, and the coatability was good.
Example 5 shows that when a urethane-modified polyether viscosity modifier is used in place of a polymer-type special nonionic surfactant, the temperature is 30 ℃ and the shear rate is 1000s -1 The shear viscosity of the polyurethane dispersant was 0.35 pas, the Trouton ratio was 4.1, and the coatability was good.
On the other hand, from the results in Table 2, it is clear that in comparative example 1, when the amount of the polymer type special nonionic surfactant is reduced and the viscosity is further reduced by heating at 50 ℃ for 30 days, the temperature is 30 ℃ and the shear rate is 1000s -1 The shear viscosity of the polyurethane dispersant was 0.24 pas, and the coating property was poor.
Comparative example 2 shows that when the amount of the polymer type special nonionic surfactant is reduced, the temperature is 30 ℃ and the shear rate is 1000s -1 The shear viscosity of the polyurethane dispersant in the case of the dispersion was 0.26 pas, and the coatability was slightly poor.
Comparative example 3 shows that when a layered hectorite is used in place of the polymer-type special nonionic surfactant and the amount of the layered hectorite added is reduced, the temperature is 30 ℃ and the shear rate is 1000 seconds -1 The shear viscosity of the polyurethane dispersant was 0.05 pas, and the coating property was poor. Further, since the drawing speed at the start of the drawing hardening is low and the drawing hardening occurs, the extensional viscosity and the trouton ratio cannot be measured.
Comparative example 4 shows that when the amount of layered hectorite was further reduced, the temperature was 30 ℃ and the shear rate was 1000 seconds -1 Polyurethane dispersion ofThe shear viscosity of the agent was 0.08 pas, and the coatability was poor. Further, since the drawing speed at the start of the drawing hardening is low and the drawing hardening occurs, the extensional viscosity and the trouton ratio cannot be measured.
Comparative example 5 shows that when an alkali-soluble thickener is used in place of layered hectorite, the temperature is 30 ℃ and the shear rate is 1000 seconds -1 The shear viscosity of the polyurethane dispersant was 0.17 pas, the Trouton ratio was 8.1, and the coatability was poor.
Claims (7)
1. An aqueous resin composition comprising an aqueous polyurethane (A), a matting agent (B) and an additive (C),
at a temperature of 30 ℃ and a shear rate of 1000s -1 The shear viscosity of the aqueous resin composition is in the range of 0.3 pas to 3.0 pas,
at a temperature of 30 ℃ as a shear rate of 3000s -1 Shear viscosity and drawing speed at 3000s -1 The ratio of the elongational viscosities of the aqueous resin compositions is in the range of 3.0 to 8.0 inclusive, i.e., the elongational viscosity/shear viscosity.
2. The aqueous resin composition according to claim 1, wherein,
the shear viscosity is 0.3Pa · s or more and 1.0Pa · s or less.
3. The aqueous resin composition according to claim 1, wherein,
the extensional viscosity is 1.0Pa · s or more and 10.0Pa · s or less.
4. The aqueous resin composition according to any one of claims 1 to 3,
the content of the aqueous polyurethane (a) is 3.0 mass% or more and 50.0 mass% or less, assuming that the total amount of the aqueous resin composition is 100 mass%.
5. The aqueous resin composition according to any one of claims 1 to 4,
the additive (C) contains a viscosity modifier of a nonionic surfactant.
6. An aqueous surface treatment agent comprising the aqueous resin composition according to any one of claims 1 to 5.
7. An article having a coating film of the aqueous resin composition according to any one of claims 1 to 5.
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| JP2021021933A JP2022124265A (en) | 2021-02-15 | 2021-02-15 | Aqueous resin composition, and aqueous surface treatment agent and article using the aqueous resin composition |
| JP2021-021933 | 2021-02-15 |
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| CN (1) | CN114940820A (en) |
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