CN108350309A - Aqueous resin coating composition, heat ray shielding film and their manufacturing method using it - Google Patents
Aqueous resin coating composition, heat ray shielding film and their manufacturing method using it Download PDFInfo
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- CN108350309A CN108350309A CN201680064321.5A CN201680064321A CN108350309A CN 108350309 A CN108350309 A CN 108350309A CN 201680064321 A CN201680064321 A CN 201680064321A CN 108350309 A CN108350309 A CN 108350309A
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- Prior art keywords
- coating composition
- mass parts
- ester
- resin coating
- aqueous resin
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- 239000008199 coating composition Substances 0.000 title claims abstract description 108
- 229920005989 resin Polymers 0.000 title claims abstract description 65
- 239000011347 resin Substances 0.000 title claims abstract description 65
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 58
- 239000002245 particle Substances 0.000 claims abstract description 64
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 55
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 55
- 229920005749 polyurethane resin Polymers 0.000 claims abstract description 44
- 239000007787 solid Substances 0.000 claims abstract description 42
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000000839 emulsion Substances 0.000 claims abstract description 28
- 239000011787 zinc oxide Substances 0.000 claims abstract description 20
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910001887 tin oxide Inorganic materials 0.000 claims abstract description 15
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910003437 indium oxide Inorganic materials 0.000 claims abstract description 10
- -1 polyols compound Chemical class 0.000 claims description 62
- 238000000034 method Methods 0.000 claims description 35
- 239000000470 constituent Substances 0.000 claims description 33
- 229920005862 polyol Polymers 0.000 claims description 25
- 239000003795 chemical substances by application Substances 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 239000004970 Chain extender Substances 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 13
- 239000005056 polyisocyanate Substances 0.000 claims description 10
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- 239000007795 chemical reaction product Substances 0.000 claims description 6
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052733 gallium Inorganic materials 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
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- 239000011701 zinc Substances 0.000 claims description 4
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- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 abstract description 28
- 230000006641 stabilisation Effects 0.000 abstract description 17
- 238000011105 stabilization Methods 0.000 abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 56
- 239000004615 ingredient Substances 0.000 description 52
- 239000006210 lotion Substances 0.000 description 35
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 25
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 24
- 150000002148 esters Chemical class 0.000 description 23
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 20
- 150000001875 compounds Chemical class 0.000 description 19
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 18
- 238000000576 coating method Methods 0.000 description 16
- 239000011248 coating agent Substances 0.000 description 15
- 239000006087 Silane Coupling Agent Substances 0.000 description 13
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- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 12
- 239000002904 solvent Substances 0.000 description 11
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 10
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 9
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- 238000013329 compounding Methods 0.000 description 8
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 8
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- 239000006097 ultraviolet radiation absorber Substances 0.000 description 8
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 7
- 239000001273 butane Substances 0.000 description 7
- 125000005442 diisocyanate group Chemical group 0.000 description 7
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 7
- 239000012948 isocyanate Substances 0.000 description 7
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
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- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
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- 239000004611 light stabiliser Substances 0.000 description 6
- 239000011859 microparticle Substances 0.000 description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 6
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 150000003077 polyols Chemical class 0.000 description 6
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 description 5
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 5
- 239000003595 mist Substances 0.000 description 5
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 5
- 235000019260 propionic acid Nutrition 0.000 description 5
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
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- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 4
- 239000012964 benzotriazole Substances 0.000 description 4
- 239000004305 biphenyl Substances 0.000 description 4
- 235000010290 biphenyl Nutrition 0.000 description 4
- 239000007822 coupling agent Substances 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 4
- RTWNYYOXLSILQN-UHFFFAOYSA-N methanediamine Chemical compound NCN RTWNYYOXLSILQN-UHFFFAOYSA-N 0.000 description 4
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
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- DIVDFFZHCJEHGG-UHFFFAOYSA-N oxidopamine Chemical compound NCCC1=CC(O)=C(O)C=C1O DIVDFFZHCJEHGG-UHFFFAOYSA-N 0.000 description 4
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- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 4
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 4
- DBXBTMSZEOQQDU-UHFFFAOYSA-N 3-hydroxyisobutyric acid Chemical compound OCC(C)C(O)=O DBXBTMSZEOQQDU-UHFFFAOYSA-N 0.000 description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 3
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
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- 238000007254 oxidation reaction Methods 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 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
- 150000002989 phenols Chemical class 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- WIYYWMWBBUEWSN-UHFFFAOYSA-N phosphorous acid tridecane Chemical compound P(O)(O)O.CCCCCCCCCCCCC WIYYWMWBBUEWSN-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920006289 polycarbonate film Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- GGHDAUPFEBTORZ-UHFFFAOYSA-N propane-1,1-diamine Chemical compound CCC(N)N GGHDAUPFEBTORZ-UHFFFAOYSA-N 0.000 description 1
- 150000004672 propanoic acids Chemical class 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 150000003839 salts Chemical group 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical class OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000026676 system process Effects 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229960001295 tocopherol Drugs 0.000 description 1
- 229930003799 tocopherol Natural products 0.000 description 1
- 235000010384 tocopherol Nutrition 0.000 description 1
- 239000011732 tocopherol Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- XTTGYFREQJCEML-UHFFFAOYSA-N tributyl phosphite Chemical compound CCCCOP(OCCCC)OCCCC XTTGYFREQJCEML-UHFFFAOYSA-N 0.000 description 1
- NESLVXDUKMNMOG-UHFFFAOYSA-N triethoxy-(propyltetrasulfanyl)silane Chemical compound CCCSSSS[Si](OCC)(OCC)OCC NESLVXDUKMNMOG-UHFFFAOYSA-N 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- JRSJRHKJPOJTMS-MDZDMXLPSA-N trimethoxy-[(e)-2-phenylethenyl]silane Chemical compound CO[Si](OC)(OC)\C=C\C1=CC=CC=C1 JRSJRHKJPOJTMS-MDZDMXLPSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- GVJHHUAWPYXKBD-IEOSBIPESA-N α-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-IEOSBIPESA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
-
- 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
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/004—Reflecting paints; Signal paints
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/02—Emulsion paints including aerosols
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
- Laminated Bodies (AREA)
Abstract
The present invention provide metal oxide particle dispersion stabilization is excellent, the aqueous resin coating composition more than solid content, heat ray shielding film and their manufacturing method using it.A kind of aqueous resin coating composition, it contains the case of wet attrition object of ester-polyurethane resin emulsion (A) and metal oxide particle (B), the metal oxide particle (B) is at least one kind of in the group being made of antimony-doped tin oxide, stibium-doped zinc oxide, Ga-doped zinc oxide and tin-doped indium oxide, and the average grain diameter of case of wet attrition object is 70nm or less.
Description
Technical field
The present invention relates to aqueous resin coating composition, use its heat ray shielding film and their manufacturing method
(being also briefly referred to as below " coating composition ", " film " and " manufacturing method "), specifically, is related to metal oxide particle
Dispersion stabilization is excellent, the aqueous resin coating composition more than solid content, using its heat ray shielding film and it
Manufacturing method.
Background technology
In recent years, from the viewpoint of energy saving, for the mesh of the heat rays such as infrared ray, the near infrared ray shielded in sunlight
, develop the gold that there is heat ray shielding effect containing such as antimony-doped tin oxide, tin-doped indium oxide, stibium-doped zinc oxide etc.
Belong to the heat ray shielding coating of the coating window of the particle of oxide.On the other hand, the bad shadow due to environmental problem, to human body
Loud problem and the use for limiting organic solvent.Therefore, from organic solvent system coating to the water for hardly including organic solvent
It is that the displacement of cold coating is also promoted, it is proposed that the heat of the particle comprising the metal oxide with heat ray shielding effect
The aqueous polyurethane resin coating compositions (for example, patent document 1,2) of alpha ray shield.
Existing technical literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2013-087228 bulletins
Patent document 2：Japanese Unexamined Patent Publication 2013-230613 bulletins
Invention content
Problems to be solved by the invention
In the aqueous polyurethane resin coating compositions of existing heat ray shielding, since metal oxide microparticle is poly-
Dispersion stabilization in urethane resin is insufficient, therefore 15~30 mass % water dispersions of metal oxide microparticle are added to
In aqueous polyurethane resin.However, in order to be compounded the metal oxide microparticle for the amount for being enough to shield heat ray, it is originated from metal and aoxidizes
The moisture of the water dispersion of object particle becomes more, can only obtain the few coating composition of solid content.
In addition, the evaporation latent heat due to water is big, compared with solvent system coating, the drying of aqueous resin coating is time-consuming,
The film of the few aqueous resin coating of solid content adequate thickness in order to obtain needs further to be overlapped coating, workability production
Raw problem.In addition, in the case where having used the water dispersion of metal oxide microparticle, the dispersibility of metal oxide microparticle is not
Fully, therefore there is the insufficient this problem of the transparency.
Therefore, that the purpose of the present invention is to provide the dispersion stabilizations of metal oxide particle is excellent, solid content is more
Aqueous resin coating composition, heat ray shielding film and their manufacturing method using it.
The solution to the problem
The inventors of the present invention have made intensive studies in order to solve the above problems, as a result, it has been found that making by using prescriptive procedure
Ester-polyurethane resin emulsion and metal oxide with heat ray shielding reduce grain size, can improve metal oxide particle
Dispersion stabilization, and the aqueous resin coating composition more than solid content can be obtained, so as to complete the present invention.
That is, the aqueous resin coating composition of the present invention is characterized in that, contain ester-polyurethane resin emulsion (A) and metal
The case of wet attrition object of oxide particle (B), the metal oxide particle (B) is selected to be aoxidized by antimony-doped tin oxide, Sb doped
At least one kind of in the group of zinc, Ga-doped zinc oxide and tin-doped indium oxide composition, the average grain diameter of aforementioned case of wet attrition object is
70nm or less.Herein, average grain diameter refers to the average grain diameter using the volume reference of dynamic light scattering determination.
For the coating composition of the present invention, solid constituent is 15~45 mass %, relative to from aforementioned polyurethane tree
The content of 100 mass parts of solid constituent of fat liquor (A), aforementioned metal oxides particle (B) is preferably 18~80 mass parts.Separately
Outside, for the present invention coating composition, aforementioned ester-polyurethane resin emulsion (A) be as molecular weight be 500 or more macromolecule
The polyurethane resin of weight polyalcohol compound, the reaction product of polyisocyanates, hydrophilic group imported agent and chain extender, aforementioned high score
Sub- weight polyalcohol compound is preferably polyester polyol.
In addition, the heat ray shielding film of the present invention is characterized in that, it is to be formed by this on resin base material film
Made of the heat ray shielding layer that the aqueous resin coating composition of invention is formed.
In turn, the manufacturing method of aqueous resin coating composition of the invention is characterized in that the manufacturing method has
Following process：Using case of wet attrition by ester-polyurethane resin emulsion (A) and selected from by antimony-doped tin oxide, stibium-doped zinc oxide, gallium
At least one kind of metal oxide particle (B) in the group of doping zinc-oxide and tin-doped indium oxide composition crushes, is dispersed to average grain
Diameter is 70nm or less.
In the manufacturing method of the present invention, solid constituent is 15~45 mass %, relative to from aforementioned polyurethane resin breast
The content of 100 mass parts of solid constituent of liquid (A), aforementioned metal oxides particle (B) is preferably 18~80 mass parts.In addition,
In the manufacturing method of the present invention, aforementioned ester-polyurethane resin emulsion (A) be as molecular weight be 500 or more high molecular weight polyols
The polyurethane resin of compound, the reaction product of polyisocyanates, hydrophilic group imported agent and chain extender, aforementioned high molecular weight polyhydric
Alcoholic compound is preferably polyester polyol.
In addition, the manufacturing method of the heat ray shielding film of the present invention is characterized in that the manufacturing method has as follows
Process：Using case of wet attrition by ester-polyurethane resin emulsion (A) and selected from by antimony-doped tin oxide, stibium-doped zinc oxide, gallium doping
At least one kind of metal oxide particle (B) in the group of zinc oxide and tin-doped indium oxide composition, which crushes, is dispersed to average grain diameter, is
70nm or less and the process that aqueous resin coating composition is made；And
The process aqueous resin coating composition being coated on resin base material film.
The effect of invention
In accordance with the invention it is possible to which the dispersion stabilization for providing metal oxide particle is excellent, the water system more than solid content
Resin coating compositions, heat ray shielding film and their manufacturing method using it.
Specific implementation mode
Hereinafter, successively to the present invention aqueous resin coating composition, using its heat ray shielding film and they
Manufacturing method is described in detail.
＜ aqueous resin coating compositions ＞
The coating composition of the present invention contains ester-polyurethane resin emulsion (A) (hereinafter also referred to as " (A) ingredient ") and metal
The case of wet attrition object of oxide particle (B) (hereinafter also referred to as " (B) ingredient "), the metal oxide particle (B) be selected from by
It is at least one kind of in the group that antimony-doped tin oxide, stibium-doped zinc oxide, Ga-doped zinc oxide and tin-doped indium oxide form.For
The coating composition of the present invention, these case of wet attrition objects i.e. average grain diameter of (A) ingredient and (B) ingredient are 70nm or less.
In the aqueous polyurethane resin coating compositions of existing heat ray shielding, added into ester-polyurethane resin emulsion
The water dispersion of the metal oxide microparticle of heat ray shielding, however in the case of the coating composition of the present invention, due to
Ester-polyurethane resin emulsion and metal oxide particle are crushed using case of wet attrition, dispersion, therefore it is more to obtain solid constituent
Composition.In general, when metal oxide particle is dispersed stably in the aqueous solvents such as water, alcohol, surface-active has been used
Agent, dispersant (referring for example to Japanese Unexamined Patent Publication 2005-187580 etc.), but for the coating composition of the present invention, polyurethane resin
Lotion helps to disperse stability, even if can make metal oxide particle steadily if without using surfactant, dispersant
Dispersion.As its reason, it is believed that although being difficult to directly determine the dispersity of metal oxide particle, in polyurethane resin
With multiple carbamate groups, urea groups, and when with from the amino of chain extender, carboxyl or sulfonic group, the absorption of these groups
Inhibit reassociating for metal oxide particle on metal oxide particle surface.
In addition, compared with the aqueous polyurethane resin coating compositions of existing heat ray shielding, coating of the invention
Composition can obtain transparency high film solid content is identical.Speculate the reason for this is that：Existing Coating material composition
Object is simply mixed made of the water dispersion of ester-polyurethane resin emulsion and metal oxide particle, the particle of polyurethane resin
Absorption to metal oxide particle is weak, however the coating composition of the present invention passes through powder in the presence of ester-polyurethane resin emulsion
The broken second particle of metal oxide, to which the particle of polyurethane resin adsorbs or be attached to strongly the table of metal oxide
Face improves dispersibility.
In general, the smaller easier second particle for forming particle and assembling each other of the grain size of the particle of metal oxide, water,
Dispersion stabilization in solvent reduces.However, the case where coating composition of the present invention, crush by using case of wet attrition
(B) second particle of ingredient controls the average grain diameter of coating composition in 70nm hereinafter, above-mentioned so as to obtain well
Effect, therefore dispersion stabilization improves.
The preferably small person of average grain diameter of the coating composition of the present invention, if but keep grain size too small, it is difficult to obtain industrial
Raw material, when manufacture needs costly labour.Therefore, the average grain diameter of the particle of coating composition of the invention is preferably
30~65nm, further preferably 45~60nm.It should be noted that the average grain diameter of the coating composition of the present invention is not
(B) average grain diameter of the second particle of ingredient, but the average grain diameter of (A) ingredient and (B) ingredient.Below to the coating of the present invention
The ester-polyurethane resin emulsion (A) and metal oxide (B) of composition are described in detail.
＜ ester-polyurethane resin emulsions (A) ＞
In the coating composition of the present invention, ester-polyurethane resin emulsion (A) refers to made of polyurethane resin is dispersed in water
Substance.(A) ingredient can utilize well known method to manufacture.Such as there are as below methods：What is do not reacted with isocyanate group
Then water is marginally added to carry out Phase inversion emulsification, root in the higher carbamate prepolymer of synthetic molecular weight in solvent every time
According to the method needed using decompression removal solvent；The method that emulsifier is added and is dispersed in water by violent stirring；Or
Make to be imported with carbamate prepolymer of the hydrophilic radical such as polyoxyethylene groups, carboxyl in molecule and be dispersed in water, so
The method etc. that addition chain extender is reacted afterwards.As (A) ingredient of the present invention, preferably：To make molecular weight is 500 or more height
Carbamate prepolymer is dispersed in water made of molecular polyol alcoholic compound, polyisocyanates and the reaction of hydrophilic group imported agent
In, then add polyurethane resin made of chain extender.
For the coating composition of the present invention, the high molecular weight polyols compound that molecular weight is 500 or more preferably has
At least two hydroxyl.Such as it can enumerate：Pass through phthalic acid, adipic acid, dimerization leukotrienes, maleic acid, 12- hydroxy stearates
The glycol such as the organic acids such as acid and ethylene glycol, propylene glycol, butanediol, diethylene glycol, neopentyl glycol, 12- hydroxystearyl alcohols, three hydroxyl first
Polyester polyol obtained from the dehydration condensation of base propane, hexanetriol, glycerine, trimethylolethane, pentaerythrite etc.；It is logical
Cross the polyester polyol that the ring-opening polymerisation of glycolide, lactide, 6-caprolactone, Lanthanum Isopropoxide etc. obtains；In ethylene glycol, two
Ethylene glycol, triethylene glycol, 1,2- propylene glycol, 1,3- propylene glycol, 1,2- butanediols, 1,3 butylene glycol, 1,4- butanediols, new penta 2
Addition of ethylene oxide and/or epoxy third in the low molecular weight polyols such as alcohol, 1,6-HD, bisphenol-A, hydrogenated bisphenol A or polyphenol
Addition reaction product, polyethylene glycol, polypropylene glycol, polyethylene/polypropylene glycol, polytetramethylene glycol etc. obtained from alkane are poly-
Ethoxylated polyhydric alcohol；By 1,4- butanediols, 1,6-HD, ethylene glycol, propylene glycol, 3- methyl-1s, 5- pentanediols, neopentyl glycol,
The glycol such as diethylene glycol, 1,4- cyclohexanediols, 1,4 cyclohexane dimethanol and dimethyl carbonate, diethyl carbonate, carbonic acid Asia second
Polycarbonate polyol etc. obtained from the condensation reaction of the carbonate products such as ester.In high molecular weight polyols compound, by
It is excellent in the dispersibility of (B) ingredient, the high film of the transparency, therefore preferred polyester polyol can be obtained.
As the polyisocyanates used in (A) ingredient, diisocyanate can be enumerated and have in 1 molecule 3 with
The polyisocyanates etc. of upper isocyanate group.It as diisocyanate, such as can enumerate, toluene di-isocyanate(TDI), diphenyl
Methane -4,4 '-diisocyanate, to phenylene vulcabond, xylylene diisocyanate, 1,5- naphthalene diisocyanates,
3,3 '-dimethyl diphenyls -4,4 '-diisocyanate, dimethoxyaniline diisocyanate, two isocyanide of durol dimethyl
The aromatic diisocyanates class such as acid esters；It is isophorone diisocyanate, dicyclohexyl methyl hydride -4,4 '-diisocyanate, trans-
And/or the ester ring types diisocyanates such as cis- -1,4- cyclohexane diisocyanates, norbornene diisocyanate；1,6- oneself
Diisocyanate, 2,2,4 and/or the fat such as (2,4,4)-trimethyl hexamethylene diisocyanate, lysine diisocyanate
(cyclo) aliphatic diisocyanates class；And their mixture etc..
As the polyisocyanates with 3 or more isocyanate group in 1 molecule, such as can enumerate：Triphenyl first
Alkane triisocyanate, 1- methylbenzene -2,4,6- triisocyanates, dimethyl triphenyl methane tetraisocyanate, comprising they
The carbodiimide modified of isocyanates more than isocyanates, these 3 functions more than 3 functions of mixture etc., isocyanuric acid
Modifier that ester modified, biuret is modified etc., they are blocked using various end-capping reagents made of blocked isocyanate, aforementioned two
The isocyanuric acid ester (tripolymer) of isocyanates and biuret tripolymer etc..
Wherein, from the aspect of the excellent film such as being easy and weatherability and intensity can be obtained, preferred fat
(cyclo) aliphatic diisocyanates, ester ring type diisocyanate, more preferable hexamethylene diisocyanate,-two isocyanide of dicyclohexyl methyl hydride -4,4 '
Acid esters, isophorone diisocyanate.
In the coating composition of the present invention, hydrophilic group imported agent refers to the hydrogen reacted with isocyanate group containing at least one
Atom and at least one tertiary amino, carboxyl or sulfonic compound.As hydrophilic group imported agent, can enumerate：Triethanolamine,
The tri-alkanolamines compound such as triisopropanolamine；The N- alkane such as N methyldiethanol amine, N- ethyldiethanolamines, N butyl diethanol amine
Base dialkanol amine compound；N, N- dimethylethanolamine, N, N, N- the dialkyl amine compounds such as N- diethyl ethylene diamines；2-
Hydroxyacetic acid, 4 hydroxybutyric acid etc. have the single methanol compound of carboxyl；2,2- dihydromethyl propionic acids, 2,2- dimethylolpropionic acids,
2,2- dihydroxymethyl valeric acids etc. have the diol compound of carboxyl；1,4- butanediol -2- sulfonic acid etc. is containing sulfonic diolation
Close object etc..From the aspect of applying film strength raising, the hydrogen atom reacted with isocyanate group is preferably 2, from (B) ingredient
From the aspect of dispersion stabilization improves, the further preferably diol compound of carboxyl.It is improved from the water dispersible of (A) ingredient
From the aspect of, the dosage of hydrophilic group imported agent is 5~50 moles of % preferably with respect to high molecular weight polyols compound.
In the coating composition of the present invention, chain extender refers to the hydrogen atom that there is at least two to be reacted with isocyanate group
Low molecular weight compound is the compound in addition to hydrophilic group imported agent.As chain extender, can enumerate：Ethylene glycol, the third two
Alcohol, 1,4- butanediols, 1,5- pentanediols, 1,6-HD, 1,12- dodecanediols, 12- hydroxystearyl alcohols, glycerine, three hydroxyl first
The low molecular weight polyols compound such as base ethane, trimethylolpropane, pentaerythrite, D-sorbite；Ethylenediamine, propane diamine, six
Methylene diamine, phenylenediamine, toluenediamine, diphenyl diamine, diamino-diphenyl bismethane, diamino-dicyclohexyl methane,
The polyamine compounds such as piperazine, isophorone diamine, diethylenetriamines, dipropylenetriamine, melamine；Hydrazine, monoalkylhydrazine,
The hydrazine compounds such as 1,4- diazanyl divinyls；Dihydrazide compounds, the water such as two hydrazides such as carbohydrazide, adipic dihydrazide etc..Wherein,
From with the reactivity of isocyanates it is excellent from the aspect of, preferred polyamine compounds, and from the few side of the influence to film physical property
Face consideration, preferably water.
The compounding of high molecular weight polyols compound, polyisocyanates and hydrophilic group imported agent when for manufacture prepolymer
Than, relative to isocyanate group, the molar ratio of isocyanate-reactive group and isocyanate group be preferably 30~99 moles of %,
More preferable 50~99 moles of %.It can use solvent, when using solvent, preferably react urethane when manufacturing prepolymer
For the big solvent of nonactive and with water compatibility, from the aspect of being easy by depressurizing removal, preferably acetone, methyl ethyl ketone,
Dioxanes, tetrahydrofuran, n-methyl-2-pyrrolidone.Prepolymer is added in water and is dispersed in water, for prepolymer and water
Ratio, relative to the total amount of prepolymer and water, prepolymer is preferably 15~40 mass %.
For the coating composition of the present invention, for example, chain extender is added after prepolymer is dispersed in water, with prepolymer
Isocyanate group is reacted.For using dosage when chain extender than water, relative to the isocyanates in prepolymer
The hydrogen atom of base, chain extender reacted with isocyanate group is preferably 10~200 moles of %, more preferably 50~90 moles of %.
When less than 10 moles of %, the molecular weight of (A) ingredient is small sometimes reduces to the physical property of film, on the other hand, is more than 200 moles of %
When, unreacted chain extender can remain sometimes reduces to the physical property of film.
From the viewpoint of the water dispersible of (A) ingredient, tertiary amino, carboxyl or the sulfonic group for being originated from hydrophilic group imported agent are excellent
Choosing is neutralized.Such neutralization can be dispersed in water rear and addition before prepolymer is dispersed in water, by prepolymer
Before chain extender, after prepolymer and chain extender reaction in it is arbitrary when.For using the compound with tertiary amino as hydrophilic
Neutralizer when base imported agent can enumerate：The organic sulfonic acids such as the carboxylic acids such as formic acid, acetic acid, succinic acid, p-methyl benzenesulfonic acid, hydrochloric acid,
The quaternary salts agents such as the inorganic acids such as phosphoric acid, dialkyl group sulfuric acid, alkyl halide.In addition, for using with carboxyl or sulfonic chemical combination
Neutralizer when object is as hydrophilic group imported agent, can enumerate：Trimethylamine, triethylamine, tripropyl amine (TPA), tri-n-butylamine, N- methyl diethyls
The inorganic bases such as the organic amines such as hydramine, triethanolamine, sodium hydroxide, potassium hydroxide, ammonia.The amount of neutralizer, which can be used, to be enough to neutralize
(A) amino in ingredient, carboxyl or sulfonic amount.
(A) ingredient of coating composition as the present invention, can use commercially available ester-polyurethane resin emulsion.As commercially available
Ester-polyurethane resin emulsion, such as can enumerate：" ADEKA BONTIGHTER " series of ADEKA Corp., San Jingdong
Press " FORESTER " series of Chemical Co., Ltd., " Bondic " system of Dainippon Ink＆Chemicals, Inc.
Row, " HYDRAN " series, " Impranil " series of Bayer corporations, Nippon Soflan Co., Ltd.'s
" Soffranate " series, " POIZ " of Kao Corp are serial, Sanyo Chemical Industries, Ltd.
" Sanprene " series, " Aizerakkusu " series of Baotugu Chemical Industrial Co., Ltd, the first industrial pharmaceutical strain formula meeting
" Superflex " series, " NeoRez " series etc. of Zeneca Co., Ltd. of society.
＜ metal oxide particles (B) ＞
For the coating composition of the present invention, metal oxide particle (B) is selected from by antimony-doped tin oxide, Sb doped oxygen
Change at least one kind of metal oxide particle in the group of zinc, Ga-doped zinc oxide and tin-doped indium oxide composition.(B) ingredient is pair
Coating composition assigns the ingredient of the heat ray shielding effect of infrared ray, near infrared ray etc..As (B) ingredient, the room from sunlight
From the aspect of the shield effectiveness height of the high near infrared ray of interior temperature rise effect etc., preferred antimony-doped tin oxide.
For the coating composition of the present invention, (B) of the heat ray shielding effect in addition to assigning infrared ray, near infrared ray etc.
Other than ingredient, commonly known other heat ray shielding ingredients can also be applied in combination.As such compound, such as can be with
It enumerates：The lanthanide series compounds such as tungsten system complex oxide, lanthanum hexaboride.
For the coating composition of the present invention, just (A) ingredient and (B) ingredient ratio for, (B) ingredient relative to from
(A) content of 100 mass parts of solid constituent of ingredient is preferably 18~80 mass parts.(B) content of ingredient is less than 18 mass parts
When, thick film is made in sufficient heat ray shielding and needing in order to obtain, and the workability for application reduces, higher than 80
When mass parts, the adaptation to the flatness of film, relative to base material generates harmful effect sometimes.(B) ingredient relative to from
(A) more preferable 20~70 mass parts of content, further preferred 25~60 mass parts of 100 mass parts of solid constituent of ingredient.
It should be noted that from the viewpoint of dispersion stabilization, film the transparency, the grain size of (B) ingredient is preferably most
Small person is measured, but from the aspect of the easiness industrially obtained, for the grain size of (B) ingredient, the average grain diameter of primary particle is excellent
It is selected as 2~50nm, more preferably 5~30nm.
The coating composition of the present invention is characterized in that, is crushed (A) ingredient and (B) ingredient using case of wet attrition, dispersion
It is 70nm or less to average grain diameter.For the coating composition of the present invention, average grain diameter refers to utilizing dynamic light scattering determination
Volume reference average grain diameter.The grain size of the particle of metal oxide is smaller, it is easier formed particle assemble each other it is secondary
Particle, dispersion stabilization reduce.For the coating composition of the present invention, carry out crushing metal oxide by using case of wet attrition
Second particle controls the average grain diameter of coating composition in 70nm hereinafter, so as to improve dispersion stabilization.The present invention's
The preferably small person of the average grain diameter of coating composition, if but keep grain size too small, it is difficult to obtain industrial raw material, when manufacture needs
Costly labour.Therefore, the average grain diameter of the particle of coating composition of the invention is preferably 30~65nm, is more preferably
45~60nm.
In order to adjust the solid constituent of coating composition of the invention, water, coating composition of the invention can also be added
Solid constituent be preferably 15~45 mass %.Solid constituent refers to according to JIS K6828-1 (synthetic resin emulsions-the 1 herein
Portion：Nonvolatile component seeks method) condition B (temperature：105 DEG C, heating time：1 hour) measure when nonvolatile component.This hair
When the solid constituent of bright coating composition is less than 15 mass %, the drying of film is time-consuming sometimes, in order to obtain sufficient shielding
Effect and need overlapping to be coated with, when more than 45 mass %, the case of wet attrition of (A) ingredient and (B) ingredient becomes difficult or golden sometimes
Belonging to the dispersion stabilization of oxide particle reduces.More preferable 20~43 mass % of solid constituent of the coating composition of the present invention,
Further preferred 25~40 mass %.
The other blend ＞ of ＜
For the coating composition of the present invention, from the side that the weatherability that can shield harmful ultraviolet light, film also improves
Face considers, preferably further contains ultra-violet absorber.As ultra-violet absorber, can enumerate：Gaultherolin, salicylic acid
To tert-butyl benzene base ester, salicylic acid to salicyclic acid derivatives such as octyl phenyl esters；ESCALOL 567,2- hydroxyls
The benzophenone cpds such as base -4- oxy-octyl benzophenones, 4- dodecyloxy -2- dihydroxy benaophenonels；2- (2 '-hydroxyls-
5 '-aminomethyl phenyls) benzotriazole, 2- (2 '-hydroxyls -3 '-tertiary butyl -5 '-aminomethyl phenyl) benzotriazole, 2- (2 '-hydroxyls -3 ',
5 '-di-tert-pentyl-phenyls) benzotriazole cpds such as benzotriazole；3- phenyl -7- (4 '-methyl -5 '-n-butoxy benzo three
Azoles -2-) coumarin compounds such as cumarin；Inorganic system's ultra-violet absorber such as cerium oxide, zinc oxide, iron oxide, titanium oxide etc..
When the compounding amount of ultra-violet absorber is very few, it is unable to fully ground shielding ultraviolet rays and is not only unable to get and matches in addition, when excessive
The increment effect that mixed amount matches, and sometimes reduce the physical property of the film obtained by coating composition of the invention.Therefore, phase
For 100 mass parts of solid constituent from (A) ingredient of the coating composition of the present invention, ultra-violet absorber preferably 1~15
Mass parts, more preferable 5~10 mass parts.
From the aspect of the raising of the weatherability of film, aqueous resin coating composition of the invention preferably further contains
Amine system of being obstructed light stabilizer, antioxidant (phosphorus system, phenols or sulfur antioxidant).
As the amine system light stabilizer that is obstructed, such as can enumerate：2,2,6,6- tetramethyl -4- piperidyls stearate, 1,
2,2,6,6- pentamethyl -4- piperidyls stearate, 2,2,6,6- tetramethyl -4- piperidyls benzoic ether, bis- (2,2,6,6- tetra-
Methyl -4- piperidyls) sebacate, bis- (1,2,2,6,6- pentamethyl -4- piperidyls) sebacates, it is bis- (octyloxy -2,2 1-,
6,6- tetramethyl -4- piperidyls) sebacate, 1,2,2,6,6- pentamethyl -4- piperidyl methyls methyl acrylate, 2,2,6,
6- tetramethyl -4- piperidyl methyls methyl acrylate, four (2,2,6,6- tetramethyl -4- piperidyls) -1,2,3,4- butane four
Carboxylate, four (1,2,2,6,6- pentamethyl -4- piperidyls) -1,2,3,4- butane tetracarboxylics acid esters, bis- (2,2,6,6- tetramethyls -
4- piperidyls) bis- (tridecyl) -1,2,3,4- butane tetracarboxylics acid esters, bis- (1,2,2,6,6- pentamethyl -4- piperidyls)
Bis- (tridecyl) -1,2,3,4- butane tetracarboxylics acid esters, bis- (1,2,2,6,6- pentamethyl -4- piperidyls) -2- butyl -2- (3,
5- di-tert-butyl-4-hydroxyl benzyls) malonate, 1- (2- hydroxyethyls) -2,2,6,6- tetramethyls -4- piperidine alcohols/succinic acid
Bis- (2,2,6,6- tetramethyl -4- piperidyl aminos) hexanes/Bromofume condensation polymer of diethylester condensation polymer, 1,6-, 1,6- it is bis- (2,
2,6,6- tetramethyl -4- piperidyl aminos) bis- chloro- 6- morpholinyls-s-triazine condensation polymers of hexane/2,4-, the bis- (2,2,6,6- of 1,6-
Tetramethyl -4- piperidyl aminos) bis- chloro- 6- t-octyls amino-s-triazine condensation polymers of hexane/2,4-, tetra- [2,4- of 1,5,8,12-
Bis- (N- butyl-N- (2,2,6,6- tetramethyl -4- piperidyls) amino)-s-triazine -6- bases] four azepines 12 of -1,5,8,12-
Alkane, 1,5,8,12- tetra- [bis- (N- butyl-N- (1,2,2,6,6- pentamethyl -4- piperidyls) amino)-s-triazine -6- bases of 2,4-] -
1,5,8,12- teteaazacyclododecanes, [bis- (N- butyl-N- (2,2,6,6- tetramethyl -4- piperidyls) ammonia of 2,4- of 1,6,11- tri-
Base)-s-triazine -6- bases amino] hendecane, the [bis- (N- butyl-N- (1,2,2,6,6- pentamethyl -4- piperidines of 2,4- of 1,6,11- tri-
Base) amino)-s-triazine -6- bases amino] hendecane, the bis- (1,1- dimethyl -2- [three (2,2,6,6- tetramethyl -4- piperidines of 3,9-
Base oxygroup carbonyloxy group) butyl carbonyloxy group] ethyl) -2,4,8,10- four oxaspiro (5.5) hendecane, bis- (the 1,1- dimethyl-of 3,9-
2- [three (1,2,2,6,6- pentamethyl -4- piperidyl oxygroups carbonyloxy group) butyl carbonyloxy groups] ethyl) four oxaspiros of -2,4,8,10-
(5.5) hendecane etc..
As phosphorous antioxidant, such as can enumerate：Triphenyl phosphite, phosphorous acid three (2,4- di-tert-butyl-phenyls)
Ester, phosphorous acid three (2,5- di-tert-butyl-phenyls) ester, phosphorous acid three (nonyl phenyl) ester, phosphorous acid three (dinonylphenyl) ester,
Phosphorous acid three (mono-, di- mixes nonyl phenyl) ester, diphenyl acid phosphite ester, 2,2 '-di-2-ethylhexylphosphine oxides (4,6- di-tert-butyls
Base) octyl phosphite ester, phosphorous acid diphenyl last of the ten Heavenly stems ester, phosphorous acid diphenyl monooctyl ester, two (nonyl phenyl) pentaerythrites, two phosphorous
Acid esters, phenyl diisodecyl ester, tributyl phosphite, phosphorous acid three (2- ethylhexyls) ester, phosphorous acid tridecane base ester,
Trilauryl, dibutyl acid phosphite ester, dilauryl acid phosphite ester, three lauryls, three thiophosphorous acid
Ester, bis- (neopentyl glycol) 1,4- cyclohexanedimethyls diphosphites, bis- (2,4- di-tert-butyl-phenyls) pentaerythrites two are sub-
Phosphate, bis- (2,5- di-tert-butyl-phenyls) pentaerythritol diphosphites, bis- (2,6- di-t-butyl -4- aminomethyl phenyls) seasons penta
Tetrol diphosphites, bis- (2,4- dicumylphenyls) pentaerythritol diphosphites, distearyl pentaerythrite diphosphorous acid
Ester, four (C12-C15 mixed alkyls) -4,4 '-isopropylidene diphenylphosphite, bis- [2,2 '-di-2-ethylhexylphosphine oxides (4,6- diamyls
Base phenyl)] isopropylidene diphenylphosphite, the bis- (2- tertiary butyl -5- methyl of four (tridecyl) 4,4 '-butanes
Phenol) diphosphites, six (tridecyl) 1,1,3- tri- (2- methyl -5- tert-butyl-hydroxy phenyls) butane Sanyas
Phosphate, four (2,4- di-tert-butyl-phenyls) biphenylene diphosphonites, three (2- ((2,4,7,9- tetra-terts dibenzo (d,
F) seven ring -6- bases of (1,3,2) dioxy phospha) oxygroup) ethyl) amine, the miscellaneous -10- phospho hetero phenanthrenes -10- oxides of 9,10- dihydro-9-oxies,
Three (2- ((seven ring -6- bases of 2,4,8,10- tetra-terts dibenzo (d, f) (1,3,2) dioxy phospha) oxygroup) ethyl) amine, 2-
(1,1- dimethyl ethyls) -6- methyl -4- [3- [[2,4,8,10- tetra- (1,1- dimethyl ethyls) dibenzo [d, f] [1,3,2]
Seven ring -6- bases of dioxy phospha] oxygroup] propyl] phenol -2- butyl -2- ethyl glycol 2,4,6- tri-butyl-phenols Dan Ya
Phosphate etc..
As phenol antioxidant, such as can enumerate：DBPC 2,6 ditertiary butyl p cresol, 2,6- diphenyl -4- octadecanes
Oxygroup phenol, (3,5- di-tert-butyl-hydroxy phenyls) propionic acid stearyl, (3,5- di-tert-butyl-4-hydroxyl benzyls) phosphonic acids
Distearyl base ester, tridecyl 3,5- di-tert-butyl-4-hydroxyl benzyls thiacetate, the bis- [(3,5- bis- of thiodiethylene
Tert-butyl-hydroxy phenyl) propionic ester], 4,4 '-thiobis (6- tertiary butyls-metacresol), two (3,5- of 2- octylsulfos -4,6-
Di-t-butyl -4- hydroxyphenoxies)-s-triazine, 2,2 '-di-2-ethylhexylphosphine oxides (4- methyl-6-tert-butylphenols), bis- [bis- (4- of 3,3-
Hydroxyl -3- tert-butyl-phenyls) butyric acid] diol ester, 4,4 '-butane bis(2,6-di-butyl phenol)s, 4,4 '-butanes are double
(6- tertiary butyl -3- methylphenols), 2,2 '-ethidines bis- (4,6- DI-tert-butylphenol compounds), (2- methyl -4- hydroxyls-of 1,1,3- tri-
5- tert-butyl-phenyls) butane, bis- [2- tertiary butyl -4- methyl -6- (2- hydroxyl -3- tertiary butyl -5- methylbenzyls) phenyl] to benzene
Dicarboxylic acid esters, 1,3,5- tri- (2,6- dimethyl -3- hydroxyl -4- t-butylbenzyls) isocyanuric acid ester, (bis- uncles of 3,5- of 1,3,5- tri-
Butyl -4- hydroxybenzyls) isocyanuric acid ester, 1,3,5- tri- (3,5- di-tert-butyl-4-hydroxyl benzyls) -2,4,6- trimethylbenzenes,
1,3,5- tri- [(3,5- di-tert-butyl-hydroxy phenyls) propionyloxyethyl] isocyanuric acid ester, four [methylene -3- (3 ', 5 ' -
Di-t-butyl -4 '-hydroxy phenyl) propionic ester] methane, 2- tertiary butyl -4- methyl -6- (2- acryloxy -3- tertiary butyls -5-
Methylbenzyl) phenol, bis- [2- (3- tertiary butyl-4-hydroxy -5- methylhydroxies the cinnamoyloxy group) -1,1- dimethyl second of 3,9-
Base] -2,4,8,10- four oxaspiro [5.5] hendecane, the bis- [β-(3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) third of triethylene glycol
Acid esters], tocopherol etc..
As sulfur antioxidant, such as can enumerate：The dilauryl of thio-2 acid, two myristins, nutmeg
The dialkyls dipropionic acid esters such as base stearyl ester, distearyl ester and pentaerythrite four (β-dodecy propionic ester) etc. are more
The β of first alcohol-alkylmercaptopropionates class.
When the compounding amount of amine system of being obstructed light stabilizer and antioxidant is very few, sufficient compound effects are unable to get, in addition,
When excessive, it is not only unable to get the increment effect to match with compounding amount, but also obtained sometimes by the coating composition of the present invention
The physical property of film reduces.Accordingly, with respect to the present invention coating composition 100 mass of solid constituent from (A) ingredient, by
Hinder compounding amount part preferably 0.001~5 mass parts, more preferable 0.01~3 mass parts of amine system light stabilizer and antioxidant.
From the aspect of being improved with the adaptation of glass, coating composition of the invention preferably comprises silane coupling agent.Make
For silane coupling agent, can enumerate：The silane containing vinyl such as vinyltrimethoxysilane, vinyltriethoxysilane
Coupling agent；2- (3,4- epoxycyclohexyls) ethyl trimethoxy silane, 3- glycydoxy methyl dimethoxy oxygroup silicon
Alkane, 3- glycidyl ether oxypropyltrimethoxysilanes, 3- glycydoxies methyldiethoxysilane, 3- contractings
The silane coupling agent containing epoxy group such as water glyceryl ether oxypropyl triethoxysilane；To styryltrimethoxysilane etc.
Silane coupling agent containing styryl；3- (methyl) acryloxypropyls dimethoxysilane, 3- (methyl) propylene
Acryloxypropylethoxysilane trimethoxy silane, 3- (methyl) acryloxypropyls diethoxy silane, 3- (methyl) acryloyl
Oxygroup propyl-triethoxysilicane etc. contains the silane coupling agent of (methyl) acryloyl group；N-2- (amino-ethyl) -3- aminopropans
Ylmethyl dimethoxysilane, N-2- (amino-ethyl) -3- TSL 8330s, 3- aminopropyl trimethoxy silicon
Alkane, 3-aminopropyltriethoxysilane, 3- triethoxysilyls-N- (1,3- dimethyl-butane) propyl amine, N- benzene
The silicon containing amino such as base -3- TSL 8330s, N- (vinyl benzyl) -2- amino-ethyl -3- aminopropyls
Alkane coupling agent；The silane coupling agents containing isocyanuric acid ester such as three-(trimethoxy-silylpropyl) isocyanuric acid esters；3- ureas
The silane coupling agent containing urea groups such as base propyl trialkoxy silane；3- mercapto propyl methyl dimethoxy silanes, 3- sulfydryls third
The silane coupling agent containing sulfydryl such as base trimethoxy silane；Bis- (triethoxysilylpropyltetrasulfide) tetrasulfides etc. contain sulphur
The silane coupling agent of ether；The silane coupling agent etc. containing isocyanate group such as 3- isocyanate group propyl-triethoxysilicanes.
It is insufficient with the effect of the adaptation of glass when the compounding amount of silane coupling agent is very few, when in addition excessive, be not only unable to get with
The increment effect that compounding amount matches, and the physical property of the film obtained sometimes by the coating composition of the present invention reduces.Therefore, phase
For 100 mass parts of solid constituent from (A) ingredient of the coating composition of the present invention, the compounding amount of silane coupling agent is preferred
0.01~10 mass parts, more preferable 0.1~5 mass parts.
The coating composition of the present invention can additionally further use well known various additives as needed.As this
The additive of sample, such as can enumerate：Inorganic system's ultra-violet absorber, curing agent, anti-blocking agent, levelling agent, is prevented coalescents
Gelating agent, epoxide, plasticizer, lubricant, antistatic agent, catalyst, antiseptic, mould inhibitor, is prevented dispersion stabilizer
Rotten agent, antifoaming agent, viscous regulator, tackifier, organic solvent, sagging inhibitor etc..
Addition ultra-violet absorber, amine system of being obstructed light stabilizer, antioxidant, silane into the coating composition of the present invention
It is preferably pre- in the stage of manufacture ester-polyurethane resin emulsion since these compounds are difficult to be dispersed in water whens coupling agent etc.
It is first compounded into high molecular weight polyols or prepolymer.
For the film that the coating composition using the present invention obtains, since heat ray shielding is excellent, coating group
Closing object can suitably use as the heat ray shielding coating of glass pane.The method for being coated with coating composition to glass pane
It is not particularly limited, when being coated on the glass pane set, from the aspect of it can easily be coated with, preferably sponge applies
Cloth, spraying.In addition, when being coated on the production line of factory, preferably sponge is coated with, sprays, curtain coating (flow coat).Film
Thickness it is excessively thin when, the shield effectiveness of heat ray becomes inadequate, in addition, when blocked up, cost increase and visible light sometimes it is saturating
Cross rate reduction.Therefore, the thickness of film with the thickness gauge after drying be preferably 2~50 μm, more preferably 5~40 μm, further
Preferably 10~30 μm.It, can also be on two sides, in the single side of glass it should be noted that when being coated on glass
If glass pane on when being coated, from the aspect of the pollution that can reduce the film from facility exterior, preferably only inner
Face (indoor surface) is coated.The case where for 2 layers or more of glass pane, it is calm it is easy working from the aspect of, it is also preferred that only existing
The inside is coated with.
By the way that the coating composition of the present invention to be coated on glass pane, to heat ray of the shielding outside room, knot
Fruit inhibit within doors temperature steeply rise, can save the electric power needed for summer air-conditioning.If in addition, the coating composition of the present invention
It is used in front screen, side window glass, skylight of vehicle etc., then can inhibit interior temperature rise.The coating of the present invention
Composition can not only be suitable for unorganic glass, moreover it is possible to be suitable for transparent resin plate, resin sheet.
＜ heat ray shielding films ＞
Then, the heat ray shielding film of the present invention is illustrated.The film of the present invention is in resin base material film
It is upper to be formed made of the heat ray shielding layer formed by the coating composition of aforementioned present invention.
As the resin base material film that uses in the film of the present invention, preferably by polyester film, acrylic film, poly-
Carbonic ester film, fluorine film, Kapton etc. have the resin film of weatherability as base film.In these resin systems
The film of the coating composition of the present invention is formed on base film and carries out the film conduct that bonding is process is attached to window glass
Glass, vehicle front screen etc. and the heat ray shielding piece that uses is useful.Consider that resin base material is thin from the operability of piece
Preferably 50~200 μm of the thickness of film.In addition, the thickness of film with the thickness gauge after drying is preferably 2~50 μm, more preferably 5
~40 μm, further preferably 10~30 μm.
The manufacturing method ＞ of ＜ aqueous resin coating compositions
Then, the manufacturing method of the aqueous resin coating composition of the present invention is illustrated.The manufacturing method of the present invention
With following process：By ester-polyurethane resin emulsion (A) and selected from by antimony-doped tin oxide, stibium-doped zinc oxide, gallium doping oxidation
It is 70nm that at least one kind of metal oxide particle (B) in the group of zinc and tin-doped indium oxide composition, which crushes, is dispersed to average grain diameter,
Below.Herein, case of wet attrition is used as the means for crushing, disperseing for the manufacturing method of the present invention.Its reason is as follows.
As described above, in general, the grain size of the particle of metal oxide it is smaller it is easier formed particle assemble each other it is secondary
Particle, the dispersion stabilization in water, solvent reduce.Therefore, in the manufacturing method of the present invention, carry out powder by using case of wet attrition
The second particle of broken (B) ingredient controls the average grain diameter of coating composition in 70nm hereinafter, to improve stably dispersing
Property.However, the preferably small person of average grain diameter of the coating composition of the present invention, if but keep grain size too small, it is difficult to obtain industrial
Raw material, when manufacture needs costly labour.Therefore, the average grain diameter of the particle of coating composition of the invention is preferably
30~65nm, more preferably 45~60nm.It should be noted that the average grain diameter of the manufacturing method of the present invention not for (B) at
The average grain diameter of the second particle divided, but the average grain diameter of (A) ingredient and (B) ingredient.
As the method for case of wet attrition, have using the cylinders such as stick, roller or cylinder；The method of ball, pearl isosphere, from can be into
, it is preferable to use the method for sphere from the aspect of the fine crushing of row.As preferred wet crushing mill, can enumerate：Sledge mill
Machine, rotation grinding machine, vibrating mill, planet mill, grater (attritor), ball mill etc., from dispersion stabilization can be obtained
Well, from the aspect of the small dispersion of grain size, preferred ball mill.As the material of workable pearl, can enumerate：Metal,
Glass, ceramics etc., from the aspect of excellent wear resistance, preferably ceramic.The small person of grain size of pearl can obtain small point of grain size
Dissipate object, but due to when the grain size of pearl is too small operability it is poor, it is preferably 30~300 μm of the grain size of pearl, 50~100 μm more preferable.
As described above, the manufacturing method of (A) ingredient is not particularly limited, well known method can be used, but from manufacture
From the perspective of the dispersion stabilization of easiness and resin, preferably：The prepolymer is added after reacting synthetic prepolymer in a solvent
It adds in water and makes the prepolymer method that feed disperses, the prepolymer method for making prepolymer be dispersed in water, more preferably make prepolymer point
Dissipate prepolymer method in water.Polyester polyol compound, polyisocyanates and chain extender when for manufacture prepolymer are matched
Mixed ratio, relative to isocyanate group, the molar ratio of isocyanate-reactive group and isocyanate group, preferably 30~99 rub
You are %, more preferable 50~99 moles of %.Preferably it is non-live to urethane reaction as the solvent for prepolymer method
Property and the solvent big with the compatibility of water, from be easy by depressurize removal from the aspect of, preferably：Acetone, methyl ethyl ketone, two dislike
Alkane, tetrahydrofuran, n-methyl-2-pyrrolidone.For the ratio of prepolymer and water, relative to the total amount of prepolymer and water, pre-polymerization
Object is preferably 15~40 mass %.
When using alkamine compound as chain extender, there is carboxyl or sulfonic low molecular weight polyols compound,
From the viewpoint of the water dispersible of (A) ingredient, preferably after the manufacture of prepolymer and into water add prepolymer before or to
After being added in water, neutralized by neutralizer.For using neutralizer of the alkamine compound as chain extender when, can enumerate
Go out：The inorganic acids such as the organic sulfonic acids such as the carboxylic acids such as formic acid, acetic acid, succinic acid, p-methyl benzenesulfonic acid, hydrochloric acid, phosphoric acid, dialkyl group sulfuric acid,
The quaternizing agents such as alkyl halide.In addition, for using with carboxyl or sulfonic low molecular weight polyols compound as chain extension
Neutralizer when agent can enumerate：Trimethylamine, triethylamine, tripropyl amine (TPA), tri-n-butylamine, N methyldiethanol amine, triethanolamine etc. have
The inorganic bases such as machine amine, sodium hydroxide, potassium hydroxide, ammonia.The amount of neutralizer can be used the amino for being enough to neutralize prepolymer, carboxyl or
Sulfonic amount.
For the manufacturing method of the present invention, in addition ultra-violet absorber, amine system of being obstructed light stabilizer, antioxidant, silicon
Whens alkane coupling agent etc., since these compounds are difficult to be dispersed in water, not preferably in case of wet attrition or after case of wet attrition
Addition, and it is preferred that in the stage of manufacture ester-polyurethane resin emulsion is compounded to high molecular weight polyols or prepolymer in advance.
It should be noted that the solid constituent of the coating composition in order to adjust the present invention, can add water, water is added
When, it can also be after distribution before case of wet attrition.
The manufacturing method ＞ of ＜ heat ray shielding films
There is the manufacturing method of the heat ray shielding film of the present invention coating composition by the present invention to be coated on resin system
Process on base film.That is, having following process：Using case of wet attrition by ester-polyurethane resin emulsion (A) and selected from being mixed by antimony
At least one kind of metal oxide in the group that miscellaneous tin oxide, stibium-doped zinc oxide, Ga-doped zinc oxide and tin-doped indium oxide form
Particle (B) crushes, is dispersed to the process that aqueous resin coating composition is made for 70nm or less in average grain diameter；And by the water system
Resin coating compositions are coated on the process on resin base material film.
As described above, as resin base material film, preferably by polyester film, acrylic film, polycarbonate film,
Fluorine film, Kapton etc. have the resin film of weatherability as base film.In addition, as coating method, preferably
Sponge coating, spraying, curtain coating (flow coat).When the thickness of film is excessively thin, the shield effectiveness of heat ray becomes inadequate, separately
Outside, when blocked up, cost increases and the transmitance of visible light reduces sometimes.Therefore, the thickness of film is excellent with the thickness gauge after drying
It is selected as 2~50 μm, more preferably 5~40 μm, further preferably 10~30 μm.
Embodiment
The present invention will be described in more detail by the following examples.If without special declaration, " part " and " % " point
It Biao Shi " mass parts " and " quality % ".
＜ high molecular weight polyols compounds ＞
A1：The reaction product number-average molecular weight of neopentyl glycol/12- hydroxy stearic acids/adipic acid=10/9/6 (molar ratio)
1030
A2：The reaction product number-average molecular weight of neopentyl glycol/12- hydroxystearyl alcohols/adipic acid=3/7/7 (molar ratio)
1020
A3：1,6-HD system polycarbonate glycol (Asahi Kasei Chemical systems, product name T6002) number is divided equally
Son amount 2000
A4：Polytetramethylene glycol (Mitsubishi Chemical's system, product name PTMG2000) number-average molecular weight 2000
＜ Production Examples 1：Lotion B1 ＞
By 222 mass parts of high molecular weight polyols compound A1,78 mass parts of hexamethylene diisocyanate (HDI), two
22 mass parts of hydroxymethyl propionic acid, 83 mass parts of n-methyl-2-pyrrolidone are taken into reaction vessel, while being maintained at 80~100 DEG C
While making its reaction, prepolymer has been manufactured.17.8 mass parts of triethylamine are added into the prepolymer to be neutralized, it is sub- to be then added six
8.3 mass parts of methanediamine, side addition waterside carry out cross-linking reaction at 35 DEG C or less, and addition water is 30% up to solid constituent,
To manufacture lotion B1.
＜ Production Examples 2：Lotion B2 ＞
By 166 mass parts of high molecular weight polyols compound A2,108 mass parts of isophorone diisocyanate (IPDI),
5 mass parts of 1,4- butanediols, 25 mass parts of N methyldiethanol amine, 75 mass parts of n-methyl-2-pyrrolidone are taken into reaction
Container makes its reaction when being maintained at 80~100 DEG C, has manufactured prepolymer.Into the prepolymer be added 15 mass parts of acetic acid into
Row neutralizes, and water then is added until solid constituent is 30%, to manufacture lotion B2.
＜ Production Examples 3：Lotion B3 ＞
By 490 mass parts of high molecular weight polyols compound A-13,120 mass parts of 1,12- dodecanediols, isophorone
519 mass parts of diisocyanate, 71.7 mass parts of dihydromethyl propionic acid and 246 mass parts of n-methyl-2-pyrrolidone be taken into
Reaction vessel makes its reaction when being maintained at 100~110 DEG C, has manufactured prepolymer.60 matter of triethylamine is added into the prepolymer
Amount part is neutralized, and water then is added until solid constituent is 30%, to manufacture lotion B3.
＜ Production Examples 4：Lotion B4 ＞
By 818 mass parts of high molecular weight polyols compound A-13,24 mass parts of 12- hydroxystearyl alcohols, 4,4 '-diphenyl
Methane diisocyanate (hydrogenation MDI) 26 matter of 319 mass parts, 43 mass parts of dihydromethyl propionic acid and n-methyl-2-pyrrolidone
Amount part is taken into reaction vessel, its reaction is made when being maintained at 100~110 DEG C, has manufactured prepolymer.It is added into the prepolymer
39 mass parts of triethylamine are neutralized, and water then is added until solid constituent is 30%, to manufacture lotion B4.
＜ Production Examples 5：Lotion B5 ＞
By 222 mass parts of high molecular weight polyols compound A1,78 mass parts of hexamethylene diisocyanate (HDI), two
22 mass parts of hydroxymethyl propionic acid, 83 mass parts of n-methyl-2-pyrrolidone are taken into reaction vessel, while being maintained at 80~100 DEG C
While making its reaction, prepolymer has been manufactured.17.8 mass parts of triethylamine are added into the prepolymer to be neutralized, it is sub- to be then added six
Waterside is added at 35 DEG C in 20 mass parts of 8.3 mass parts of methanediamine and aminopropyltriethoxywerene werene (silane coupling agent), side
Cross-linking reaction is carried out below, and water is added until solid constituent is 30%, to manufacture lotion B5.
＜ Production Examples 6：Lotion B6 ＞
By 222 mass parts of high molecular weight polyols compound A1,78 mass parts of hexamethylene diisocyanate (HDI), two
22 mass parts of hydroxymethyl propionic acid, 83 mass parts of n-methyl-2-pyrrolidone are taken into reaction vessel, while being maintained at 80~100 DEG C
While making its reaction, prepolymer has been manufactured.17.8 mass parts of triethylamine are added into the prepolymer to be neutralized, it is sub- to be then added six
8.3 mass parts of methanediamine, side addition waterside carry out cross-linking reaction at 35 DEG C or less, and addition water is 35% up to solid constituent,
To manufacture lotion B6.
＜ Production Examples 7：Lotion B7 ＞
By 490 mass parts of high molecular weight polyols compound A4,120 mass parts of 1,12- dodecanediols, isophorone
519 mass parts of diisocyanate, 71.7 mass parts of dihydromethyl propionic acid and 246 mass parts of n-methyl-2-pyrrolidone be taken into
Reaction vessel makes its reaction when being maintained at 100~110 DEG C, has manufactured prepolymer.60 matter of triethylamine is added into the prepolymer
Amount part is neutralized, and water then is added until solid constituent is 30%, to manufacture lotion B7.
＜ metal oxide particles ＞
C1：The antimony-doped tin oxide powder of primary particle size 20nm
C2：Aqueous dispersion (the Mitsubishi Materials of the antimony-doped tin oxide powder of average 62nm
Corporation systems, trade name TDL-S, 17.5 mass % of solid constituent)
1 ＞ of ＜ embodiments
Using ball mill (longevity industry system, model UAM-015), by 90 mass parts of lotion B1 and metal oxide particle C1
The variation that 10 mass parts crushed, were dispersed to average grain diameter is constant, is prepared for the aqueous resin coating composition of embodiment 1.It needs
It is noted that pearl uses the zirconium oxide bead of grain size 0.1mm, the space filling factor of the pearl of the crushing groove of ball mill is 50%.
2 ＞ of ＜ embodiments
90 mass parts of lotion B2 are used instead of lotion B1, operation similarly to Example 1 is carried out in addition to this, is prepared for
The aqueous resin coating composition of embodiment 2.
3 ＞ of ＜ embodiments
90 mass parts of lotion B3 are used instead of lotion B1, operation similarly to Example 1 is carried out in addition to this, is prepared for
The aqueous resin coating composition of embodiment 3.
4 ＞ of ＜ embodiments
90 mass parts of lotion B4 are used instead of lotion B1, operation similarly to Example 1 is carried out in addition to this, is prepared for
The aqueous resin coating composition of embodiment 4.
5 ＞ of ＜ embodiments
Instead of 90 mass parts of lotion B1, using 30 mass parts of 60 mass parts of lotion B1 and water, carry out in addition to this and real
It applies example 1 similarly to operate, is prepared for the aqueous resin coating composition of embodiment 5.
6 ＞ of ＜ embodiments
Lotion B1 is changed to 87 mass parts from 90 mass parts, metal oxide particle C1 is changed to 13 from 10 mass parts
Mass parts, in addition to this operation similarly to Example 1 are prepared for the aqueous resin coating composition of embodiment 6.
7 ＞ of ＜ embodiments
Lotion B1 is changed to 93 mass parts from 90 mass parts, metal oxide particle C1 is changed to 7 from 10 mass parts
Mass parts, in addition to this operation similarly to Example 1 are prepared for the aqueous resin coating composition of embodiment 7.
8 ＞ of ＜ embodiments
90 mass parts of lotion B5 are used instead of lotion B1, operation similarly to Example 1 is carried out in addition to this, is prepared for
The aqueous resin coating composition of embodiment 8.
9 ＞ of ＜ embodiments
90 mass parts of lotion B6 are used instead of lotion B1, operation similarly to Example 1 is carried out in addition to this, is prepared for
The aqueous resin coating composition of embodiment 9.
10 ＞ of ＜ embodiments
90 mass parts of lotion B7 are used instead of lotion B1, operation similarly to Example 1 is carried out in addition to this, is prepared for
The aqueous resin coating composition of embodiment 10.
1 ＞ of ＜ comparative examples
Use high speed dispersor (PRIMIX Corporation systems, model：2.5 types of Homo Disper), with rotating speed
3000rpm to 90 mass parts of lotion B1 and 10 mass parts of metal oxide particle C1 stir within 60 minutes, is prepared for comparing
The aqueous resin coating composition of example 1.
2 ＞ of ＜ comparative examples
43 mass parts of stirring lotion B1 and metal oxide particle C257 mass parts under the conditions of same as comparative example 1,
It is prepared for the aqueous resin coating composition of comparative example 2.
3 ＞ of ＜ comparative examples
61 mass parts of stirring lotion B1 and 39 mass of metal oxide particle C2 under the conditions of same as comparative example 1
Part, it is prepared for the aqueous resin coating composition of comparative example 3.
For the aqueous resin coating composition of Examples 1 to 10 and comparative example 1~3, is measured or counted using following methods
Calculate average grain diameter, solid constituent and (B) ingredient relative to 100 mass parts of solid constituent from (A) ingredient content (B)/
(A).Show the result in 2.
＜ average grain diameters ＞
With distilled water dilute water system resin coating compositions, using dynamic light scattering method particle size distribution meter (big mound electronics system,
Model：ELSZ-1000 grain size) is determined.
＜ solid constituents ＞
According to JIS K6828-1 (synthetic resin emulsions-the 1：Nonvolatile component seeks method) condition B (temperature：105
DEG C, heating time：1 hour) it is measured.
＜ (B)/(A) ＞
Input amount based on (A) ingredient He (B) ingredient calculates (B) ingredient relative to the solid constituent from (A) ingredient
The content of 100 mass parts.
＜ storage stabilities ＞
The glass system that aqueous resin coating composition is put into 100mL preserves in container, is stood in 50 DEG C of thermostat
It preserves 1 week, according to the presence or absence of precipitation, judges storage stability using following benchmark.
○：Do not observe that precipitation, storage stability are good.
×：Observe that precipitation, storage stability are bad.
The preparation ＞ of ＜ test films
Using the aqueous resin coating composition of the good Examples 1 to 10 of storage stability and comparative example 2~3, in length
It is coated in such a way that dry film thickness becomes 20 μm on the glass-board surface of 100mm × wide 70mm × thickness 2mm, 3 is air-dried at 25 DEG C
It, has made test film.Using the test film transmitance of mist degree and visible light and infrared ray is determined using following methods.
Show the result in 2.
The measurement ＞ of ＜ mist degrees
According to JIS K7136 (the seeking method of the mist degree of plastics-transparent material), mist degree instrument (Japan's electricity color industry system, type are used
Number NHD2000) determine mist degree.
The measurement ＞ of ＜ transmitances
It is determined in wavelength 550nm (visible light) and 950nm using spectrophotometer (Japan's light splitting system, model V-670)
Transmitance under (infrared ray).
[table 1]
※：B1 is 60 mass parts and water is 30 mass parts
[table 2]
※2：(B) content of the ingredient relative to 100 mass parts of solid constituent from (A) ingredient
According to result above it is found that even if the coating composition solid content of the present invention increases, metal oxide particle
Dispersion stabilization in the coating composition is also excellent.
Claims (8)
1. a kind of aqueous resin coating composition, which is characterized in that it contains ester-polyurethane resin emulsion (A) and metal oxide
The case of wet attrition object of grain (B), the metal oxide particle (B) is selected to be adulterated by antimony-doped tin oxide, stibium-doped zinc oxide, gallium
At least one kind of in the group of zinc oxide and tin-doped indium oxide composition, the average grain diameter of the case of wet attrition object is 70nm or less.
2. aqueous resin coating composition according to claim 1, wherein solid constituent is 15~45 mass %, relatively
It is in the content of 100 mass parts of solid constituent from the ester-polyurethane resin emulsion (A), the metal oxide particle (B)
18~80 mass parts.
3. aqueous resin coating composition according to claim 1, wherein the ester-polyurethane resin emulsion (A) is conduct
The reaction production of high molecular weight polyols compound, polyisocyanates, hydrophilic group imported agent and chain extender that molecular weight is 500 or more
The polyurethane resin of object, the high molecular weight polyols compound are polyester polyol.
4. a kind of heat ray shielding film, which is characterized in that it is formed described in claim 1 on resin base material film
Aqueous resin coating composition formed heat ray shielding layer made of.
5. a kind of manufacturing method of aqueous resin coating composition, which is characterized in that the manufacturing method has following process：Profit
With case of wet attrition by ester-polyurethane resin emulsion (A) and selected from by antimony-doped tin oxide, stibium-doped zinc oxide, Ga-doped zinc oxide and
Tin-doped indium oxide composition group at least one kind of metal oxide particle (B) crush, be dispersed to average grain diameter be 70nm with
Under.
6. the manufacturing method of aqueous resin coating composition according to claim 5, wherein solid constituent is 15~45 matter
Measure %, relative to 100 mass parts of solid constituent from the ester-polyurethane resin emulsion (A), the metal oxide particle (B)
Content be 18~80 mass parts.
7. the manufacturing method of aqueous resin coating composition according to claim 5, wherein the ester-polyurethane resin emulsion
(A) be as molecular weight be 500 or more high molecular weight polyols compound, polyisocyanates, hydrophilic group imported agent and chain extension
The polyurethane resin of the reaction product of agent, the high molecular weight polyols compound are polyester polyol.
8. a kind of manufacturing method of heat ray shielding film, which is characterized in that the manufacturing method has following process：
Using case of wet attrition by ester-polyurethane resin emulsion (A) and selected from by antimony-doped tin oxide, stibium-doped zinc oxide, gallium doping oxygen
Change at least one kind of metal oxide particle (B) crushing in the group of zinc and tin-doped indium oxide composition, be dispersed to average grain diameter and is
70nm or less and the process that aqueous resin coating composition is made；And
The process aqueous resin coating composition being coated on resin base material film.
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| CN202311664614.5A CN117801648A (en) | 2015-11-26 | 2016-11-15 | Aqueous resin coating composition, heat ray shielding film using same, and method for producing same |
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| JP2015-231083 | 2015-11-26 | ||
| JP2015231083 | 2015-11-26 | ||
| PCT/JP2016/083850 WO2017090489A1 (en) | 2015-11-26 | 2016-11-15 | Aqueous resin coating composition, heat-ray-shielding film in which same is used, and methods for producing these |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111087654A (en) * | 2019-12-31 | 2020-05-01 | 宁波柔创纳米科技有限公司 | Transparent heat-insulation anti-static film and preparation method thereof, and composite film and preparation method thereof |
| CN113861741A (en) * | 2021-10-29 | 2021-12-31 | 深圳市晓帆宇科技有限公司 | Preparation method of acrylate composite conductive material |
| CN114786948A (en) * | 2019-12-23 | 2022-07-22 | Dic株式会社 | Surface treatment layer and article |
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| JP7355968B1 (en) * | 2022-07-22 | 2023-10-03 | 関西ペイント株式会社 | Water-based coating composition, coating film forming method, and multilayer coating film forming method |
| WO2024018708A1 (en) * | 2022-07-22 | 2024-01-25 | 関西ペイント株式会社 | Aqueous coating material composition, method for forming coating film, and method for forming multilayer coating film |
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Also Published As
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| JP6853183B2 (en) | 2021-03-31 |
| WO2017090489A1 (en) | 2017-06-01 |
| CN117801648A (en) | 2024-04-02 |
| MY186925A (en) | 2021-08-26 |
| JPWO2017090489A1 (en) | 2018-09-13 |
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