JP2020094086A - Coating, turbine blade and aircraft wing - Google Patents
Coating, turbine blade and aircraft wing Download PDFInfo
- Publication number
- JP2020094086A JP2020094086A JP2018230807A JP2018230807A JP2020094086A JP 2020094086 A JP2020094086 A JP 2020094086A JP 2018230807 A JP2018230807 A JP 2018230807A JP 2018230807 A JP2018230807 A JP 2018230807A JP 2020094086 A JP2020094086 A JP 2020094086A
- Authority
- JP
- Japan
- Prior art keywords
- coating
- coating film
- polyester
- fluoropolymer
- coating material
- 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.)
- Granted
Links
- 239000011248 coating agent Substances 0.000 title claims abstract description 189
- 238000000576 coating method Methods 0.000 title claims abstract description 189
- 229920000728 polyester Polymers 0.000 claims abstract description 59
- 239000010954 inorganic particle Substances 0.000 claims abstract description 39
- 229920002313 fluoropolymer Polymers 0.000 claims description 82
- 239000004811 fluoropolymer Substances 0.000 claims description 80
- 239000000463 material Substances 0.000 claims description 66
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 51
- 238000000034 method Methods 0.000 claims description 36
- 239000008199 coating composition Substances 0.000 claims description 33
- 239000003973 paint Substances 0.000 claims description 26
- 239000002253 acid Substances 0.000 claims description 19
- 239000010456 wollastonite Substances 0.000 claims description 10
- 229910052882 wollastonite Inorganic materials 0.000 claims description 10
- 238000010248 power generation Methods 0.000 claims description 6
- 230000009477 glass transition Effects 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 abstract description 14
- 230000003628 erosive effect Effects 0.000 abstract description 13
- 229910052731 fluorine Inorganic materials 0.000 abstract description 13
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 10
- 239000011737 fluorine Substances 0.000 abstract description 10
- 239000000178 monomer Substances 0.000 description 31
- 238000001723 curing Methods 0.000 description 30
- 239000003795 chemical substances by application Substances 0.000 description 27
- 239000005056 polyisocyanate Substances 0.000 description 22
- 229920001228 polyisocyanate Polymers 0.000 description 22
- 238000012360 testing method Methods 0.000 description 21
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 19
- 239000002904 solvent Substances 0.000 description 19
- 239000000758 substrate Substances 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 13
- 239000007787 solid Substances 0.000 description 13
- 239000011247 coating layer Substances 0.000 description 10
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 5
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 125000003700 epoxy group Chemical group 0.000 description 5
- 239000011151 fibre-reinforced plastic Substances 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- 125000001153 fluoro group Chemical group F* 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- 101150065749 Churc1 gene Proteins 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- 102100038239 Protein Churchill Human genes 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 150000005846 sugar alcohols Polymers 0.000 description 4
- 229920001567 vinyl ester resin Polymers 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 230000005856 abnormality Effects 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- -1 allyl ester Chemical class 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 3
- 229920001225 polyester resin Polymers 0.000 description 3
- 239000004645 polyester resin Substances 0.000 description 3
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical class O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 125000002339 acetoacetyl group Chemical group O=C([*])C([H])([H])C(=O)C([H])([H])[H] 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000002981 blocking agent Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 238000013007 heat curing Methods 0.000 description 2
- 239000001023 inorganic pigment Substances 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
- 239000004611 light stabiliser Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical class FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
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- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 description 1
- XSCLFFBWRKTMTE-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)cyclohexane Chemical compound O=C=NCC1CCCC(CN=C=O)C1 XSCLFFBWRKTMTE-UHFFFAOYSA-N 0.000 description 1
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 1
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- ATOUXIOKEJWULN-UHFFFAOYSA-N 1,6-diisocyanato-2,2,4-trimethylhexane Chemical compound O=C=NCCC(C)CC(C)(C)CN=C=O ATOUXIOKEJWULN-UHFFFAOYSA-N 0.000 description 1
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- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical compound CCCCC(CC)(CO)CO DSKYSDCYIODJPC-UHFFFAOYSA-N 0.000 description 1
- PGYJSURPYAAOMM-UHFFFAOYSA-N 2-ethenoxy-2-methylpropane Chemical compound CC(C)(C)OC=C PGYJSURPYAAOMM-UHFFFAOYSA-N 0.000 description 1
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- AIDLAEPHWROGFI-UHFFFAOYSA-N 2-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=C(C(O)=O)C=CC=C1C(O)=O AIDLAEPHWROGFI-UHFFFAOYSA-N 0.000 description 1
- SDQROPCSKIYYAV-UHFFFAOYSA-N 2-methyloctane-1,8-diol Chemical compound OCC(C)CCCCCCO SDQROPCSKIYYAV-UHFFFAOYSA-N 0.000 description 1
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- 239000012760 heat stabilizer Substances 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 1
- 150000002466 imines Chemical class 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
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- WDWDWGRYHDPSDS-UHFFFAOYSA-N methanimine Chemical compound N=C WDWDWGRYHDPSDS-UHFFFAOYSA-N 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
- 239000011259 mixed solution Substances 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 125000003566 oxetanyl group Chemical group 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000012508 resin bead Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- BPILDHPJSYVNAF-UHFFFAOYSA-M sodium;diiodomethanesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C(I)I BPILDHPJSYVNAF-UHFFFAOYSA-M 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 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
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical compound NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/70—Wind energy
- Y02E10/72—Wind turbines with rotation axis in wind direction
Landscapes
- Wind Motors (AREA)
- Paints Or Removers (AREA)
Abstract
Description
本発明は、塗料、タービンが有するブレード、及び、航空機の翼に関する。 The present invention relates to a paint, a blade of a turbine, and an aircraft wing.
タービンのブレードや航空機の翼は、耐候性付与のために塗膜によって被覆される。一方で、これらの塗膜は基材とともに高速で運動するため、雨滴、氷雪または空気中に存在する塵等により浸食されやすい。
特許文献１には、水酸基価が１１０〜２５０ｍｇＫＯＨ／ｇの樹脂である含フッ素重合体（Ａ）、水酸基価が１００〜３００ｍｇＫＯＨ／ｇの樹脂であるポリエステル重合体（Ｂ）、非ブロック化ポリイソシアネート系硬化剤（Ｃ）、及び溶剤（Ｄ）を含有する、風力発電機のブレードの表面塗布用塗料組成物が開示されている。
Turbine blades and aircraft wings are coated with a coating for weather resistance. On the other hand, since these coating films move at high speed together with the substrate, they are easily eroded by raindrops, ice and snow, dust existing in the air, or the like.
In Patent Document 1, a fluorine-containing polymer (A) which is a resin having a hydroxyl value of 110 to 250 mgKOH/g, a polyester polymer (B) which is a resin having a hydroxyl value of 100 to 300 mgKOH/g, and an unblocked polyisocyanate. A coating composition for surface coating of a blade of a wind power generator, which contains a system hardening agent (C) and a solvent (D), is disclosed.
本発明者らが特許文献１に記載の表面塗布用塗料組成物を用いて形成した塗膜について検討したところ、上記塗膜は現在の基準に照らして耐浸食性が不十分となる場合があった。
そこで、本発明は、耐浸食性に優れる塗膜を形成できる塗料、タービンが有するブレード、及び、航空機の翼の提供を課題とする。
When the present inventors examined a coating film formed by using the coating composition for surface coating described in Patent Document 1, the above coating film may have insufficient erosion resistance in view of current standards. It was
Then, this invention makes it a subject to provide the coating material which can form the coating film excellent in erosion resistance, the blade which a turbine has, and the blade|wing of an aircraft.
本発明者らは、鋭意検討した結果、以下の構成により課題を解決できるのを見出した。 As a result of intensive studies, the present inventors have found that the problems can be solved by the following configurations.
〔１〕 含フッ素重合体と、ポリエステルと、モース硬度が３．０〜５．０の無機粒子とを含む塗料であって、上記無機粒子の含有量が、上記含フッ素重合体と上記ポリエステルとの合計１００質量部に対して、２０〜６０質量部であり、タービンが有するブレード又は航空機の翼に塗布して用いられることを特徴とする、塗料。
〔２〕 上記含フッ素重合体及び上記ポリエステルが、いずれも１〜２５０ｍｇＫＯＨ／ｇの水酸基価を有する、〔１〕に記載の塗料。
〔３〕 上記ポリエステルが、１〜１０ｍｇＫＯＨ／ｇの酸価を有する、〔１〕又は〔２〕に記載の塗料。
〔４〕 上記ポリエステルの含有量に対する、上記含フッ素重合体の含有量の質量比が、０．１〜９である、〔１〕〜〔３〕のいずれかに記載の塗料。
〔５〕 ガラス転移温度の差の絶対値が５℃以上２０℃未満である、２種以上の上記含フッ素重合体を含む、〔１〕〜〔４〕のいずれかに記載の塗料。
〔６〕 上記無機粒子が、珪灰石である、〔１〕〜〔５〕のいずれかに記載の塗料。
〔７〕 上記無機粒子のアスペクト比が１．５〜４．５である、〔１〕〜〔６〕のいずれかに記載の塗料。
〔８〕 上記無機粒子の平均長径が１〜５０μｍである、〔１〕〜〔７〕のいずれかに記載の塗料。
〔９〕 グラインドゲージによる粒状法で測定される分散度が４０μｍ以下である、〔１〕〜〔８〕のいずれかに記載の塗料。
〔１０〕 風力発電用タービンが有するブレードに塗布して用いられる、〔１〕〜〔９〕のいずれかに記載の塗料。
〔１１〕 〔１〕〜〔９〕のいずれかの塗料から形成された、膜厚が２０〜１００μｍである塗膜を有する、タービンが有するブレード。
〔１２〕 〔１〕〜〔９〕のいずれかの塗料から形成された、膜厚が２０〜１００μｍである塗膜を有する、航空機の翼。
[1] A coating material containing a fluoropolymer, polyester, and inorganic particles having a Mohs hardness of 3.0 to 5.0, wherein the content of the inorganic particles is the fluoropolymer and the polyester. 20 to 60 parts by mass with respect to 100 parts by mass in total, and is used by being applied to a blade of a turbine or a wing of an aircraft.
[2] The coating material according to [1], wherein the fluoropolymer and the polyester each have a hydroxyl value of 1 to 250 mgKOH/g.
[3] The coating material according to [1] or [2], wherein the polyester has an acid value of 1 to 10 mgKOH/g.
[4] The coating material according to any one of [1] to [3], wherein the mass ratio of the content of the fluoropolymer to the content of the polyester is 0.1 to 9.
[5] The coating material according to any one of [1] to [4], which contains two or more kinds of the above-mentioned fluoropolymers having an absolute value of difference in glass transition temperature of 5°C or higher and lower than 20°C.
[6] The coating material according to any one of [1] to [5], wherein the inorganic particles are wollastonite.
[7] The coating material according to any one of [1] to [6], wherein the inorganic particles have an aspect ratio of 1.5 to 4.5.
[8] The coating material according to any one of [1] to [7], wherein the inorganic particles have an average major axis of 1 to 50 µm.
[9] The coating material according to any one of [1] to [8], which has a dispersity of 40 μm or less measured by a grain method using a grind gauge.
[10] The coating material according to any one of [1] to [9], which is used by being applied to a blade of a turbine for wind power generation.
[11] A blade included in a turbine having a coating film having a film thickness of 20 to 100 μm formed from the coating material according to any one of [1] to [9].
[12] An aircraft wing having a coating film having a film thickness of 20 to 100 μm, which is formed from the coating material according to any one of [1] to [9].
本発明によれば、耐浸食性に優れる塗膜を形成できる塗料、タービンが有するブレード、及び、航空機の翼を提供できる。 ADVANTAGE OF THE INVENTION According to this invention, the coating material which can form the coating film excellent in erosion resistance, the blade which a turbine has, and the wing of an aircraft can be provided.
本発明における用語の意味は以下の通りである。
「〜」を用いて表される数値範囲は、「〜」の前後に記載される数値を下限値及び上限値として含む範囲を意味する。
（メタ）アクリレートとは、アクリレート及びメタクリレートの総称であり、（メタ）アクリルとは、アクリル及びメタクリルの総称である。
単位とは、単量体が重合して直接形成された、上記単量体１分子に基づく原子団と、上記原子団の一部を化学変換して得られる原子団との総称である。なお、重合体が含む全単位に対する、それぞれの単位の含有量（モル％）は、重合体を核磁気共鳴スペクトル（ＮＭＲ）法により分析して求められる。
酸価及び水酸基価は、それぞれ、ＪＩＳ Ｋ ００７０−３（１９９２）の方法に準じて測定される値である。
ガラス転移温度は、示差走査熱量測定（ＤＳＣ）法で測定される、重合体の中間点ガラス転移温度である。ガラス転移温度はＴｇともいう。
数平均分子量は、ポリスチレンを標準物質としてゲルパーミエーションクロマトグラフィーで測定される値である。数平均分子量はＭｎともいう。
塗膜の膜厚は、渦電流式膜厚計（商品名「ＥＤＹ−５０００」、サンコウ電子社製）を用いて測定される値である。
塗料の固形分質量とは、塗料が溶媒を含む場合に、塗料から溶媒を除去した質量である。なお、溶媒以外の組成物の固形分を構成する成分に関して、その性状が液体状であっても、固形分とみなす。塗料の固形分質量は、塗料１ｇを１３０℃で２０分加熱した後に残存する質量として求められる。
分散度は、グラインドゲージによる粒状法で測定した、塗料等に含まれる粒子の分散性を評価した値であり、具体的には、ＪＩＳ Ｋ ５６００−２−５に記載の方法に従って測定できる。
The meanings of the terms in the present invention are as follows.
The numerical range represented by using "to" means a range including the numerical values described before and after "to" as the lower limit value and the upper limit value.
(Meth)acrylate is a general term for acrylate and methacrylate, and (meth)acrylic is a general term for acrylic and methacrylic.
The unit is a generic term for an atomic group based on one molecule of the monomer, which is directly formed by polymerizing a monomer, and an atomic group obtained by chemically converting a part of the atomic group. The content (mol %) of each unit with respect to all units contained in the polymer is determined by analyzing the polymer by a nuclear magnetic resonance spectrum (NMR) method.
The acid value and the hydroxyl value are values measured according to the method of JIS K 0070-3 (1992), respectively.
The glass transition temperature is the midpoint glass transition temperature of a polymer measured by a differential scanning calorimetry (DSC) method. The glass transition temperature is also called Tg.
The number average molecular weight is a value measured by gel permeation chromatography using polystyrene as a standard substance. The number average molecular weight is also called Mn.
The film thickness of the coating film is a value measured with an eddy current film thickness meter (trade name "EDY-5000", manufactured by Sanko Denshi Co., Ltd.).
The solid content mass of the paint is the mass obtained by removing the solvent from the paint when the paint contains the solvent. It should be noted that the components constituting the solid content of the composition other than the solvent are regarded as the solid content even if their properties are liquid. The solid content mass of the coating material is obtained as the mass remaining after heating 1 g of the coating material at 130° C. for 20 minutes.
The dispersity is a value obtained by evaluating the dispersibility of particles contained in a paint or the like, which is measured by a granular method using a grind gauge, and specifically, can be measured according to the method described in JIS K 5600-2-5.
本発明の塗料（以下、本塗料ともいう。）は、タービンが有するブレード又は航空機の翼に塗布して用いられる塗料であり、含フッ素重合体と、ポリエステルと、モース硬度が３．０〜５．０の無機粒子とを含む。
上記無機粒子の含有量は、含フッ素重合体とポリエステルとの合計１００質量部に対して、２０〜６０質量部である。
このような構成によって本発明の課題が解決されるメカニズムは必ずしも明らかではないが、以下のように考えられる。
すなわち、本塗料にモース硬度が３．０〜５．０の無機粒子が含まれることによる、本塗料を用いて形成される塗膜（以下、本塗膜ともいう。）の強固さと、本塗料にポリエステルが含まれていることによる、本塗膜の適度な柔軟さとがバランスし、本塗膜の良好な耐浸食性を実現している、と考えられる。
The paint of the present invention (hereinafter, also referred to as the present paint) is a paint used by being applied to a blade of a turbine or a wing of an aircraft, and has a fluoropolymer, a polyester, and a Mohs hardness of 3.0 to 5. .0 inorganic particles.
The content of the inorganic particles is 20 to 60 parts by mass with respect to 100 parts by mass as the total of the fluoropolymer and the polyester.
The mechanism by which the problem of the present invention is solved by such a configuration is not necessarily clear, but is considered as follows.
That is, the strength of a coating film (hereinafter, also referred to as the present coating film) formed by using the present coating material by including inorganic particles having a Mohs hardness of 3.0 to 5.0, and the present coating material. It is considered that the presence of polyester in the resin balances with the appropriate flexibility of the coating film, thereby achieving good erosion resistance of the coating film.
本発明における含フッ素重合体は、フルオロオレフィンに基づく単位（以下、単位Ｆともいう。）を有する含フッ素重合体であるのが好ましい。
フルオロオレフィンは、水素原子の１個以上がフッ素原子で置換されたオレフィンである。フルオロオレフィンは、フッ素原子で置換されていない水素原子の１個以上が塩素原子で置換されていてもよい。
The fluoropolymer in the present invention is preferably a fluoropolymer having a unit based on a fluoroolefin (hereinafter, also referred to as a unit F).
Fluoroolefins are olefins in which one or more hydrogen atoms have been replaced by fluorine atoms. In the fluoroolefin, one or more hydrogen atoms which are not substituted with fluorine atoms may be substituted with chlorine atoms.
フルオロオレフィンの具体例としては、ＣＦ２＝ＣＦ２、ＣＦ２＝ＣＦＣｌ、ＣＦ２＝ＣＨＦ、ＣＨ２＝ＣＦ２、ＣＦ２＝ＣＦＣＦ３、ＣＦ２＝ＣＨＣＦ３、ＣＦ３ＣＨ＝ＣＨＦ、ＣＦ３ＣＦ＝ＣＨ２、式ＣＨ２＝ＣＸｆ１（ＣＦ２）ｎ１Ｙｆ１（式中、Ｘｆ１及びＹｆ１は、独立に水素原子又はフッ素原子であり、ｎ１は２〜１０の整数である。）で表される単量体が挙げられ、本塗膜の耐浸食性に優れる点から、ＣＦ２＝ＣＦ２、ＣＨ２＝ＣＦ２、ＣＦ２＝ＣＦＣｌ、ＣＦ３ＣＨ＝ＣＨＦ、又は、ＣＦ３ＣＦ＝ＣＨ２が好ましく、ＣＦ２＝ＣＦＣｌが特に好ましい。
フルオロオレフィンは、２種以上を併用してもよい。
Specific examples of the fluoroolefin include CF 2 =CF 2 , CF 2 =CFCl, CF 2 =CHF, CH 2 =CF 2 , CF 2 =CFCF 3 , CF 2 =CHCF 3 , CF 3 CH=CHF, CF 3. CF = CH 2, wherein CH 2 = CX f1 (CF 2 ) n1 Y f1 ( wherein, X f1 and Y f1 are independently a hydrogen atom or a fluorine atom, n1 is an integer from 2 to 10.) Examples of the monomer represented by the formula: CF 2 =CF 2 , CH 2 =CF 2 , CF 2 =CFCl, CF 3 CH=CHF, or CF 3 from the viewpoint of excellent corrosion resistance of the present coating film. preferably CF = CH 2, CF 2 = CFCl is particularly preferred.
Two or more fluoroolefins may be used in combination.
単位Ｆの含有量は、本塗膜の耐候性の点から、含フッ素重合体が有する全単位に対して、２０〜１００モル％が好ましく、３０〜７０モル％がより好ましく、４０〜６０モル％が特に好ましい。 From the viewpoint of the weather resistance of the present coating film, the content of the unit F is preferably 20 to 100 mol%, more preferably 30 to 70 mol%, and further preferably 40 to 60 mol, based on all the units of the fluoropolymer. % Is particularly preferred.
含フッ素重合体は、水酸基及びカルボキシ基からなる群から選択される架橋性基の一方又は両方を有する単位（以下、単位１ともいう。）を有するのが好ましい。
単位１は、フッ素原子を有さない単位が好ましい。
単位１は、水酸基及びカルボキシ基の一方又は両方を有する単量体（以下、単量体１ともいう。）に基づく単位であってもよい。
また、単位１は、水酸基又はカルボキシ基に変換可能な基を有する単位を含む含フッ素重合体において、該基を水酸基及びカルボキシ基の一方又は両方に変換させて得られる単位であってもよい。このような単位の具体例としては、含フッ素重合体中の水酸基を有する単位に、ポリカルボン酸やその酸無水物等を反応させて、水酸基の一部又は全部をカルボキシ基に変換させて得られる単位が挙げられる。
単位１は、本塗料の貯蔵安定性の点からは、水酸基を有する単位が好ましい。
つまり、含フッ素重合体は、フルオロオレフィンに基づく単位及び水酸基を有するのが好ましい。
The fluoropolymer preferably has a unit having one or both crosslinkable groups selected from the group consisting of a hydroxyl group and a carboxy group (hereinafter, also referred to as unit 1).
The unit 1 is preferably a unit having no fluorine atom.
The unit 1 may be a unit based on a monomer having one or both of a hydroxyl group and a carboxy group (hereinafter, also referred to as a monomer 1).
Further, the unit 1 may be a unit obtained by converting the group into one or both of a hydroxyl group and a carboxy group in a fluoropolymer containing a unit having a group capable of being converted into a hydroxyl group or a carboxy group. As a specific example of such a unit, a unit having a hydroxyl group in the fluoropolymer is obtained by reacting a polycarboxylic acid or an acid anhydride thereof with a part or all of the hydroxyl group converted to a carboxy group. The units that can be used are listed.
The unit 1 is preferably a unit having a hydroxyl group from the viewpoint of storage stability of the present coating composition.
That is, the fluoropolymer preferably has a unit based on fluoroolefin and a hydroxyl group.
水酸基を有する単量体の具体例としては、水酸基を有する、ビニルエーテル、ビニルエステル、アリルエーテル、アリルエステル、（メタ）アクリル酸エステル、アリルアルコールが挙げられる。水酸基を有する単量体は、本塗膜の耐候性の点から、ビニルエーテルが好ましい。
水酸基を有する単量体１の具体例としては、ＣＨ２＝ＣＨＯ−ＣＨ２−ｃｙｃｌｏＣ６Ｈ１０−ＣＨ２ＯＨ、ＣＨ２＝ＣＨＣＨ２Ｏ−ＣＨ２−ｃｙｃｌｏＣ６Ｈ１０−ＣＨ２ＯＨ、ＣＨ２＝ＣＨＯ−ＣＨ２−ｃｙｃｌｏＣ６Ｈ１０−ＣＨ２−（ＯＣＨ２ＣＨ２）１５ＯＨ、ＣＨ２＝ＣＨＯＣＨ２ＣＨ２ＯＨ、ＣＨ２＝ＣＨＣＨ２ＯＣＨ２ＣＨ２ＯＨ、ＣＨ２＝ＣＨＯＣＨ２ＣＨ２ＣＨ２ＣＨ２ＯＨ、ＣＨ２＝ＣＨＣＨ２ＯＣＨ２ＣＨ２ＣＨ２ＣＨ２ＯＨが挙げられ、フルオロオレフィンとの共重合性の点から、ＣＨ２＝ＣＨＣＨ２ＯＣＨ２ＣＨ２ＯＨ又はＣＨ２＝ＣＨＯＣＨ２ＣＨ２ＣＨ２ＣＨ２ＯＨが好ましい。
なお、「−ｃｙｃｌｏＣ６Ｈ１０−」はシクロへキシレン基を表し、「−ｃｙｃｌｏＣ６Ｈ１０−」の結合部位は、通常１，４−である。
Specific examples of the monomer having a hydroxyl group include vinyl ether, vinyl ester, allyl ether, allyl ester, (meth)acrylic acid ester and allyl alcohol having a hydroxyl group. The monomer having a hydroxyl group is preferably vinyl ether from the viewpoint of weather resistance of the present coating film.
Specific examples of the monomer 1 having a hydroxyl group, CH 2 = CHO-CH 2 -cycloC 6 H 10 -CH 2 OH, CH 2 = CHCH 2 O-CH 2 -cycloC 6 H 10 -CH 2 OH, CH 2 = CHOCH 2 -cycloC 6 H 10 -CH 2 - (OCH 2 CH 2) 15 OH, CH 2 = CHOCH 2 CH 2 OH, CH 2 = CHCH 2 OCH 2 CH 2 OH, CH 2 = CHOCH 2 CH 2 CH 2 CH 2 OH, CH 2 ═CHCH 2 OCH 2 CH 2 CH 2 CH 2 OH, and CH 2 ═CHCH 2 OCH 2 CH 2 OH or CH 2 ═ from the viewpoint of copolymerizability with fluoroolefins. CHOCH 2 CH 2 CH 2 CH 2 OH is preferred.
Incidentally, "- cycloC 6 H 10 -" represents cyclohexylene, "- cycloC 6 H 10 -" binding site is usually 1,4.
カルボキシ基を有する単量体としては、不飽和カルボン酸、（メタ）アクリル酸、上記水酸基を有する単量体の水酸基にカルボン酸無水物を反応させて得られる単量体等が挙げられる。
カルボキシ基を有する単量体の具体例としては、ＣＨ２＝ＣＨＣＯＯＨ、ＣＨ（ＣＨ３）＝ＣＨＣＯＯＨ、ＣＨ２＝Ｃ（ＣＨ３）ＣＯＯＨ、ＨＯＯＣＣＨ＝ＣＨＣＯＯＨ、ＣＨ２＝ＣＨ（ＣＨ２）ｎ１１ＣＯＯＨで表される単量体（ただし、ｎ１１は１〜１０の整数を示す。）、ＣＨ２＝ＣＨＯ（ＣＨ２）ｎ１２ＯＣ（Ｏ）ＣＨ２ＣＨ２ＣＯＯＨで表される単量体（ただし、ｎ１２は１〜１０の整数を示す。）が挙げられ、フルオロオレフィンとの共重合性の点から、ＣＨ２＝ＣＨ（ＣＨ２）ｎ１１ＣＯＯＨで表される単量体又はＣＨ２＝ＣＨＯ（ＣＨ２）ｎ１２ＯＣ（Ｏ）ＣＨ２ＣＨ２ＣＯＯＨで表される単量体が好ましい。
Examples of the monomer having a carboxy group include unsaturated carboxylic acid, (meth)acrylic acid, and a monomer obtained by reacting a carboxylic acid anhydride with the hydroxyl group of the above-mentioned monomer having a hydroxyl group.
Specific examples of the monomer having a carboxyl group, CH 2 = CHCOOH, CH ( CH 3) = CHCOOH, CH 2 = C (CH 3) COOH, HOOCCH = CHCOOH, CH 2 = CH (CH 2) n11 COOH in monomer represented (where n11 is an integer of 1~10.), CH 2 = CHO (CH 2) n12 OC (O) monomer represented by CH 2 CH 2 COOH (where n12 is an integer from 1 to 10.) can be mentioned from the viewpoint of copolymerizability with the fluoroolefin, CH 2 = CH (CH 2 ) n11 monomers or CH 2 = CHO represented by COOH (CH 2 ) A monomer represented by n12 OC(O)CH 2 CH 2 COOH is preferable.
単量体１は、２種以上を併用してもよい。
単位１の含有量は、本塗料が硬化剤を含む場合に、本塗膜の架橋密度が高くなり本塗膜の耐久性（耐水性、耐薬品性等）に優れる点から、含フッ素重合体の全単位に対して、０．５〜４０モル％が好ましく、１０〜３５モル％がより好ましく、１５〜３０モル％が特に好ましい。
The monomer 1 may be used in combination of two or more kinds.
The content of the unit 1 is a fluoropolymer from the viewpoint that when the coating composition contains a curing agent, the crosslinking density of the coating film becomes high and the durability (water resistance, chemical resistance, etc.) of the coating film is excellent. 0.5 to 40 mol% is preferable, 10 to 35 mol% is more preferable, and 15 to 30 mol% is particularly preferable with respect to all the units.
含フッ素重合体は、更に、水酸基及びカルボキシ基を有さない単量体（以下、単量体２ともいう。）に基づく単位（以下、単位２ともいう。）を含んでよい。単位２は、フッ素原子を有さない単位であることが好ましい。
単位２は、水酸基及びカルボキシ基以外の架橋性基等を有していてもよい。このような基としては、アミノ基、エポキシ基、オキセタニル基、加水分解性シリル基等が挙げられる。
単量体２は架橋性基を有さないのも好ましい。
The fluoropolymer may further include a unit (hereinafter, also referred to as unit 2) based on a monomer having no hydroxyl group and no carboxy group (hereinafter, also referred to as monomer 2). The unit 2 is preferably a unit having no fluorine atom.
The unit 2 may have a crosslinkable group other than a hydroxyl group and a carboxy group. Examples of such a group include an amino group, an epoxy group, an oxetanyl group, and a hydrolyzable silyl group.
It is also preferable that the monomer 2 does not have a crosslinkable group.
単量体２としては、アルケン、ビニルエーテル、ビニルエステル、アリルエーテル、アリルエステル、及び、（メタ）アクリル酸エステルからなる群から選択される１種以上が挙げられる。単量体２としては、フルオロオレフィンとの共重合性及び含フッ素重合体の耐候性の点から、ビニルエーテル及びビニルエステルの一方又は両方が好ましく、ビニルエーテルが特に好ましい。 Examples of the monomer 2 include one or more selected from the group consisting of alkenes, vinyl ethers, vinyl esters, allyl ethers, allyl esters, and (meth)acrylic acid esters. As the monomer 2, one or both of vinyl ether and vinyl ester are preferable, and vinyl ether is particularly preferable, from the viewpoint of copolymerizability with fluoroolefin and weather resistance of the fluoropolymer.
単量体２の具体例としては、エチレン、プロピレン、１−ブテン、エチルビニルエーテル、ｔｅｒｔ−ブチルビニルエーテル、２−エチルヘキシルビニルエーテル、シクロヘキシルビニルエーテル、酢酸ビニル、ピバル酸ビニルエステル、ネオノナン酸ビニルエステル（ＨＥＸＩＯＮ社製、商品名「ベオバ９」）、ネオデカン酸ビニルエステル（ＨＥＸＩＯＮ社製、商品名「ベオバ１０」）、安息香酸ビニルエステル、ｔｅｒｔ−ブチル安息香酸ビニルエステル、ｔｅｒｔ−ブチル（メタ）アクリレート、ベンジル（メタ）アクリレートが挙げられる。
単量体２は、２種以上を併用してもよい。
含フッ素重合体が単量体２を含む場合、単位２の含有量は、含フッ素重合体の全単位に対して、５〜６０モル％が好ましく、１０〜５０モル％が特に好ましい。
Specific examples of the monomer 2 include ethylene, propylene, 1-butene, ethyl vinyl ether, tert-butyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, vinyl acetate, pivalic acid vinyl ester, neononanoic acid vinyl ester (manufactured by HEXION). , Trade name "Beoba 9"), neodecanoic acid vinyl ester (manufactured by HEXION, trade name "Beoba 10"), benzoic acid vinyl ester, tert-butyl benzoic acid vinyl ester, tert-butyl (meth)acrylate, benzyl (meth) ) Acrylate is mentioned.
The monomer 2 may use 2 or more types together.
When the fluoropolymer contains the monomer 2, the content of the unit 2 is preferably 5 to 60 mol%, and particularly preferably 10 to 50 mol%, based on the total units of the fluoropolymer.
含フッ素重合体は、含フッ素重合体が有する全単位に対して、単位Ｆと単位１と単位２とを、この順に２０〜７０モル％、０．５〜４０モル％、５〜６０モル％含むのが好ましい。 The fluorinated polymer contains the unit F, the unit 1 and the unit 2 in this order with respect to all the units of the fluorinated polymer in the order of 20 to 70 mol%, 0.5 to 40 mol% and 5 to 60 mol%. It is preferable to include.
含フッ素重合体のＴｇは、０〜１２０℃が好ましく、１０〜５０℃が特に好ましい。含フッ素重合体のＴｇが上記範囲内にあると、含フッ素重合体の流動性が向上する。 The Tg of the fluoropolymer is preferably 0 to 120°C, particularly preferably 10 to 50°C. When the Tg of the fluoropolymer is within the above range, the fluidity of the fluoropolymer is improved.
含フッ素重合体のＭｎは、１，０００〜１００，０００が好ましく、２，０００〜３０，０００がより好ましく、３，０００〜８，０００が特に好ましい。
含フッ素重合体のＭｎが上記範囲内にあると、本塗膜の耐久性（耐水性、耐薬品性等）及び含フッ素重合体の流動性が向上する。
The Mn of the fluoropolymer is preferably 1,000 to 100,000, more preferably 2,000 to 30,000, and particularly preferably 3,000 to 8,000.
When the Mn of the fluoropolymer is within the above range, the durability (water resistance, chemical resistance, etc.) of the coating film and the fluidity of the fluoropolymer are improved.
含フッ素重合体は、Ｔｇが１０〜５０℃であり、かつＭｎが３，０００〜８，０００であるのが好ましい。この場合、含フッ素重合体の流動性が特に好適となり、ポリエステルおよび無機粒子と良好に混合するため、耐浸食性に特に優れる。
本塗料が含フッ素重合体を異なる２種以上を含む場合、１種以上の含フッ素重合体が上記範囲内であるのが好ましく、２種以上の含フッ素重合体が上記範囲内であるのがより好ましく、全種の含フッ素重合体が上記範囲内であるのが更に好ましい。
The fluoropolymer preferably has Tg of 10 to 50° C. and Mn of 3,000 to 8,000. In this case, the fluidity of the fluoropolymer becomes particularly suitable, and since it is well mixed with the polyester and the inorganic particles, the erosion resistance is particularly excellent.
When the coating composition contains two or more different fluoropolymers, one or more fluoropolymers are preferably in the above range, and two or more fluoropolymers are in the above range. More preferably, all types of fluoropolymers are still more preferably within the above range.
含フッ素重合体が水酸基価を有する場合、含フッ素重合体の水酸基価は、１〜２５０ｍｇＫＯＨ／ｇが好ましく、５０〜２３０ｍｇＫＯＨ／ｇがより好ましく、１００〜２００ｍｇＫＯＨ／ｇが更に好ましく、１５０〜１８０ｍｇＫＯＨ／ｇが特に好ましい。
含フッ素重合体が酸価を有する場合、含フッ素重合体の酸価は、１〜２５０ｍｇＫＯＨ／ｇが好ましい。
含フッ素重合体は、酸価及び水酸基価の一方のみを有してもよく、両方を有してもよい。
含フッ素重合体の酸価及び水酸基価の一方又は両方が上記範囲内にあると、特に本塗料が硬化剤を含む場合に本塗膜の架橋密度が好適になり、本塗膜の耐久性が優れる。
含フッ素重合体は、本塗料の安定性の点からは、水酸基価を有するのが好ましい。
When the fluoropolymer has a hydroxyl value, the hydroxyl value of the fluoropolymer is preferably 1-250 mgKOH/g, more preferably 50-230 mgKOH/g, further preferably 100-200 mgKOH/g, and 150-180 mgKOH/g. g is particularly preferred.
When the fluoropolymer has an acid value, the acid value of the fluoropolymer is preferably 1 to 250 mgKOH/g.
The fluoropolymer may have only one of the acid value and the hydroxyl value, or may have both.
When one or both of the acid value and the hydroxyl value of the fluoropolymer are within the above range, the cross-linking density of the present coating becomes suitable, particularly when the present coating contains a curing agent, and the durability of the present coating becomes Excel.
The fluorine-containing polymer preferably has a hydroxyl value from the viewpoint of stability of the coating composition.
含フッ素重合体は、公知の方法で製造できる。例えば、含フッ素重合体は、溶媒とラジカル重合開始剤の存在下、各単量体を共重合させて得られる。含フッ素重合体の製造方法としては、溶液重合、乳化重合が挙げられる。含フッ素重合体の製造時又は製造後には、必要に応じて、重合安定剤、重合禁止剤、界面活性剤等が使用されていてもよい。 The fluoropolymer can be produced by a known method. For example, the fluoropolymer is obtained by copolymerizing each monomer in the presence of a solvent and a radical polymerization initiator. Examples of the method for producing the fluoropolymer include solution polymerization and emulsion polymerization. If necessary, a polymerization stabilizer, a polymerization inhibitor, a surfactant, etc. may be used during or after the production of the fluoropolymer.
含フッ素重合体としては、市販品を用いてもよく、具体例としては、「ルミフロン」シリーズ（ＡＧＣ社製）、「Ｆｌｕｏｎ」シリーズ（ＡＧＣ社製）、「Ｋｙｎａｒ」シリーズ（アルケマ社製）、「ゼッフル」シリーズ（ダイキン工業社製）、「Ｅｔｅｒｆｌｏｎ」シリーズ（エターナル社製）、「Ｚｅｎｄｕｒａ」シリーズ（Ｈｏｎｅｙｗｅｌｌ社製）が挙げられる。 As the fluorine-containing polymer, a commercially available product may be used, and specific examples thereof include "Lumiflon" series (manufactured by AGC), "Fluon" series (manufactured by AGC), "Kynar" series (manufactured by Arkema), Examples thereof include "Zeffle" series (manufactured by Daikin Industries, Ltd.), "Eterflon" series (manufactured by Eternal Co., Ltd.), and "Zendura" series (manufactured by Honeywell Co.).
含フッ素重合体は異なる２種以上を併用するのも好ましい。
本塗料が含フッ素重合体を異なる２種以上を含む場合、上記異なる２種以上の含フッ素重合体のＴｇの差の絶対値が、０℃超５０℃以下であるのが好ましく、５℃以上２０℃未満であるのが特に好ましい。
例えば、本塗料が含フッ素重合体を２種含む場合、上記２種の含フッ素重合体のＴｇの差の絶対値が上記範囲内であるのが好ましい。
また、本塗料が含フッ素重合体を３種以上含む場合、上記３種以上のうちの２種の含フッ素重合体を選んだ組み合わせのうち、少なくとも１つの組み合わせにおいて、Ｔｇの差の絶対値が上記範囲内であるのが好ましい。
この場合、本塗料中、Ｔｇの差の絶対値が上記範囲内にある２種の含フッ素重合体の含有量は、本塗料の固形分質量に対して、それぞれ、１〜４５質量％が好ましく、５〜４０質量％が特に好ましい。また、本塗料中、上記差の絶対値が上記範囲内にある２種の含フッ素重合体における、相対的にＴｇが高い含フッ素重合体の含有量に対する、相対的にＴｇが低い含フッ素重合体の含有量の質量比（Ｔｇが低い含フッ素重合体／Ｔｇが高い含フッ素重合体）は、０．１〜９が好ましく、１〜９がより好ましく、１．５〜５が特に好ましい。
It is also preferable to use two or more different fluoropolymers in combination.
When the coating composition contains two or more different fluoropolymers, the absolute value of the difference in Tg of the two or more different fluoropolymers is preferably more than 0°C and 50°C or less, and 5°C or more. It is particularly preferably below 20°C.
For example, when the present coating composition contains two types of fluoropolymers, the absolute value of the difference in Tg between the two types of fluoropolymers described above is preferably within the above range.
When the present coating composition contains three or more fluoropolymers, at least one of the combinations of two or more fluoropolymers selected from the above three or more polymers has an absolute value of the difference in Tg. It is preferably within the above range.
In this case, the content of the two types of fluoropolymers in the present coating composition in which the absolute value of the difference in Tg is within the above range is preferably 1 to 45 mass% with respect to the solid content mass of the coating composition. , 5 to 40 mass% is particularly preferable. Further, in the present coating composition, the fluorine-containing weight having a relatively low Tg relative to the content of the fluorine-containing polymer having a relatively high Tg in the two types of fluorine-containing polymers having the above-mentioned difference in absolute value within the above range. The mass ratio (fluorine-containing polymer having a low Tg/fluorine-containing polymer having a high Tg) of the combined content is preferably 0.1 to 9, more preferably 1 to 9, and particularly preferably 1.5 to 5.
本塗料中、含フッ素重合体の含有量は、本塗料の固形分質量に対して、５〜５０質量％が好ましく、１０〜４０質量％が特に好ましい。
なお、本塗料が２種以上の含フッ素重合体を含む場合、その合計含有量が上記範囲内であるのが好ましい。以下、本塗料が同種成分を２種以上含む場合において同様とする。
The content of the fluoropolymer in the present coating material is preferably 5 to 50% by mass, and particularly preferably 10 to 40% by mass, based on the mass of the solid content of the present coating material.
When the present coating composition contains two or more fluoropolymers, the total content is preferably within the above range. Hereinafter, the same shall apply when the present paint contains two or more components of the same kind.
本塗料は、更に、ポリエステルを含む。
ポリエステルは優れた柔軟性を有しているため、本塗膜の柔軟性が向上し、基材への優れた追従性を得られる。そのため、基材が大きく撓んでも剥離し難い塗膜が形成される。また、柔軟性に富んだ塗膜が形成されるため、基材及びその表面上に形成された塗膜が高速で運動して、雨滴や塵等と高速で衝突しても、衝撃を吸収するので塗膜に傷が付き難いと考えられている。
The paint further comprises polyester.
Since polyester has excellent flexibility, the flexibility of the present coating film is improved, and excellent conformability to a substrate can be obtained. Therefore, a coating film is formed that is difficult to peel off even when the substrate is largely bent. In addition, since a coating film with a high degree of flexibility is formed, the substrate and the coating film formed on its surface move at high speed and absorb the impact even if it collides with raindrops or dust at high speed. Therefore, it is considered that the coating film is not easily scratched.
本塗料が含むポリエステルは、架橋性基を含むのが好ましく、水酸基及びカルボキシ基からなる群から選択される少なくとも一方を含むのが好ましい。
中でも、本塗料が含むポリエステルは、水酸基を有し、水酸基価を有するのが好ましい。ポリエステルが水酸基価を有する場合、ポリエステルの水酸基価は、１〜２５０ｍｇＫＯＨ／ｇが好ましく、１００〜２４０ｍｇＫＯＨ／ｇがより好ましく、２００〜２２０ｍｇＫＯＨ／ｇが特に好ましい。
本塗料が含むポリエステルは、酸価を有するのも好ましい。ポリエステルが酸価を有する場合、ポリエステルの酸価は、１〜２５０ｍｇＫＯＨ／ｇが好ましく、１〜１０ｍｇＫＯＨ／ｇが特に好ましい。酸価を有するポリエステルは、例えば、カルボキシ基を有する。
ポリエステルの酸価及び水酸基価の一方又は両方が上記範囲内にあると、特に本塗料が硬化剤を含む場合に本塗膜の架橋密度が高くなり、本塗膜の耐久性が優れる。
中でも、含フッ素重合体及びポリエステルが、いずれも１〜２５０ｍｇＫＯＨ／ｇの水酸基価を有すると、特に本塗料が硬化剤を含む場合に含フッ素重合体とポリエステルとが架橋され、本塗膜の耐久性がより優れる。
The polyester contained in the coating composition preferably contains a crosslinkable group, and preferably contains at least one selected from the group consisting of a hydroxyl group and a carboxy group.
Above all, the polyester contained in the coating composition has a hydroxyl group, and preferably has a hydroxyl value. When the polyester has a hydroxyl value, the hydroxyl value of the polyester is preferably 1 to 250 mgKOH/g, more preferably 100 to 240 mgKOH/g, and particularly preferably 200 to 220 mgKOH/g.
The polyester contained in the present coating material preferably has an acid value. When the polyester has an acid value, the acid value of the polyester is preferably 1-250 mgKOH/g, particularly preferably 1-10 mgKOH/g. The polyester having an acid value has, for example, a carboxy group.
When one or both of the acid value and the hydroxyl value of the polyester are within the above range, the crosslink density of the present coating film becomes high, particularly when the present coating material contains a curing agent, and the durability of the present coating film is excellent.
Among them, when both the fluoropolymer and the polyester have a hydroxyl value of 1 to 250 mgKOH/g, the fluoropolymer and the polyester are crosslinked, especially when the coating composition contains a curing agent, and the durability of the coating film is improved. More excellent.
ポリエステルのＭｎは、５００〜５，０００が好ましく、５００〜３，０００がより好ましい。Ｍｎがこの範囲内であれば、塗膜の機械的強度が向上する。ポリエステルは、常温（２５℃）で液体であるのが好ましい。
ポリエステルが１分子中に有する平均の水酸基数は、２個以上が好ましく、３個以上がより好ましく、４〜４０個が特に好ましい。
中でも、ポリエステルは、水酸基を１分子中に平均３個以上有し、かつ、Ｍｎが５００〜５，０００であるのが好ましい。
The Mn of the polyester is preferably 500 to 5,000, more preferably 500 to 3,000. When Mn is within this range, the mechanical strength of the coating film is improved. The polyester is preferably liquid at room temperature (25° C.).
The average number of hydroxyl groups in one molecule of the polyester is preferably 2 or more, more preferably 3 or more, and particularly preferably 4 to 40.
Among them, it is preferable that the polyester has an average of 3 or more hydroxyl groups in one molecule and has Mn of 500 to 5,000.
ポリエステルとしては、多価カルボン酸と多価アルコールを重合して得られるポリエステルが好ましい。上記多価カルボン酸の価数は２価又は３価であるのが好ましい。
ポリエステルの製造に用いられる多価カルボン酸の具体例としては、コハク酸、マレイン酸、フタル酸、ピロメリット酸、トリメリット酸、シクロペンタンテトラカルボン酸、１，２−ヘキサヒドロフタル酸、メチル−１，２−ヘキサヒドロフタル酸、１，２−テトラヒドロキシフタル酸、メチルテトラヒドロキシフタル酸、イソフタル酸、テレフタル酸、メチルテレフタル酸、メチルイソフタル酸、フマル酸、セバシン酸、シュウ酸、グルタル酸、アジピン酸、アゼライン酸、１，３−ヘキサヒドロフタル酸、メチル−１，３−ヘキサヒドロフタル酸、１，３−テトラヒドロキシフタル酸、１，４−ヘキサヒドロフタル酸、メチル−１，４−ヘキサヒドロフタル酸、１，４−テトラヒドロキシフタル酸、それらの酸無水物が挙げられる。
多価カルボン酸は、２種以上を併用してもよい。
As the polyester, a polyester obtained by polymerizing a polycarboxylic acid and a polyhydric alcohol is preferable. The valence of the polycarboxylic acid is preferably divalent or trivalent.
Specific examples of the polycarboxylic acid used for producing the polyester include succinic acid, maleic acid, phthalic acid, pyromellitic acid, trimellitic acid, cyclopentanetetracarboxylic acid, 1,2-hexahydrophthalic acid and methyl- 1,2-hexahydrophthalic acid, 1,2-tetrahydroxyphthalic acid, methyltetrahydroxyphthalic acid, isophthalic acid, terephthalic acid, methylterephthalic acid, methylisophthalic acid, fumaric acid, sebacic acid, oxalic acid, glutaric acid, Adipic acid, azelaic acid, 1,3-hexahydrophthalic acid, methyl-1,3-hexahydrophthalic acid, 1,3-tetrahydroxyphthalic acid, 1,4-hexahydrophthalic acid, methyl-1,4- Hexahydrophthalic acid, 1,4-tetrahydroxyphthalic acid, and their acid anhydrides are mentioned.
Two or more polycarboxylic acids may be used in combination.
ポリエステルの製造に用いられる多価アルコールの具体例としては、エチレングリコール、プロパンジオール、ブタンジオール、ペンタンジオール、１，６−ヘキサンジオール、１，９−ノナンジオール、ネオペンチルグリコール、２，２−ジエチルプロパンジオール、シクロヘキサンジオール、グリセリン、トリメチロールプロパン、ペンタエリスリトール、トリメチロールエタン、１，４−シクロヘキサンジメタノール、２，２，４−トリメチル−１，３−ペンタンジオール、２−ブチル−２−エチル−１，３−プロパンジオール、ヒドロキシビバリルヒドロキシビバレート、３−メチル−１，５−ペンタンジオール、２−メチル−１，８−オクタンジオール、２−メチル−１，３−プロパンジオール、ポリエチレングリコール、ポリプロピレングリコールが挙げられる。
多価アルコールは、２種以上を併用してもよい。
Specific examples of the polyhydric alcohol used for producing polyester include ethylene glycol, propanediol, butanediol, pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol and 2,2-diethyl. Propanediol, cyclohexanediol, glycerin, trimethylolpropane, pentaerythritol, trimethylolethane, 1,4-cyclohexanedimethanol, 2,2,4-trimethyl-1,3-pentanediol, 2-butyl-2-ethyl- 1,3-propanediol, hydroxybivalyl hydroxybivalate, 3-methyl-1,5-pentanediol, 2-methyl-1,8-octanediol, 2-methyl-1,3-propanediol, polyethylene glycol, Examples include polypropylene glycol.
Two or more polyhydric alcohols may be used in combination.
ポリエステルの製造には、上述したような多価カルボン酸や多価アルコールの他に、１分子中にカルボキシ基と水酸基とを有する化合物やその環化物も使用できる。このような化合物の具体例としては、ε−カプロラクトンが挙げられる。 In the production of polyester, a compound having a carboxy group and a hydroxyl group in one molecule or a cyclized product thereof can be used in addition to the above-described polycarboxylic acid and polyhydric alcohol. A specific example of such a compound is ε-caprolactone.
ポリエステルは、水酸基やカルボキシ基以外の他の官能基を有していてもよい。他の官能基としては、本塗膜の耐候性、機械特性、耐油性、硬化反応性等の点から、アミノ基、アセトアセチル基、又は、エポキシ基が好ましい。
これらの官能基を導入する方法の具体例としては、これらの官能基及び重合性の二重結合を有する単量体を共重合させる方法、ポリエステル中の水酸基及びカルボキシ基の一方又は両方に、これらの官能基を有する化合物を反応させる方法が挙げられる。
より具体的には、例えば、ポリエステルの製造中もしくは製造後に、水酸基及びカルボキシ基の一方又は両方と反応する反応性基と、アミノ基、アセトアセチル基、及び、エポキシ基のうちの少なくとも１つとを有する化合物を反応させることにより行える。
ポリエステルは、２種以上を併用してもよい。
The polyester may have a functional group other than a hydroxyl group and a carboxy group. As the other functional group, an amino group, an acetoacetyl group, or an epoxy group is preferable from the viewpoints of weather resistance, mechanical properties, oil resistance, curing reactivity of the coating film.
Specific examples of the method of introducing these functional groups, a method of copolymerizing a monomer having these functional groups and a polymerizable double bond, one or both of the hydroxyl group and the carboxy group in the polyester, these The method of reacting the compound having the functional group
More specifically, for example, during or after the production of the polyester, a reactive group that reacts with one or both of a hydroxyl group and a carboxy group, and an amino group, an acetoacetyl group, and at least one of an epoxy group It can be carried out by reacting a compound having the same.
You may use together 2 or more types of polyester.
ポリエステルは市販品を使用してもよく、ポリエステルの市販品の具体例としては、ニッポラン１２５Ｐ、ニッポラン１３１、ニッポラン１３３ＥＰ、ニッポラン１３９、ニッポラン１７９、ニッポラン８００、ニッポラン１１００（以上、日本ポリウレタン工業社製）、デスモフェン６５０、デスモフェン６５１、デスモフェン６７０、デスモフェン８００（以上、住友バイエルウレタン社製）、バーノック１１−４０８、バーノックＤ−２１０−８０、バーノックＤ−１６１（以上、大日本インキ化学工業社製）、ＦＬＥＸＯＲＥＺ１４８、ＦＬＥＸＯＲＥＺ１８８（以上、ＫＩＮＧ ＩＮＤＵＳＴＲＩＥＳ社製）が挙げられる。 A commercially available product may be used as the polyester, and specific examples of the commercially available product of the polyester include Nipporan 125P, Nipporan 131, Nipporan 133EP, Nipporan 139, Nipporan 179, Nipporan 800, Nipporan 1100 (above, manufactured by Nippon Polyurethane Industry Co., Ltd.). , Desmophen 650, Desmophen 651, Desmophen 670, Desmofen 800 (above, Sumitomo Bayer Urethane Co., Ltd.), Barnock 11-408, Barnock D-210-80, Barnock D-161 (all manufactured by Dainippon Ink and Chemicals, Inc.), FLEXOREZ 148 and FLEXOREZ 188 (all manufactured by KING INDUSTRIES) are mentioned.
本塗料中、ポリエステルの含有量は、本塗料の固形分質量に対して、５〜４０質量％が好ましく、７〜２０質量％が特に好ましい。
ポリエステルの含有量が上記範囲の下限値以上であれば、塗膜の基材への追従性が向上する。ポリエステルの含有量が上記範囲の上限値以下であれば、塗膜の耐候性及び密着性が向上する。
The content of polyester in the present coating material is preferably 5 to 40% by mass, and particularly preferably 7 to 20% by mass, based on the mass of the solid content of the present coating material.
When the content of the polyester is not less than the lower limit of the above range, the followability of the coating film to the base material is improved. When the content of polyester is not more than the upper limit of the above range, the weather resistance and adhesion of the coating film are improved.
本塗料中、ポリエステルの含有量に対する、含フッ素重合体の含有量の質量比（含フッ素重合体／ポリエステル）は、０．１〜９が好ましく、１．０〜７がより好ましく、１．５〜５が更に好ましく、２．０〜２．５が特に好ましい。 In the present coating composition, the mass ratio of the content of the fluoropolymer to the content of the polyester (fluoropolymer/polyester) is preferably 0.1 to 9, more preferably 1.0 to 7, and 1.5. 5 to 5 are more preferable, and 2.0 to 2.5 are particularly preferable.
本塗料が含む無機粒子は、モース硬度が３．０〜５．０であり、４．０〜５．０がより好ましく、４．５〜５．０が特に好ましい。
上記無機粒子は、モース硬度が上記範囲内であれば、着色剤として使用される無機粒子を含んでもよい。
上記無機粒子の具体例としては、珪灰石（ウォラストナイト）、炭酸カルシウム、ゼオライトが挙げられ、本塗膜の耐浸食性に優れる点から、珪灰石が好ましい。
無機粒子（好ましくは珪灰石）のアスペクト比は、１．２〜３０が好ましく、１．５〜４．５が特に好ましい。
無機粒子のアスペクト比が上記範囲の下限値以上であると、本塗膜の耐浸食性がより優れる。無機粒子のアスペクト比が上記範囲の上限値以下であると、本塗膜の美観が優れる。
なお、上記アスペクト比は、無機粒子の平均長径／平均短径の値である。ここでいう平均短径及び平均長径とは、電子顕微鏡観察により一定面積内に存在する１００個の一次粒子について短径及び長径を測長し、それぞれ平均して求めた値である。
無機粒子（好ましくは珪灰石）の平均長径は、１〜５０μｍが好ましく、１〜３０μｍが特に好ましい。
The inorganic particles contained in the coating composition have a Mohs hardness of 3.0 to 5.0, more preferably 4.0 to 5.0, and particularly preferably 4.5 to 5.0.
The inorganic particles may include inorganic particles used as a colorant as long as the Mohs hardness is within the above range.
Specific examples of the inorganic particles include wollastonite, calcium carbonate, and zeolite. Wollastonite is preferable from the viewpoint of excellent erosion resistance of the present coating film.
The aspect ratio of the inorganic particles (preferably wollastonite) is preferably 1.2 to 30, and particularly preferably 1.5 to 4.5.
When the aspect ratio of the inorganic particles is at least the lower limit value of the above range, the erosion resistance of the present coating film is more excellent. When the aspect ratio of the inorganic particles is not more than the upper limit value of the above range, the appearance of this coating film is excellent.
The aspect ratio is a value of average major axis/average minor axis of inorganic particles. The average minor axis and the average major axis here are values obtained by measuring the minor axis and the major axis of 100 primary particles existing in a certain area by electron microscope observation and averaging them.
The average major axis of the inorganic particles (preferably wollastonite) is preferably 1 to 50 μm, particularly preferably 1 to 30 μm.
無機粒子は、２種以上を併用してもよい。無機粒子を２種以上併用する場合、少なくとも珪灰石を含むのが好ましい。 Two or more types of inorganic particles may be used in combination. When two or more kinds of inorganic particles are used in combination, it is preferable that at least wollastonite is contained.
本塗料中、無機粒子の含有量は、含フッ素重合体とポリエステルとの合計１００質量部に対して、２０〜６０質量部であり、３０〜５５質量部が好ましく、３５〜５０質量部が特に好ましい。
本塗料中、無機粒子の含有量は、本塗料の固形分質量に対して、１０〜７０質量％が好ましく、１５〜６０質量％が特に好ましい。
上述の通り、無機粒子は少なくとも珪灰石を含むのが好ましく、本塗料中、珪灰石の含有量は、本塗料の固形分質量に対して、５〜５０質量％が好ましく、１０〜３０質量％がより好ましく、１３〜２５質量％が特に好ましい。
In the coating composition, the content of the inorganic particles is 20 to 60 parts by mass, preferably 30 to 55 parts by mass, and more preferably 35 to 50 parts by mass, based on 100 parts by mass of the total of the fluoropolymer and the polyester. preferable.
The content of the inorganic particles in the coating composition is preferably 10 to 70% by mass, and particularly preferably 15 to 60% by mass, based on the mass of the solid content of the coating composition.
As described above, the inorganic particles preferably include at least wollastonite, and the content of wollastonite in the present coating material is preferably 5 to 50% by mass, and 10 to 30% by mass based on the mass of the solid content of the present coating material. Is more preferable, and 13 to 25 mass% is particularly preferable.
本塗料は、本塗膜の外観が優れる点から、無機粒子等の成分が十分に分散しているのが好ましい。
具体的には、本塗料の分散度が、１００μｍ以下であるのが好ましく、４０μｍ以下であるのが特に好ましい。下限は、通常、１μｍ以上である。
In the present coating composition, components such as inorganic particles are preferably sufficiently dispersed from the viewpoint of excellent appearance of the coating film.
Specifically, the dispersity of the present coating material is preferably 100 μm or less, and particularly preferably 40 μm or less. The lower limit is usually 1 μm or more.
本塗料は、上述の成分以外の成分を含んでもよい。
このような成分の具体例としては、含フッ素重合体及びポリエステル以外の樹脂、添加剤が挙げられる。
含フッ素重合体及びポリエステル以外の樹脂の具体例としては、（メタ）アクリル樹脂、ウレタン樹脂、エポキシ樹脂、シリコーン樹脂が挙げられる。
添加剤の具体例としては、硬化剤、硬化触媒、溶媒、上述の無機粒子以外のフィラー（モース硬度が３．０未満又は５．０超の無機粒子、樹脂ビーズ等の有機フィラー等。顔料（無機顔料）であってもよい）、着色剤（染料、有機顔料等）、消泡剤、紫外線吸収剤、光安定剤、つや消し剤、レベリング剤、表面調整剤、脱ガス剤、熱安定剤、増粘剤、分散剤、界面活性剤、帯電防止剤、防錆剤、シランカップリング剤、防汚剤、低汚染化処理剤、可塑剤、接着剤が挙げられる。
The coating composition may contain components other than the above components.
Specific examples of such components include resins and additives other than the fluoropolymer and polyester.
Specific examples of resins other than the fluoropolymer and polyester include (meth)acrylic resins, urethane resins, epoxy resins, and silicone resins.
Specific examples of the additive include a curing agent, a curing catalyst, a solvent, a filler other than the above-mentioned inorganic particles (inorganic particles having a Mohs hardness of less than 3.0 or more than 5.0, an organic filler such as resin beads, etc., a pigment ( (Inorganic pigment)), colorant (dye, organic pigment, etc.), defoaming agent, ultraviolet absorber, light stabilizer, matting agent, leveling agent, surface conditioner, degassing agent, heat stabilizer, Examples thereof include thickeners, dispersants, surfactants, antistatic agents, rust preventives, silane coupling agents, antifouling agents, agents for reducing stains, plasticizers, and adhesives.
本塗料は、添加剤として、硬化剤を含むのが好ましい。
特に、含フッ素重合体やポリエステルが、水酸基やカルボキシ基を含む場合、含フッ素重合体やポリエステルが硬化剤によって架橋され、本塗膜の耐久性（耐水性、耐薬品性等）が優れる。
The present coating composition preferably contains a curing agent as an additive.
In particular, when the fluoropolymer or polyester contains a hydroxyl group or a carboxy group, the fluoropolymer or polyester is crosslinked by the curing agent, and the durability (water resistance, chemical resistance, etc.) of the present coating film is excellent.
硬化剤は、含フッ素重合体やポリエステルが有していてもよい、架橋性基と反応し得る基を１分子中に２以上有する化合物である。硬化剤と、含フッ素重合体が有する水酸基等とが反応すると、含フッ素重合体が硬化剤を介して架橋し、フッ素樹脂が形成される。硬化剤は、水酸基及びカルボキシ基の少なくとも一方と反応し得る基を、通常２〜３０個有する。
硬化剤としては、イソシアネート基、エポキシ基、オキサゾリン基、β−ヒドロキシアルキルアミド基等を１分子中に２以上有する化合物が挙げられる。
含フッ素重合体が水酸基を有する場合、硬化剤としては、イソシアネート基を１分子中に２以上有する化合物であるポリイソシアネートが好ましい。
含フッ素重合体がカルボキシ基を有する場合、硬化剤としては、エポキシ基、オキサゾリン基、又は、β−ヒドロキシアルキルアミド基等を１分子中に２以上有する化合物が好ましい。
The curing agent is a compound having two or more groups capable of reacting with the crosslinkable group in one molecule, which the fluoropolymer or polyester may have. When the curing agent reacts with the hydroxyl group or the like of the fluoropolymer, the fluoropolymer is crosslinked through the curing agent to form a fluororesin. The curing agent usually has 2 to 30 groups capable of reacting with at least one of a hydroxyl group and a carboxy group.
Examples of the curing agent include compounds having two or more isocyanate groups, epoxy groups, oxazoline groups, β-hydroxyalkylamide groups and the like in one molecule.
When the fluoropolymer has a hydroxyl group, the curing agent is preferably polyisocyanate, which is a compound having two or more isocyanate groups in one molecule.
When the fluoropolymer has a carboxy group, the curing agent is preferably a compound having two or more epoxy groups, oxazoline groups, β-hydroxyalkylamide groups or the like in one molecule.
ポリイソシアネートとは、イソシアネート基又はブロック化イソシアネート基を１分子中に２以上有する化合物である。
ポリイソシアネートとしては、ポリイソシアネート単量体、又は、ポリイソシアネート誘導体が好ましい。
ポリイソシアネート単量体としては、脂環族ポリイソシアネート、脂肪族ポリイソシアネート、又は、芳香族ポリイソシアネートが好ましい。ポリイソシアネート誘導体としては、ポリイソシアネート単量体の多量体又は変性体（アダクト体、アロファネート体、ビウレット体、イソシアヌレート体等）が好ましい。
Polyisocyanate is a compound having two or more isocyanate groups or blocked isocyanate groups in one molecule.
As the polyisocyanate, a polyisocyanate monomer or a polyisocyanate derivative is preferable.
The polyisocyanate monomer is preferably an alicyclic polyisocyanate, an aliphatic polyisocyanate or an aromatic polyisocyanate. The polyisocyanate derivative is preferably a multimer or modified polyisocyanate monomer (adduct, allophanate, biuret, isocyanurate, etc.).
脂肪族ポリイソシアネートの具体例としては、テトラメチレンジイソシアネート、ペンタメチレンジイソシアネート、ヘキサメチレンジイソシアネート、２，２，４−トリメチル−１，６−ジイソシアナトヘキサン、リジンジイソシアネート等の脂肪族ジイソシアネート、リジントリイソシアネート、４−イソシアナトメチル−１，８−オクタメチレンジイソシアネート、ビス（２−イソシアナトエチル）２−イソシアナトグルタレートが挙げられる。
脂環族ポリイソシアネートの具体例としては、イソホロンジイソシアネート、１，３−ビス（イソシアナトメチル）−シクロヘキサン、４，４’−ジシクロヘキシルメタンジイソシアネート、ノルボルネンジイソシアネート、水添キシリレンジイソシアネート等の脂環族ジイソシアネートが挙げられる。
芳香族ポリイソシアネートの具体例としては、２，４−トリレンジイソシアネート、２，６−トリレンジイソシアネート、４，４’−ジフェニルメタンジイソシアネート、ナフタレンジイソシアネート、キシリレンジイソシアネート等の芳香族ジイソシアネートが挙げられる。
Specific examples of the aliphatic polyisocyanates include tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-diisocyanatohexane, aliphatic diisocyanates such as lysine diisocyanate, and lysine triisocyanate. , 4-isocyanatomethyl-1,8-octamethylene diisocyanate and bis(2-isocyanatoethyl)2-isocyanatoglutarate.
Specific examples of the alicyclic polyisocyanate include isophorone diisocyanate, 1,3-bis(isocyanatomethyl)-cyclohexane, 4,4′-dicyclohexylmethane diisocyanate, norbornene diisocyanate and hydrogenated xylylene diisocyanate. Is mentioned.
Specific examples of the aromatic polyisocyanate include aromatic diisocyanates such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene diisocyanate and xylylene diisocyanate.
ポリイソシアネートは、上述したポリイソシアネート単量体又はポリイソシアネート誘導体が有する２以上のイソシアネート基が、ブロック化剤によってブロックされている化合物（ブロック化ポリイソシアネート）であってもよいし、ブロックされていない化合物（非ブロック化ポリイソシアネート）であってもよい。
ブロック化剤は、活性水素を有する化合物であり、具体例としては、アルコール、フェノール、活性メチレン、アミン、イミン、酸アミド、ラクタム、オキシム、ピラゾール、イミダゾール、イミダゾリン、ピリミジン、グアニジンが挙げられる。
The polyisocyanate may be a compound (blocked polyisocyanate) in which two or more isocyanate groups of the above-mentioned polyisocyanate monomer or polyisocyanate derivative are blocked by a blocking agent, or may not be blocked. It may be a compound (unblocked polyisocyanate).
The blocking agent is a compound having active hydrogen, and specific examples thereof include alcohol, phenol, active methylene, amine, imine, acid amide, lactam, oxime, pyrazole, imidazole, imidazoline, pyrimidine and guanidine.
硬化剤は、２種以上を併用してもよい。
本塗料が硬化剤を含む場合、硬化剤の含有量は、本塗料が含む含フッ素重合体とポリエステルとの合計質量に対して、１０〜２００質量％が好ましく、３０〜８０質量％が特に好ましい。
Two or more curing agents may be used in combination.
When the present coating composition contains a curing agent, the content of the curing agent is preferably 10 to 200% by mass, and particularly preferably 30 to 80% by mass, based on the total mass of the fluoropolymer and polyester contained in the coating composition. ..
本塗料は、添加剤として、上述の無機粒子以外のフィラーを含むのが好ましい。このようなフィラーとしては、顔料（無機顔料）が好ましい。上記顔料の具体例としては、酸化チタンが挙げられる。
本塗料が上述の無機粒子以外のフィラーを含む場合、上述の無機粒子以外のフィラーの含有量は、本塗料の固形分質量に対して、５〜５０質量％が好ましく、１０〜４０質量％が特に好ましい。
It is preferable that the present coating material contains a filler other than the above-mentioned inorganic particles as an additive. As such a filler, a pigment (inorganic pigment) is preferable. Specific examples of the pigment include titanium oxide.
When this coating material contains a filler other than the above-mentioned inorganic particles, the content of the filler other than the above-mentioned inorganic particles is preferably 5 to 50% by mass, and 10 to 40% by mass with respect to the solid content mass of the present coating material. Particularly preferred.
本塗料は、含フッ素重合体等の成分が溶媒（水、有機溶剤等）に溶解又は分散している塗料（水系塗料、溶剤型塗料等）であってもよく、溶媒を実質的に含まない塗料（粉体塗料等）であってもよい。本塗料は、緻密な塗膜を形成でき耐候性に優れる点から、溶剤型塗料であるのが好ましい。
有機溶剤の具体例としては、アルコール、ケトン、エステル、炭化水素が挙げられる。
本塗料が溶媒（好ましくは有機溶剤）を含む場合、本塗料における溶媒（好ましくは有機溶剤）の含有量は、本塗料の全質量に対して、１０〜９０質量％が好ましく、１０〜４０質量％がより好ましく、１５〜３５質量％が特に好ましい。つまり、本塗料における固形分の含有量は、本塗料の全質量に対して、１０〜９０質量％が好ましく、６０〜９０質量％がより好ましく、６５〜８５質量％が特に好ましい。
The paint may be a paint (water-based paint, solvent-based paint, etc.) in which a component such as a fluoropolymer is dissolved or dispersed in a solvent (water, organic solvent, etc.), and does not substantially contain the solvent. It may be paint (powder paint, etc.). The present coating composition is preferably a solvent-based coating composition because it can form a dense coating film and is excellent in weather resistance.
Specific examples of the organic solvent include alcohols, ketones, esters and hydrocarbons.
When this coating material contains a solvent (preferably an organic solvent), the content of the solvent (preferably an organic solvent) in this coating material is preferably 10 to 90% by mass, and 10 to 40% by mass with respect to the total mass of the coating material. % Is more preferable, and 15 to 35 mass% is particularly preferable. That is, the content of the solid content in the present coating material is preferably 10 to 90% by mass, more preferably 60 to 90% by mass, and particularly preferably 65 to 85% by mass, based on the total mass of the present coating material.
本塗料は、タービンが有するブレード及び航空機の翼に用いられ、タービンが有するブレードに用いられるのが好ましく、風力タービンが有するブレードに用いられるのがより好ましく、風力発電用タービンが有するブレード（風力発電機のブレード）に用いられるのが特に好ましい。
つまり、本塗料は、タービンが有するブレード又は航空機の翼である基材に塗布して用いられ、基材（タービンが有するブレード又は航空機の翼）上に本塗膜を形成する。また、このように基材上に本塗膜を形成して、塗膜を有する基材である、塗膜付き基材（塗膜付きブレード又は塗膜付き翼）が得られる。
図１、２は本塗膜を有する風力発電機のブレード（塗膜付きブレード）の一例を示した図であり、図１は部分断面図、図２は正面図である。
本例の風力発電機１０１は、塔体１１０と、塔体１１０の上部に設けられた塔頂回動部１２０と、塔頂回動部１２０に回動支持部を介して取り付けられた塗膜付きブレード１３０とを有する。塗膜付きブレード１３０はブレード１１の表面に本塗料を用いて形成された塗膜１２（本塗膜）が設けられている。
図３、４は集風体を備えた風力発電機の一例を示したものであり、図３は斜視図、図４は側面図である。本例の風力発電機は、塔体１４０と、塔体１４０の上部に設けられた塔頂回動部１５０と、塔頂回動部１５０に回動支持部を介して取り付けられた塗膜付きブレード１６０と、塗膜付きブレード１６０の周囲に設けられた略円環状の集風体１７０を有する。
集風体１７０は集風体の表面に本塗料を用いて形成された本塗膜（図示略）が設けられていてもよい。
The coating composition is used for a blade of a turbine and a wing of an aircraft, preferably for a blade of a turbine, more preferably for a blade of a wind turbine, and more preferably for a blade of a turbine for wind power generation (wind power generation). It is particularly preferable to be used for a machine blade).
That is, the present coating composition is used by being applied to a base material that is a blade of a turbine or a wing of an aircraft, and forms the main coating film on a base material (a blade of a turbine or a wing of an aircraft). Further, by forming the present coating film on the substrate in this manner, a substrate with a coating film (a blade with a coating film or a blade with a coating film), which is a substrate having a coating film, is obtained.
1 and 2 are views showing an example of a blade (blade with a coating) of a wind power generator having the present coating, FIG. 1 is a partial sectional view, and FIG. 2 is a front view.
The wind power generator 101 of the present example is a tower 110, a tower top rotation part 120 provided on the top of the tower body 110, and a coating film attached to the tower top rotation part 120 via a rotation support part. With a blade 130. The coating-coated blade 130 has a coating film 12 (main coating film) formed by using the present coating material on the surface of the blade 11.
3 and 4 show an example of a wind power generator including a wind collector, FIG. 3 is a perspective view, and FIG. 4 is a side view. The wind power generator of this example includes a tower body 140, a tower top rotating portion 150 provided on an upper portion of the tower body 140, and a coating film attached to the tower top rotating portion 150 via a rotation supporting portion. It has a blade 160 and a substantially annular wind collector 170 provided around the blade 160 with a coating film.
The air collecting body 170 may be provided with a main coating film (not shown) formed using the present paint on the surface of the air collecting body.
以下、本塗料を風力発電機のブレードに塗布して本塗膜を形成する場合の例から、本塗膜の好ましい形成方法を説明する。
まず、図１に示すように、風力発電機のブレード１１表面に、本塗料を塗布して塗布層１２Ａを形成する。
本塗料の塗布方法の具体例としては、刷毛、ローラ、スプレー、フローコータ、アプリケータ等を使用する方法が挙げられる。本塗料の塗布量は、目的とする乾燥膜厚に応じて適宜選定すればよい。
次いで、本塗料が溶媒を含む場合は塗布層１２Ａから溶媒を除去し、また、本塗料が硬化剤を含む場合は塗布層１２Ａを硬化させて、塗膜１２（本塗膜）を形成でき、塗膜付きブレード１３０が得られる。
Hereinafter, a preferred method for forming the present coating film will be described from an example of forming the present coating film by applying the present coating material to a blade of a wind power generator.
First, as shown in FIG. 1, the coating material 12 is applied to the surface of the blade 11 of the wind power generator to form a coating layer 12A.
Specific examples of the method for applying the present paint include a method using a brush, a roller, a spray, a flow coater, an applicator, or the like. The coating amount of the present coating material may be appropriately selected according to the target dry film thickness.
Next, when the main coating material contains a solvent, the solvent is removed from the coating layer 12A, and when the main coating material contains a curing agent, the coating layer 12A can be cured to form the coating film 12 (main coating film), The coated blade 130 is obtained.
塗布層１２Ａから溶媒を除去する方法としては、自然乾燥させる方法でもよいし、加熱等により溶媒を揮発させる方法でもよい。塗布層１２Ａの加熱方法の具体例としては、塗布層１２Ａに熱風を当てる方法が挙げられる。
溶媒を除去する際の温度は、常温（２５℃程度）〜１００℃が好ましく、常温〜８０℃が特に好ましい。上記温度が上記範囲の下限値以上であれば、溶媒が除去されやすい。上記温度が上記範囲の上限値以下であれば、塗膜１２（本塗膜）に発泡跡が生じにくい。
The method of removing the solvent from the coating layer 12A may be a method of natural drying or a method of volatilizing the solvent by heating or the like. A specific example of the heating method of the coating layer 12A is a method of applying hot air to the coating layer 12A.
The temperature for removing the solvent is preferably room temperature (about 25°C) to 100°C, particularly preferably room temperature to 80°C. If the temperature is at least the lower limit value of the above range, the solvent is easily removed. When the temperature is equal to or lower than the upper limit of the above range, the coating film 12 (main coating film) is less likely to have a foaming trace.
本塗料が、硬化剤を含み、かつ、本塗料中の含フッ素重合体及びポリエステルの一方又は両方が架橋性基（好ましくは、水酸基又はカルボキシ基）を有する場合において、上記架橋性基と硬化剤とが反応（硬化反応）して塗布層１２Ａが硬化する。
硬化剤として非ブロック化ポリイソシアネートを用いる場合、塗布層１２Ａを硬化させる方法は、室温で養生する方法でもよい。また、密封系乾燥炉や、連続乾燥が可能なトンネル炉等で、熱風循環、赤外線加熱、高周波加熱等により熱硬化させる方法でもよい。中でも、連続生産性の点ではトンネル炉を使用する方法が好ましく、熱の伝わり方の均一性に優れ、均一な硬化塗膜が得られやすい点からは、熱風循環又は赤外線加熱により熱硬化させる方法が好ましい。
硬化剤としてブロック化ポリイソシアネートを用いる場合、塗布層１２Ａを硬化させる方法は、密封系乾燥炉や、連続乾燥が可能なトンネル炉等で、熱風循環、赤外線加熱、又は、高周波加熱等により熱硬化させる方法が好ましい。中でも、連続生産性の点ではトンネル炉を使用する方法が好ましく、熱の伝わり方の均一性に優れ、均一な硬化塗膜が得られやすい点からは、熱風循環又は赤外線加熱により熱硬化させる方法が好ましい。
形成される塗膜１２（本塗膜）の膜厚は、２０〜１００μｍが好ましく、２０〜８０μｍが特に好ましい。
In the case where the coating composition contains a curing agent, and one or both of the fluoropolymer and the polyester in the coating composition have a crosslinking group (preferably a hydroxyl group or a carboxy group), the crosslinking group and the curing agent React with each other (curing reaction) to cure the coating layer 12A.
When the unblocked polyisocyanate is used as the curing agent, the method of curing the coating layer 12A may be a method of curing at room temperature. Alternatively, a method of heat curing by hot air circulation, infrared heating, high-frequency heating, or the like may be used in a sealed drying oven, a tunnel oven capable of continuous drying, or the like. Among them, a method of using a tunnel furnace is preferable in terms of continuous productivity, excellent in uniformity of heat transfer, and easy to obtain a uniform cured coating film. Is preferred.
When the blocked polyisocyanate is used as the curing agent, the method for curing the coating layer 12A is to heat cure by hot air circulation, infrared heating, high frequency heating, or the like in a sealed drying oven or a tunnel oven capable of continuous drying. The method of allowing is preferred. Among them, a method of using a tunnel furnace is preferable in terms of continuous productivity, excellent in uniformity of heat transfer, and easy to obtain a uniform cured coating film. Is preferred.
20-100 micrometers is preferable and, as for the film thickness of the coating film 12 (main coating film) formed, 20-80 micrometers is especially preferable.
ブレード１１又は集風体の材質の具体例としては、樹脂（プラスチック等）、金属（アルミ、ステンレス、鋼等）、木材等を適宜選択でき、表面が繊維強化プラスチック（ＦＲＰ：Ｆｉｂｅｒ Ｒｅｉｎｆｏｒｃｅｄ Ｐｌａｓｔｉｃｓ）により補強された木材が特に好ましい。
ブレードの基体１１又は集風体は公知の方法で製造できる。ブレードの基体１１又は集風体の基体の形状は図１〜４に示した例に限らず、適宜変更可能である。
なお、ブレード１１と塗膜１２（本塗膜）の間に、別の層を形成してもよい。
具体的には、アルキッド樹脂、エポキシ樹脂、アクリル樹脂等を使用して樹脂層を形成した後に、樹脂層上に本塗料により本塗膜を形成する方法、本塗膜の密着性を向上させるためのシランカップリング剤からなる層を形成した後に、上記層上に本塗料を塗布して本塗膜を形成する方法等であってもよい。
As a specific example of the material of the blade 11 or the air collecting body, resin (plastic etc.), metal (aluminum, stainless steel, steel etc.), wood, etc. can be appropriately selected, and the surface is reinforced with fiber reinforced plastics (FRP: Fiber Reinforced Plastics). Wood is particularly preferred.
The blade base 11 or the wind collector can be manufactured by a known method. The shape of the blade base body 11 or the wind collector body base body is not limited to the examples shown in FIGS.
It should be noted that another layer may be formed between the blade 11 and the coating film 12 (main coating film).
Specifically, after forming a resin layer using an alkyd resin, an epoxy resin, an acrylic resin or the like, a method of forming the main coating film on the resin layer with the present coating material, in order to improve the adhesion of the main coating film A method of forming a layer comprising the silane coupling agent and then coating the coating material on the layer to form the coating film may be used.
上述の本塗膜の形成方法は、風力発電用タービンが有するブレード以外の基材に適用されてもよい。
例えば、本塗料を、航空機の翼に塗布して本塗膜を形成する場合における本塗膜の形成方法の具体例としては、上述の本塗膜の形成方法において、本塗料が塗布される風力発電機のブレードを航空機の翼に置き換えた方法が挙げられる。
また、上述の本塗膜の形成方法は、風力発電用タービン以外の他のタービンが有するブレードにも適用されてもよい。
風力発電用タービンが有するブレード以外の基材に塗膜を塗布して、塗膜を形成して得られる塗膜付き基材においても、本塗膜の膜厚は、２０〜１００μｍが好ましく、２０〜８０μｍが特に好ましい。
The method for forming the present coating film described above may be applied to a base material other than the blade of the turbine for wind power generation.
For example, as a specific example of the method for forming the present coating when the present coating is applied to an aircraft wing to form the present coating, the wind force to which the present coating is applied in the above-mentioned method for forming the present coating. One method is to replace the blade of the generator with the wing of the aircraft.
Further, the method for forming the present coating film described above may be applied to a blade of a turbine other than the turbine for wind power generation.
Even in a coated substrate obtained by applying a coating film to a substrate other than a blade of a wind turbine for forming a coating film, the thickness of the present coating film is preferably 20 to 100 μm, ˜80 μm is particularly preferred.
以上説明した製造方法により、タービンが有するブレード又は航空機の翼の表面上に形成された本塗膜は、追従性に優れ、剥離が生じにくく、耐候性に優れ、耐浸食性にも優れる。
したがって、例えば、上記ブレードや翼が高速で運動して基体が大きく撓んでも、塗膜の剥離が生じ難い。また、上記ブレードや翼に対して雨滴や塵等が高速で衝突しても、十分な強固さと柔軟さを有するため、塗膜に傷が付き難く、浸食されにくい。
The coating film formed on the surface of the blade of the turbine or the blade of the aircraft by the manufacturing method described above has excellent followability, is less likely to cause peeling, is excellent in weather resistance, and is also excellent in erosion resistance.
Therefore, for example, even if the blade or blade moves at a high speed and the substrate largely bends, the coating film is unlikely to peel off. Further, even if raindrops, dust or the like collide with the blades or wings at a high speed, the coating film has sufficient strength and flexibility so that the coating film is not easily scratched and eroded.
以下、例を挙げて本発明を詳細に説明する。例１〜２は実施例であり、例３〜６は比較例である。ただし本発明はこれらの例に限定されない。 Hereinafter, the present invention will be described in detail with reference to examples. Examples 1-2 are examples, and Examples 3-6 are comparative examples. However, the present invention is not limited to these examples.
（化合物等の略称）
含フッ素重合体溶液１：ルミフロンＬＦ９７１６（水酸基価１６２ｍｇＫＯＨ／ｇ、Ｔｇ４０℃の含フッ素重合体を含む、固形分濃度７０％のキシレン溶液、ＡＧＣ社商品）
含フッ素重合体溶液２：ルミフロンＬＦ９７２１（水酸基価１７０ｍｇＫＯＨ／ｇ、Ｔｇ３０℃の含フッ素重合体を含む、固形分濃度７０％のキシレン溶液、ＡＧＣ社商品）
ポリエステル樹脂１：ニッポラン１１００（水酸基価２１３ｍｇＫＯＨ／ｇ、酸価４ｍｇＫＯＨ／ｇ、東ソー社商品）
ポリエステル樹脂２：ＦＬＥＸＯＲＥＺ１４８（水酸基価２３５ｍｇＫＯＨ／ｇ、ＫＩＮＧ ＩＮＤＵＳＴＲＩＥＳ社製社商品）
ポリエステル樹脂３：ＦＬＥＸＯＲＥＺ１８８（水酸基価２３０ｍｇＫＯＨ／ｇ、ＫＩＮＧ ＩＮＤＵＳＴＲＩＥＳ社製社商品）
無機粒子：ＮＹＡＤ ４００（アスペクト比３、平均長径２７μｍ、モース硬度４．５であるウォラストナイト、ＮＹＣＯ社商品）
分散剤：ＤｉｓｐｅｒＢＹＫ−１１０（ビックケミー・ジャパン社商品）
ＥＥＰ：エトキシエチルプロピオネート
消泡剤：ディスパロン１９９３（楠本化成社商品）
顔料：タイペーク ＰＦＣ１０５（石原産業社商品）
硬化触媒：ジブチルスズジラウレート
紫外線吸収剤：ＴＩＮＵＶＩＮ ３８４−２（ＢＡＳＦ社商品）
光安定剤：ＴＩＮＵＶＩＮ １２３（ＢＡＳＦ社商品）
増粘剤：フローノンＳＰ−１０００（共栄社化学社商品）
なお、含フッ素重合体溶液１及び２に記載した水酸基価、Ｔｇは、それぞれの溶液が含む含フッ素重合体の水酸基価、Ｔｇである。
また、表中のＥＥＰと酢酸ブチルとは溶剤として使用した。
(Abbreviation of compound etc.)
Fluoropolymer solution 1: Lumiflon LF9716 (hydroxyl value 162 mgKOH/g, Tg 40°C fluoropolymer, xylene solution with 70% solid content, AGC product)
Fluoropolymer solution 2: Lumiflon LF9721 (hydroxyl value 170 mgKOH/g, Tg 30°C fluoropolymer, xylene solution with solid content concentration of 70%, product of AGC Co.)
Polyester resin 1: Nipporan 1100 (hydroxyl value 213 mgKOH/g, acid value 4 mgKOH/g, product of Tosoh Corporation)
Polyester resin 2: FLEXOREZ 148 (hydroxyl value 235 mg KOH/g, KING INDUSTRIES company product)
Polyester resin 3: FLEXOREZ 188 (hydroxyl value 230 mgKOH/g, KING INDUSTRIES company product)
Inorganic particles: NYAD 400 (wollastonite having aspect ratio 3, average major axis 27 μm, Mohs hardness 4.5, product of NYCO)
Dispersant: DisperBYK-110 (product of Big Chemie Japan)
EEP: Ethoxyethyl propionate Defoaming agent: Disparlon 1993 (Kusumoto Kasei Co. product)
Pigment: Taipaque PFC105 (product of Ishihara Sangyo Co., Ltd.)
Curing catalyst: dibutyltin dilaurate UV absorber: TINUVIN 384-2 (BASF product)
Light stabilizer: TINUVIN 123 (BASF product)
Thickener: Flownon SP-1000 (product of Kyoeisha Chemical Co., Ltd.)
The hydroxyl value and Tg described in the fluoropolymer solutions 1 and 2 are the hydroxyl value and Tg of the fluoropolymer contained in each solution.
Moreover, EEP and butyl acetate in the table were used as solvents.
（塗料の製造）
表１の組成物１欄に記載の成分をビーズミルにて混合した後、表１の組成物２欄に記載の成分を添加し、ディスパーにて混合した。得られた混合溶液の全質量に対して２０質量％の硬化剤（デュラネートＴＰＡ−１００、ＨＤＩ系イソシアネート、旭化成社製）を添加して混合し、各例の塗料を得た。
(Manufacture of paint)
After the components listed in the first column of composition in Table 1 were mixed with a bead mill, the components listed in the second column of composition of Table 1 were added and mixed with a disper. 20% by mass of a curing agent (duranate TPA-100, HDI-based isocyanate, manufactured by Asahi Kasei Co., Ltd.) was added to and mixed with the total mass of the obtained mixed solution to obtain a coating material of each example.
（塗膜の製造）
各例の塗料を、１００ｍｍ×２００ｍｍのＦＲＰ（Ｆｉｂｅｒ Ｒｅｉｎｆｏｒｃｅｄ Ｐｌａｓｔｉｃｓ）基材にエアースプレーを用いて２回塗布した後、２３℃にて７日間乾燥させて、乾燥膜厚８０μｍの塗膜を形成して、各例の塗料からなる塗膜を有する塗膜付き基材を得て試験片Ａとし、後述の通り評価した。
また、各例の塗料を、１４０ｍｍ×２５０ｍｍのアート紙に６ｍｉｌのアプリケータを用いて塗布した後、１２０℃にて１０分乾燥させて乾燥膜厚８０μｍの塗膜を形成して、各例の塗料からなる塗膜を有する塗膜付き基材を得て試験片Ｂとし、後述の通り評価した。
(Production of coating film)
The coating material of each example was applied twice to a 100 mm×200 mm FRP (Fiber Reinforced Plastics) substrate using an air spray, and then dried at 23° C. for 7 days to form a coating film having a dry film thickness of 80 μm. Then, a coated substrate having a coating composed of the coating material of each example was obtained as a test piece A and evaluated as described below.
In addition, the coating material of each example was applied to 140 mm×250 mm art paper using a 6 mil applicator, and then dried at 120° C. for 10 minutes to form a coating film having a dry film thickness of 80 μm. A coated substrate having a coating film made of a paint was obtained as a test piece B and evaluated as described below.
（分散度の確認）
各例の塗料について、ＪＩＳ Ｋ ５６００−２−５に記載の方法に従ったグラインドゲージによる粒状法で、分散度を測定した。顕著なはん点が現れ始める点を、各例の塗料の分散度（μｍ）とした。
(Check dispersion)
The degree of dispersion of the coating material of each example was measured by the granular method using a grind gauge according to the method described in JIS K 5600-2-5. The point at which remarkable spots started to appear was defined as the dispersity (μm) of the paint of each example.
（評価方法）
［耐浸食性］
試験片Ａに対し、ブラスト処理装置を用いて、研削材としてアルミナ Ａ４６を圧力０．４５ＭＰａにて射出して、塗膜の耐浸食性を以下の基準によって評価した。
試験片Ａは、投入口からコンベア上に投入された後、コンベア速度１０ｃｍ／分で一定方向にブラスト機内を通過させた。この際に、コンベアの進行方向に対して直列に配置した６本の射出ノズルから塗膜に向けて研削剤を射出した。これにより、研削材が塗膜に衝突して生じる塗膜の浸食の有無を目視により確認した。なお、ブラスト機を通過し終わるまでを１サイクルとした。
Ａ：２サイクル実施後にも塗膜に異常はない（基材の露出が見られなかった）。
Ｂ：１サイクル実施後には塗膜に異常がなく、２サイクル実施後には基材の一部が露出している。
Ｃ：１サイクル実施後に基材の一部が露出している。
(Evaluation method)
[Erosion resistance]
Alumina A46 was injected as a grinding material at a pressure of 0.45 MPa to the test piece A using a blasting device, and the erosion resistance of the coating film was evaluated according to the following criteria.
The test piece A was loaded on the conveyor through the loading port and then passed through the blast machine in a fixed direction at a conveyor speed of 10 cm/min. At this time, the abrasive was injected toward the coating film from six injection nozzles arranged in series with respect to the traveling direction of the conveyor. Thereby, the presence or absence of erosion of the coating film caused by the abrasive material colliding with the coating film was visually confirmed. It should be noted that one cycle was taken to complete the passage through the blast machine.
A: There is no abnormality in the coating film even after two cycles have been carried out (no exposure of the substrate was observed).
B: There is no abnormality in the coating film after one cycle is performed, and a part of the substrate is exposed after two cycles.
C: A part of the base material is exposed after one cycle.
［塗膜外観］
試験片Ｂの塗膜外観を、目視により以下の基準によって評価した。
Ａ：塗膜が平滑でブツ等の異常がない。
Ｂ：塗膜が平滑でないか、ブツ等が認められる
[Appearance of coating film]
The coating film appearance of the test piece B was visually evaluated according to the following criteria.
A: The coating film is smooth and has no abnormalities such as spots.
B: The coating film is not smooth, or spots are observed.
［耐候性］
試験片Ａに対し、サンシャインウェザーメーター（スガ試験機社製）を用いて、ＪＩＳ Ｂ ７７５３：２００７に準拠し、４，０００時間の促進耐候性試験を行った。
試験開始前の塗膜の６０度鏡面光沢値の初期値を１００％としたときの試験後の塗膜の６０度鏡面光沢値の保持率（光沢保持率）（％）を、光沢計（商品名「ＵＧＶ−６Ｐ」、スガ試験機社商品）を用いて測定した。また、試験後の塗膜と試験前の塗膜との色差を、分光測色計（商品名「ＣＭ−５」、コニカミノルタ社商品）を用いて測定した。
なお、上記色差は下記計算式によって求めた。
色差（ΔＥ＊ａｂ）＝[（ΔＬ＊）２＋（Δａ＊）２＋（Δｂ＊）２]１/２
ΔＬ＊＝試験後の塗膜のＬ＊値−試験前の塗膜のＬ＊値
Δａ＊＝試験後の塗膜のａ＊値−試験前の塗膜のａ＊値
Δｂ＊＝試験後の塗膜のｂ＊値−試験前の塗膜のｂ＊値
[Weatherability]
A sunshine weather meter (manufactured by Suga Test Instruments Co., Ltd.) was used for the test piece A, and an accelerated weather resistance test was performed for 4,000 hours in accordance with JIS B 7753:2007.
The retention rate (gloss retention rate) (%) of the 60-degree specular gloss value of the coating film after the test when the initial value of the 60-degree specular gloss value of the coating film before the test was set to 100% was measured by a gloss meter (product. The measurement was performed using the name "UGV-6P", a product of Suga Test Instruments Co., Ltd.). In addition, the color difference between the coating film after the test and the coating film before the test was measured using a spectrocolorimeter (trade name "CM-5", a product of Konica Minolta Co., Ltd.).
The color difference was calculated by the following formula.
Color difference (ΔE * ab)=[(ΔL * ) 2 +(Δa * ) 2 +(Δb * ) 2 ] 1/2
ΔL * = L * value of the coating film after the test - L * value of the coating film before the test
Δa * = a * value of the coating film after test - a * value of the coating film before the test
Δb * = b * value of the coating film after test - b * values of the paint film before the test
試験前後の塗膜の光沢保持率を、以下の基準によって評価した。
Ａ：塗膜の光沢保持率が８０％以上である。
Ｂ：塗膜の光沢保持率が８０％未満６０％以上である。
Ｃ：塗膜の光沢保持率が６０％未満である。
The gloss retention of the coating film before and after the test was evaluated according to the following criteria.
A: The gloss retention of the coating film is 80% or more.
B: The gloss retention of the coating film is less than 80% and 60% or more.
C: The gloss retention of the coating film is less than 60%.
試験前後の塗膜の色差を、以下の基準によって評価した。
Ａ：塗膜のΔＥ＊ａｂが３．００以下である。
Ｂ：塗膜のΔＥ＊ａｂが３．００超５．００以下である。
Ｃ：塗膜のΔＥ＊ａｂが５．００超である。
The color difference of the coating film before and after the test was evaluated according to the following criteria.
A: The ΔE * ab of the coating film is 3.00 or less.
B: The ΔE * ab of the coating film is more than 3.00 and 5.00 or less.
C: ΔE * ab of the coating film is more than 5.00.
結果をまとめて表１に示す。
表１中、「無機粒子含有量（質量部）」の欄は、塗料中における、含フッ素重合体とポリエステルとの合計質量１００質量部に対する、モース硬度が３．０〜５．０の無機粒子の含有量（質量部）を意味する。
The results are summarized in Table 1.
In Table 1, the column of "inorganic particle content (parts by mass)" is an inorganic particle having a Mohs hardness of 3.0 to 5.0 with respect to 100 parts by mass of the total weight of the fluoropolymer and the polyester in the coating material. Means the content (parts by mass) of.
表に示す結果より、本発明の塗料を用いて形成される塗膜は、耐浸食性に優れることが確認された。 From the results shown in the table, it was confirmed that the coating film formed using the coating material of the present invention had excellent erosion resistance.
１１ ブレード
１２ 塗膜
１２Ａ 塗布層
１０１ 風力発電機
１１０、１４０ 塔体
１２０、１５０ 塔頂回動部
１３０、１６０ 風力発電機の塗膜付きブレード
１７０ 風力発電機の集風体
11 blade 12 coating film 12A coating layer 101 wind power generator 110, 140 tower body 120, 150 tower top rotating part 130, 160 blade with coating film of wind power generator 170 wind collector of wind power generator
Claims (12)
前記無機粒子の含有量が、前記含フッ素重合体と前記ポリエステルとの合計１００質量部に対して、２０〜６０質量部であり、
タービンが有するブレード又は航空機の翼に塗布して用いられることを特徴とする、塗料。 A coating material containing a fluoropolymer, polyester, and inorganic particles having a Mohs hardness of 3.0 to 5.0,
The content of the inorganic particles is 20 to 60 parts by mass based on 100 parts by mass of the total amount of the fluoropolymer and the polyester,
A paint, which is used by being applied to a blade of a turbine or a wing of an aircraft.
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| WO2023074316A1 (en) * | 2021-10-29 | 2023-05-04 | 東レ株式会社 | Hollow structure and propeller blade |
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