CN100413601C - 涂料组合物 - Google Patents
涂料组合物 Download PDFInfo
- Publication number
- CN100413601C CN100413601C CNB018068456A CN01806845A CN100413601C CN 100413601 C CN100413601 C CN 100413601C CN B018068456 A CNB018068456 A CN B018068456A CN 01806845 A CN01806845 A CN 01806845A CN 100413601 C CN100413601 C CN 100413601C
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- China
- Prior art keywords
- priming paint
- weight
- component
- paint
- weights
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000008199 coating composition Substances 0.000 title description 10
- 230000037452 priming Effects 0.000 claims abstract description 81
- 238000000034 method Methods 0.000 claims abstract description 49
- 239000000049 pigment Substances 0.000 claims abstract description 31
- 230000005855 radiation Effects 0.000 claims abstract description 31
- 239000000945 filler Substances 0.000 claims abstract description 12
- 239000000654 additive Substances 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 239000000975 dye Substances 0.000 claims abstract description 8
- 239000003973 paint Substances 0.000 claims description 117
- 238000000576 coating method Methods 0.000 claims description 45
- 239000000203 mixture Substances 0.000 claims description 43
- 239000011248 coating agent Substances 0.000 claims description 40
- 238000003801 milling Methods 0.000 claims description 27
- 239000004576 sand Substances 0.000 claims description 27
- 239000002904 solvent Substances 0.000 claims description 15
- -1 acyl group phosphine oxides Chemical class 0.000 claims description 11
- 230000007797 corrosion Effects 0.000 claims description 11
- 238000005260 corrosion Methods 0.000 claims description 11
- 239000004927 clay Substances 0.000 claims description 9
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 claims description 9
- 230000002401 inhibitory effect Effects 0.000 claims description 7
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 238000003847 radiation curing Methods 0.000 claims description 6
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical group C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 claims description 5
- 239000000443 aerosol Substances 0.000 claims description 5
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 3
- 239000006254 rheological additive Substances 0.000 claims description 3
- 238000009736 wetting Methods 0.000 claims description 3
- 239000005083 Zinc sulfide Substances 0.000 claims description 2
- 239000003380 propellant Substances 0.000 claims description 2
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 description 17
- 239000002184 metal Substances 0.000 description 17
- 230000008439 repair process Effects 0.000 description 17
- 244000137852 Petrea volubilis Species 0.000 description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
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- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
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- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 4
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- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
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- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
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- 229910000831 Steel Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
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- 238000007796 conventional method Methods 0.000 description 2
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- 238000011156 evaluation Methods 0.000 description 2
- 230000001815 facial effect Effects 0.000 description 2
- 239000008397 galvanized steel Substances 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
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- 238000007711 solidification Methods 0.000 description 2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 2
- 229910000165 zinc phosphate Inorganic materials 0.000 description 2
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 description 1
- GZBSIABKXVPBFY-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)CO GZBSIABKXVPBFY-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- LVGFPWDANALGOY-UHFFFAOYSA-N 8-methylnonyl prop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C=C LVGFPWDANALGOY-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 101100256368 Arabidopsis thaliana SBP3 gene Proteins 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- 229910000611 Zinc aluminium Inorganic materials 0.000 description 1
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- SSOONFBDIYMPEU-UHFFFAOYSA-N [3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propyl] prop-2-enoate Chemical compound OCC(CO)(CO)COCC(CO)(CO)COC(=O)C=C SSOONFBDIYMPEU-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
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- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
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- QBLDFAIABQKINO-UHFFFAOYSA-N barium borate Chemical compound [Ba+2].[O-]B=O.[O-]B=O QBLDFAIABQKINO-UHFFFAOYSA-N 0.000 description 1
- 239000010428 baryte Substances 0.000 description 1
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- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
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- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
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- 229940119545 isobornyl methacrylate Drugs 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
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- 239000010445 mica Substances 0.000 description 1
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- 239000000178 monomer Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
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- 238000010526 radical polymerization reaction Methods 0.000 description 1
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- NVKTUNLPFJHLCG-UHFFFAOYSA-N strontium chromate Chemical compound [Sr+2].[O-][Cr]([O-])(=O)=O NVKTUNLPFJHLCG-UHFFFAOYSA-N 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/52—Two layers
- B05D7/53—Base coat plus clear coat type
- B05D7/536—Base coat plus clear coat type each layer being cured, at least partially, separately
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/10—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by other chemical means
- B05D3/107—Post-treatment of applied coatings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- 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
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
- B05D3/061—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation using U.V.
- B05D3/065—After-treatment
- B05D3/067—Curing or cross-linking the coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/12—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by mechanical means
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31511—Of epoxy ether
- Y10T428/31515—As intermediate layer
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31511—Of epoxy ether
- Y10T428/31515—As intermediate layer
- Y10T428/31522—Next to metal
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31678—Of metal
Landscapes
- Chemical & Material Sciences (AREA)
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Abstract
公开了一种在表面(优选汽车部分)上涂底漆的方法,包括:i)在要涂底漆的区域涂布可UV辐射固化的底漆;ii)用UV-B∶UV-A之比为1∶1或更低而且基本上不含UV-C的一或多个UV灯提供的UV辐射使所述底漆固化,所述可UV辐射固化的底漆含有:A.0-84%(重)的一或多种每分子含一个可自由基聚合的烯属不饱和基的化合物;B.5-50%(重)的一或多种每分子含两或多个可自由基聚合的烯属不饱和基的化合物;C.10-70%(重)的一或多种颜料、填料和/或染料;D.1-8%(重)的一或多种光引发剂;E.0-20%(重)的挥发性有机溶剂;和F.0-15%(重)的常用添加剂。优选所述方法还包括:砂磨所述底漆并在所述底漆上涂布一或多种面漆。还公开了通过本发明方法处理的表面。
Description
本发明涉及一种在表面特别是汽车表面上涂底漆的方法,例如作为修补的一部分,其中
1.先涂布一种可辐射固化的底漆组合物,通过UV辐射使之固化,和
2.在所述底漆上面涂布一或多种面漆。
机动车修补上漆所用涂料一般包括几层不同的涂料组合物。最初涂层通常是底涂层。所述底涂层提供与基质的粘附力,所述基质可以是裸露金属,也可以是已存在的底漆或面漆或其混合物,取决于所述修补的性质。所述底漆也配制成提供较厚的涂层,可用砂纸或玻璃砂纸砂磨(也称为“平整”)从而涂掉基质中的小缺陷,为后续涂层提供完美的平表面。因而所述底漆通常含有颜料和/或填料使之易于砂磨。所述底涂层的厚度典型地为50至200μm。在所述底漆之上涂布面漆,面漆本身可包含多于一类涂料如底基涂层和透明涂层。
公知用于底漆的一类涂料组合物包括羟基官能的聚合物如聚酯或丙烯酸类聚合物、和多异氰酸酯。这两种组分涂于基质之后反应生成聚氨酯涂层。因此这些组合物常称为“聚氨酯涂料组合物”,但严格地说仅当所述涂料交联后才形成聚氨酯。此类聚氨酯底漆已经知道至少20年。
使用聚氨酯底漆的问题之一是在它们可被砂磨和涂面漆之前必须有足够长的时间使之固化。如果在它未充分固化之前砂磨和涂面漆,则砂磨很难且费时,所述面漆可能与底漆相互作用导致涂布制品的外观差。典型地在可砂磨和涂面漆之前,必须使底漆在环境温度下固化2-4小时。或者可在近60℃下烘烤约30分钟。这通常是不优选的,因为需利用通常用于固化面漆的宝贵烘烤空间。
聚氨酯底漆的第二个问题是它们含有较高含量的有机溶剂。由于环境问题,涂料工业的总趋势是溶剂含量减少的涂料组合物。降低溶剂含量的方法之一是使用所谓的高固含量组合物。高固含量组合物是溶剂基组合物,含有较高含量的非挥发物如成膜聚合物、颜料和填料及较低含量的有机溶剂。配制适用于涂布机动车的高固含量涂料组合物的问题在于所述组合物有不能接受的高粘度。这是因为此领域中传统使用的成膜聚合物在高固含量的溶液中溶液粘度很高。此高粘度在涂布过程中造成流出差因而外观差的问题。
聚氨酯底漆的第三个问题是存在以下缺点:已知多异氰酸酯是呼吸激敏物,因而使用时必须相当小心,特别是喷涂期间要防止操作者吸入涂料喷雾。这通常要求操作者戴供给空气的呼吸面具。显然是一类不理想的涂料。
聚氨酯底漆的第四个问题是涂于裸露金属时通常不能提供极好的耐湿性和耐腐蚀性。使用聚氨酯底漆之前需在金属上涂布单独的磷化底漆或粘合打底剂。这使完成修补所需时间进一步延长。
我们发现一种方法,利用可通过受到有极低UV-B含量和基本上无UV-C含量的UV辐射固化的底漆组合物。该方法可容易且安全地在典型的汽车修理车间内操作。所述底漆的涂布和固化过程中几乎不或不放出有机溶剂,而且所述底漆可在极短的时间周期内涂布和固化。甚至在没有单独的磷化底漆或粘合打底剂的情况下使用时,所述UV固化的底漆也提供极好的耐湿性和抗腐蚀性。
辐射固化的涂料组合物是公知的。1999年9月出版的EuropeanCoatings Journal,p21-49中概述了该领域的现状。应用大多限于在生产线上涂布的平基质。有时在惰性气氛下进行固化。
这与车辆修补的情况很不同。由熟练的工匠进行涂布,每次修补都不同,通常在用于进行固化的同一区域涂布所述涂料。适用于车辆修补的辐射固化涂料必须比上述文献中所述组合物更安全、更结实和适应性更强。此外,在车间当然很难在惰性气氛下操作。
已公开了一些用于车辆修补的辐射固化组合物,但没有完全满足上述要求的。
WO98 40170描述了一种涂料组合物,通过两种类型的交联固化。系统A可通过加成和/或缩合热固化,不含可自由基聚合的双键,系统B可通过自由基聚合固化,不能与系统A交联。该申请限于透明涂料组合物。
DE196 35 447描述了一种修补方法,涉及用脉冲式高能UV辐射使透明涂料或着色面漆固化。
GB2 226 566描述了一种用于汽车车身底部的涂料组合物。通过高能UV辐射使所述组合物固化。
以上文献均未公开涉及UV辐射固化的底漆而且能在不涉及贵重设备或安全措施使人员与固化区域隔绝的情况下在典型的车间操作的修补方法。
本发明提供一种在表面(优选汽车部分)上涂底漆的方法,包括:
i)在要涂底漆的区域涂布可UV辐射固化的底漆;
ii)用UV-B∶UV-A之比为1∶1或更低而且基本上不含UV-C的一或多个UV灯提供的UV辐射使所述底漆固化,
其中所述可UV辐射固化的底漆含有:
A.0-84%(重)的一或多种每分子含一个可自由基聚合的烯属不饱和基的化合物;
B.5-50%(重)的一或多种每分子含两或多个可自由基聚合的烯属不饱和基的化合物;
C.10-70%(重)的一或多种颜料、填料和/或染料;
D.1-8%(重)的一或多种光引发剂;
E.0-20%(重)的挥发性有机溶剂;和
F.0-15%(重)的常用添加剂。
本发明所述方法可以是一种修补方法,例如汽车的修补方法。修补是修复或重涂已经涂漆的表面例如汽车表面的方法。
优选所述方法还包括以下步骤:
iii)砂磨所述底漆并在所述底漆上涂布一或多种面漆。
给定辐射源的光谱输出可用包括单色仪和光检测器的能量色散摄谱仪测量,其在相关波长的灵敏度是已知的。通过各波长范围内光谱输出强度积分获得UB-B∶UV-A之比。适用仪器之一例是来自SpectralInstruments,Tucson Arizona,USA的440型光谱仪。
一般地,选择组分A的类型和含量使所述组合物具有适合的粘度并溶解组分B和D。组分A的选择和含量还影响所述涂料的硬度。组分C的类型和含量这样选择以使所述组合物有适合的粘度、柔韧性、硬度和耐溶剂性。优选组分A和组分B中的烯属不饱和基主要是丙烯酸基,因为这样导致固化速度快。
适用作组分A的化合物的例子是α-β不饱和脂族化合物如1-辛烯、1-己烯和1-癸烯、乙烯酯如乙酸乙烯酯、苯乙烯、取代的苯乙烯如α-甲基苯乙烯或对甲基苯乙烯、甲基丙烯酸酯和丙烯酸酯。优选组分A主要由丙烯酸烷基酯如丙烯酸丁酯、丙烯酸叔丁酯、丙烯酸异冰片酯、丙烯酸异癸酯、丙烯酸2-乙基己酯、丙烯酸月桂酯、丙烯酸环己酯和丙烯酸辛酯组成。更优选组分A主要由丙烯酸异冰片酯和/或丙烯酸2-乙基己酯组成。优选所述底漆含有5-50%(重)的组分A,更优选10-40%(重),甚至更优选25至35%(重)。
适用作组分B的化合物的例子包括二丙烯酸酯如己二醇二丙烯酸酯或三丙二醇二丙烯酸酯、三丙烯酸酯如三羟甲基丙烷三丙烯酸酯、烷氧基化三羟甲基丙烷三丙烯酸酯或季戊四醇三丙烯酸酯、多丙烯酸酯如季戊四醇四丙烯酸酯或二季戊四醇六丙烯酸酯、环氧丙烯酸酯(例如通过环氧化物与丙烯酸反应获得的)如来自Croda的UVE 100和UVE150或来自Akcros Chemicals的Actilane 320或Actilane 330、尿烷丙烯酸酯如来自UCB Chemicals的Ebecryl 264或来自AkcrosChemicals的Actilane 251、或不饱和聚酯如用马来酐作为单体组分之一制备的聚酯。优选组分B主要由一或多种环氧丙烯酸酯和/或一或多种尿烷丙烯酸酯组成,更优选组分B主要由一或多种环氧丙烯酸酯组成。优选所述底漆含有10-40%(重)组分B,更优选25至35%(重)。
原则上任何已知的颜料或填料均可用作组分C。可包括常用颜料如二氧化钛和氧化锌。
适用的填料包括粘土、重晶石、云母、滑石和碳酸钙。
组分C可包括已知抑制腐蚀的那些颜料如铬酸锶、磷酸锌和偏硼酸钡。
优选的颜料和填料是基本上不干扰所述自由基固化的那些。优选组分C主要由硫化锌、硫酸钡、陶土和防腐蚀颜料组成。更优选组分C主要由陶土和防腐蚀颜料组成。陶土是由沉积高岭土获得的水合硅酸铝。适用陶土之一例是来自ECC International的Speswhite陶土。
原则上选择颜料的类型和含量以达到极好的砂磨性和抗腐蚀性。优选选择颜料和填料的类型和含量使颜料体积浓度(PVC)达到10-50%、更优选15-25%。所述PVC是以百分率表示的颜料体积与总组合物中存在的非挥发性物质总体积之比。
含有优选颜料的底漆组合物通常是透明或半透明的。许多情况下希望在涂布过程中可估计涂层的厚度。方法之一是所述组合物中包含染料。适用的染料包括金属络合染料如来自BASF Aktiengesellschaft的范围。存在染料时,其存在量优选为总组合物的0.005-1%(重),更优选0.02-0.05%(重)。实现该效果的另一方式是在组合物中包括金属碎箔颜料。适用的金属碎箔颜料包括铝箔颜料如来自Eckart-Werke的Stappa范围。存在金属碎箔颜料时,其存在量优选为总组合物的0.1-10%(重),更优选0.25-1%(重)。
组分D可由受到UV-B∶UV-A之比为1∶1或更小的辐射时能产生自由基的任何光引发剂组成。优选所述光引发剂受到UV-B∶UV-A之比为0.2∶1或更小、更优选0.05∶1或更小、甚至更优选0.025∶1或更小的辐射时能产生自由基。一类优选的光引发剂是双酰基氧膦,例如来自Ciba的Irgacure 819。
优选所述底漆含有1-3%(重)组分D。
所述挥发性有机溶剂可以是溶解组分A、B、D和F的任何溶剂。可以是脂族或芳族烃如Solvesso 100TM、甲苯或二甲苯,醇如丁醇或异丙醇,酯如乙酸丁酯或乙酸乙酯,酮如丙酮、甲基异丁基酮或甲基乙基酮,醚,醚醇或醚酯如3-乙氧基丙酸乙酯或其混合物。优选为丙酮和/或甲基乙基酮和/或3-乙氧基丙酸乙酯。
所用溶剂的含量和类型取决于其它组分的粘度和涂布方法。一优选实施方案中,所述底漆不含挥发性有机溶剂。
所述底漆组合物可还含有常用添加剂如光协同剂(photosynergists)、增粘剂、颜料分散剂、助流剂、润湿助剂和流变改性剂。
一优选实施方案中,所述底漆含有:
25至35%(重)的丙烯酸异冰片酯和/或丙烯酸2-乙基己酯,
25至35%(重)的环氧丙烯酸酯,
20至30%(重)的陶土,
5至15%(重)的防腐蚀颜料,
1至3%(重)的双酰基氧膦,
0.1至10%(重)的增粘剂、颜料分散剂、助流剂、润湿助剂和流变改性剂。
所述涂料组合物可通过常规手段如刷、辊、海绵、喷枪或气溶胶(优选刷或气溶胶)涂布。通过气溶胶涂布时,所述底漆组合物还包括一或多种喷射剂。所述基质可以是例如金属、塑料、木制品或玻璃。可通过涂布一或多遍达到适合的膜厚。
通过受到UV辐射使所述底漆组合物固化。涂布几遍时,可在每次涂布之后或仅在最后一次涂布之后使所述底漆固化。所述辐射的UV-B含量与UV-A含量之比为1∶1或更小。优选所述UV-B∶UV-A之比为0.2∶1或更小,更优选0.05∶1或更小,甚至更优选0.025∶1或更小。所述辐射基本上不含UV-C。UV-A辐射是落入320-400nm波长范围内的任何辐射,UV-B辐射是落入280-320nm波长范围内的任何辐射,UV-C辐射是落入100-280nm波长范围内的任何辐射。
所述辐射可由任何适合的UV灯提供,优选所述灯这样放置使之与底漆表面的距离在5和60cm之间。更优选所述灯这样放置使之与底漆表面的距离为10至30cm。
优选使所述底漆受到UV辐射30秒至10分钟,更优选1至3分钟。
涂面漆之前可用砂纸或玻璃纸砂磨所述底漆。
在任选地进行或不进行砂磨和涂面漆之前优选用挥发性有机清洗溶剂擦拭所述底漆表面除去任何粘附的未固化表面层。所述挥发性有机清洗溶剂可以是脂族或芳族烃如Solvesso 100TM、甲苯或二甲苯,醇如丁醇或异丙醇,酯如乙酸丁酯或乙酸乙酯,酮如丙酮、甲基异丁基酮或甲基乙基酮,醚,醚醇或醚酯或这些溶剂的混合物。优选为一或多种石油馏出物如购自Carless Refing and Marketing的SBP范围。
可用任何适合的修补体系在所述底漆上涂布面漆以获得要求的最终颜色和外观。例如,可用水性底涂料如购自ICI Autocolor的Aquabase P965 Line涂布所述底漆,然后涂布溶剂基双组分聚氨酯透明涂料如购自ICI Autocolor的P190-670。也可在其上涂布溶剂基底涂料如购自ICI Autocolor的2K P422 Line,然后涂布溶剂基双组分聚氨酯透明涂料如购自ICI Autocolor的P190-643。也可在其上涂布单层溶剂基双组分聚氨酯面漆如购自ICI Autocolor的2K HS PlusP471 Line。
所述方法特别适用于但不限于损坏汽车的局部修理。局部修理意指汽车面板的小面积通常小于40cm2的损坏修理。
本发明还提供通过本发明方法涂布或部分涂布的表面。
现通过以下实施例说明本发明。
实施例I-VI
底漆组合物
按以下方法制备表1中所示底漆配方I-VI。
将组分A和B及溶剂全部加入适合的容器中,搅拌至均匀。然后在搅拌下加入光引发剂和分散剂。需要时使混合物的温度升至不高于80℃以形成透明的均匀混合物。
然后将所述容器移至高速分散器中。在搅拌下缓慢加入增量剂。加完后,继续分散直至达到50-60μm的研细度(约30分钟)。然后加入任何增粘剂,将所述底漆缓慢地搅拌5分钟。
表1
上表中所有量均为重量份。
UVE 150 Crodamer UVE 150-购自Croda的环氧丙烯酸酯
UVU 316 Crodamer UVU 316-购自Croda的尿烷丙烯酸酯
UVS 500 Crodamer UVS 500-购自Croda的硅氧烷丙烯酸酯
SR 349购自Sartomer的环氧丙烯酸酯
500A Roskydal 500A-购自Bayer plc的不饱和聚酯
SR 9050购自Sartomer的酸性增粘剂
E 170 Ebecryl 170-购自UCB Chemicals的酸性增粘剂
IBoMa 甲基丙烯酸异冰片酯
EHA 丙烯酸2-乙基己酯
Byk 116购自Byk的颜料分散剂
S24 000 Solsperse 24 000-购自Avecia的颜料分散剂
I149 Irgacure 149-购自Ciba的光引发剂
I819 Irgacure 819-购自Ciba的光引发剂
D4265 Darocur 4265-购自Ciba的光引发剂
防腐蚀颜料 磷酸锌/铝防腐蚀颜料
实施例I-VI
用150微米滑块展涂机(blockspreader)将底漆组合物I-VI涂于干净的玻璃板上。然后受到由UV H253 UV灯(购自UV LightTechnologies-该装置包含配有黑玻璃滤光镜的250W掺铁金属卤化物灯提供在320和400nm之间的UV-A输出光谱)提供的UV辐射1分钟使所述涂料固化。灯与面板的距离为20cm。用等重量份数的SBP3和SBP6(购自Carless Refining and Marketing)的混合物擦拭之后,所述底漆都容易用P360砂纸砂磨。
测试面板的制备
在几块约45cm×45cm的钢板上涂布20-25微米无铬环氧粘附底漆P565-895(购自ICI Autocolor,按产品数据表上的说明使用),然后涂布100-120微米底漆填料/二道底漆P565-481(购自ICIAutocolor,按产品数据表上的说明使用)。将所述面板在60℃烘烤30分钟,然后用P360砂纸砂磨。
使100重量份Aquabase中粗铝基P968-9987与10.3重量份Aquabase活化剂P935-2018和3重量份Aquabase添加剂稀释剂P275-366(均购自ICI Autocolor)混合。将其涂于全部面板上形成12-15微米的膜。用P190-670透明涂料(购自ICI Autocolor,按数据表上的说明使用)涂布这些面板。然后使所述面板老化1周。
老化后,用P120砂纸从各面板的中心区除去约25cm2的油漆。用这样制备的测试面板模拟局部修理过程。
实施例VII
以下实施例代表在汽车修理车间用于修补小面积损坏油漆的过程。
本发明UV法
使100重量份表1的底漆组合物I与10重量份丙酮混合。然后喷涂在所制测试面板的暴露金属和小面积周围油漆上形成100-120微米的干膜。使所述底漆组合物闪蒸5分钟,然后通过受到由UV H253 UV灯(购自UV Light Technologies-该装置包含配有黑玻璃滤光镜的250W掺铁金属卤化物灯提供在320和400nm之间的UV-A输出光谱)提供的UV辐射1分钟使之固化。灯与面板的距离为20cm。照射后用酒精擦拭剂P850-1402(购自ICI Autocolor)擦拭所述底漆,然后用P360砂纸砂磨所述面板。砂磨后,裸露金属上的底漆膜为约100微米,所述底漆至周围油漆的过渡平滑。
使100重量份Aquabase中粗铝基P968-9987与10.3重量份Aquabase活化剂P935-2018和3重量份Aquabase添加剂稀释剂P275-366(均购自ICI Autocolor)混合。将其涂于全部面板上形成12-15微米的膜。用P190-670透明涂料(购自ICI Autocolor,按数据表上的说明使用)涂布所述面板,将所述面板在60℃烘烤30分钟。每隔一周仔细研究所述面板的外观。光泽和图像界限极好,不能确定已进行修补。涂布所述底漆和开始涂布所述Aquabase之间的时间是18分钟。
传统方法
将无铬的环氧粘附底漆P565-895(购自ICI Autocolor,按产品数据表上的说明使用)喷涂在所制测试面板的暴露金属和小面积周围油漆上形成20-25微米的干膜。5分钟后,将Fast Hi-buildFiller/Surfacer P565-481(购自ICI Autocolor,按产品数据表上的说明使用)涂于稍大面积得到100-120微米的膜。需要涂布三遍,每遍之间闪蒸3分钟。将所述面板在60℃烘烤25分钟,冷却后,用P360砂纸砂磨。砂磨后,裸露金属上的底漆膜为约100微米,所述底漆至周围油漆为平滑过渡。
使100重量份Aquabase中粗铝基P968-9987与10.3重量份Aquabase活化剂P935-2018和3重量份Aquabase添加剂稀释剂P275-366(均购自ICI Autocolor)混合。将其涂于全部面板上形成12-15微米的膜。用P190-670透明涂料(购自ICI Autocolor,按数据表上的说明使用)涂布所述面板,将所述面板在60℃烘烤30分钟。每隔一周仔细研究所述面板的外观。光泽和图像界限极好,不能确定已进行修补。涂布所述底漆和开始涂布所述Aquabase之间的时间是50分钟。
实施例VIII
以下实施例代表在没有适合热源的汽车修理车间用于修补小面积损坏油漆的过程。
本发明UV法
使表1的底漆组合物I涂布在所制测试面板的暴露金属和小面积周围油漆上形成100-120微米的干膜。所述涂布用专业品质的纯猪鬃毛刷进行。通过受到由UV H253 UV灯(购自UV Light Technologies-该装置包含配有黑玻璃滤光镜的250W掺铁金属卤化物灯提供在320和400nm之间的UV-A输出光谱)提供的UV辐射1分钟使所述底漆组合物固化。灯与面板的距离为20cm。照射后用酒精擦拭剂P850-1402(购自ICI Autocolor)擦拭所述底漆,然后用P360砂纸砂磨所述面板。砂磨后,裸露金属上的底漆膜为约100微米,所述底漆至周围油漆为平滑过渡。
使100重量份Aquabase中粗铝基P968-9987与10.3重量份Aquabase添加剂活化剂P935-2018和3重量份Aquabase稀释剂P275-366(均购自ICI Autocolor)混合。将其涂于全部面板上形成12-15微米的膜。用P190-670透明涂料(购自ICI Autocolor,按数据表上的说明使用)涂布所述面板,将所述面板在环境温度下干燥过夜。每隔一周仔细研究所述面板的外观。光泽和图像界限极好,不能确定已进行修补。涂布所述底漆和开始涂布所述Aquabase之间的时间是13分钟。
传统方法
将IK Etch Primer Aerosol P565-908(购自ICI Autocolor,按产品数据表上的说明使用)喷涂在所制测试面板的暴露金属和小面积周围油漆上形成20-25微米的干膜。5分钟后,将Fast Hi-buildFiller/Surfacer P565-481(购自ICI Autocolor,按产品数据表上的说明使用)涂于稍大面积得到100-120微米的膜。需要涂布三遍,每遍之间闪蒸3分钟。将所述面板在环境温度下干燥4小时,然后用P360砂纸砂磨。砂磨后,裸露金属上的底漆膜为约100微米,所述底漆至周围油漆为平滑过渡。
使100重量份Aquabase中粗铝基P968-9987与10.3重量份Aquabase活化剂P935-2018和3重量份Aquabase添加剂稀释剂P275-366(均购自ICI Autocolor)混合。将其涂于全部面板上形成12-15微米的膜。用P190-670透明涂料(购自ICI Autocolor,按数据表上的说明使用)涂布所述面板,将所述面板在60℃烘烤30分钟。每隔一周仔细研究所述面板的外观。光泽和图像界限极好,不能确定已进行修补。涂布所述底漆和开始涂布所述Aquabase之间的时间是260分钟。
实施例IX
如下研究按本发明制备的修补涂层的薄膜性能。
A.在镀锌钢板上的粘附力和耐湿性
将四块镀锌钢板用P120砂纸轻轻砂磨,用松节油擦拭。然后在两块板上涂布20-25微米的无铬环氧粘附底漆P565-895(购自ICIAutocolor,按产品数据表上的说明使用),再涂100-120微米的底漆填料/二道底漆P565-481(购自ICI Autocolor,按产品数据表上的说明使用)。将所述面板在60℃下烘烤30分钟,然后用P360砂纸砂磨。
使100重量份表1的底漆组合物I与10重量份丙酮混合。然后喷涂在其它面板上形成100-120微米的干膜。通过受到由PhillipsHB171面部日光浴室提供的UV辐射2分钟使所述底漆组合物固化。灯与面板之间的距离为10cm。辐射后,用酒精擦拭剂P850-1402(购自ICI Autocolor)擦拭所述底漆,然后用P360砂纸砂磨。
使100重量份Aquabase中粗铝基P968-9987与10.3重量份Aquabase活化剂P935-2018和3重量份Aquabase添加剂稀释剂P275-366(均购自ICI Autocolor)混合。将其涂于全部面板上形成12-15微米的膜。然后用P190-670透明涂料(购自ICI Autocolor,按数据表上的说明使用)涂布所述面板。所有面板都有极好的外观,经过1个月没有可辨别的外观损坏。用涂有每种底漆的面板之一在涂布后一天、一周和一个月按ASTM D3359测量划格法粘附力。其它面板在室温下放置一周,然后在38℃的水中浸泡10天。浸泡3、7和10天后评定外观和划格法粘附力。结果示于表2中。
表2
结果表明在没有单独的粘附底漆的情况下所述UV固化的底漆的性能至少与有所述粘附底漆的传统底漆一样好。
B.在裸钢板上的粘附力和耐湿性
将四块冷轧钢测试面板用P120砂纸轻轻砂磨,用松节油擦拭。然后在两块板上涂布20-25微米的无铬磷化底漆P565-713(购自ICIAutocolor,按产品数据表上的说明使用),再涂100-120微米的FastHi-build Filler/Surfacer P565-888(购自ICI Autocolor,按产品数据表上的说明使用)。将所述面板在60℃下烘烤30分钟,然后用P360砂纸砂磨。
使100重量份表1的底漆组合物III与10重量份丙酮混合。然后喷涂在其它面板上形成100-120微米的干膜。通过受到由PhillipsHB171面部日光浴室提供的UV辐射2分钟使所述底漆组合物固化。灯与面板之间的距离为10cm。辐射后,用酒精擦拭剂P850-1402(购自ICI Autocolor)擦拭所述底漆,然后用P360砂纸砂磨。
用2份(体积)Standard Medium Temperature Hardener P210-770使4份(体积)2K Super White Basic P425-900活化,用0.5份(体积)Low VOC Medium Thinner P850-1693(均购自ICI Autocolor)稀释。将其涂于全部面板上形成约50微米的膜。所有面板都有极好的外观,经过1个月没有可辨别的外观损坏。用涂有每种底漆的面板之一在涂布后一天、一周和一个月按ASTM D3359测量划格法粘附力。其它面板在室温下放置一周,然后在38℃的水中浸泡10天。浸泡3、7和10天后评定外观和划格法粘附力。结果示于表3中。
表3
结果表明在没有单独的粘附底漆的情况下所述UV固化的底漆的性能至少与有所述粘附底漆的传统底漆一样好。
Claims (24)
1. 一种在表面上涂底漆的方法,包括:
i)在要涂底漆的区域涂布可UV辐射固化的底漆;
ii)用UV-B∶UV-A之比为1∶1或更低的一或多个UV灯提供的UV辐射使所述底漆固化,
其中所述可UV辐射固化的底漆含有:
A.0-84%(重)的一或多种每分子含一个可自由基聚合的烯属不饱和基的化合物;
B.5-50%(重)的一或多种每分子含两或多个可自由基聚合的烯属不饱和基的化合物;
C.10-70%(重)的一或多种颜料、填料和/或染料;
D.1-8%(重)的一或多种光引发剂;
E.0-20%(重)的挥发性有机溶剂;和
F.0-10%(重)的常用添加剂。
2. 权利要求1的方法,还包括:
iii)砂磨所述底漆并在所述底漆上涂布一或多种面漆。
3. 权利要求2的方法,其中在固化之后并在砂磨和涂面漆之前用溶剂擦拭所述表面。
4. 权利要求1、2或3的方法,其中所述UV灯的UV-B∶UV-A之比为0.2∶1或更低。
5. 权利要求1、2或3的方法,其中所述UV灯的UV-B∶UV-A之比为0.05∶1或更低。
6. 权利要求1、2或3的方法,其中所述UV灯的UV-B∶UV-A之比为0.025∶1或更低。
7. 权利要求1、2或3的方法,其中组分C主要由硫化锌、硫酸钡、陶土和防腐蚀颜料和/或其它UV透明或半透明的颜料或染料组成。
8. 权利要求1、2或3的方法,其中所述底漆有10至50%的PVC。
9. 权利要求1、2或3的方法,其中组分D包括双酰基氧膦。
10. 权利要求1、2或3的方法,其中所述底漆不含挥发性有机溶剂。
11. 权利要求1、2或3的方法,其中组分A和/或组分B含有丙烯酸酯基。
12. 权利要求1、2或3的方法,其中组分A主要是丙烯酸异冰片酯和/或丙烯酸2-乙基己酯。
13. 权利要求1、2或3的方法,其中组分B主要由一或多种环氧丙烯酸酯和/或一或多种尿烷丙烯酸酯组成。
14. 权利要求1、2或3的方法,其中组分B主要是环氧丙烯酸酯。
15. 权利要求1、2或3的方法,其中所述表面是机动车的一部分。
16. 权利要求1、2或3的方法,其中所述可固化的底漆包含5至50%(重)的组分A。
17. 权利要求1、2或3的方法,其中所述可固化的底漆包含10至40%(重)的组分A。
18. 权利要求1、2或3的方法,其中所述可固化的底漆包含25至35%(重)的组分A。
19. 权利要求1、2或3的方法,其中所述底漆包含10至40%(重)的组分B。
20. 权利要求1、2或3的方法,其中所述底漆包含25至35%(重)的组分B。
21. 权利要求1、2或3的方法,其中所述底漆包含:
25至35%(重)的丙烯酸异冰片酯和/或丙烯酸2-乙基己酯,
25至35%(重)的环氧丙烯酸酯,
20至30%(重)的陶土,
5至15%(重)的防腐蚀颜料,
1至3%(重)的双酰基氧膦,
0.1至10%(重)的增粘剂、颜料分散剂、助流剂、润湿助剂和流变改性剂。
22. 权利要求1、2或3的方法,其中用气溶胶涂布所述底漆,所述底漆组合物还包括一或多种喷射剂。
23. 权利要求1、2或3的方法,是一种修补方法。
24. 通过上述权利要求之任一所述方法处理的表面。
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Families Citing this family (34)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001040386A2 (en) * | 1999-12-06 | 2001-06-07 | Krohn Industries, Inc. | Uv curable compositions for producing multilayer pain coatings |
US7361383B2 (en) † | 2001-06-04 | 2008-04-22 | E.I. Dupont De Nemours & Company | Process for multilayer coating of substrates |
DE10202565A1 (de) * | 2002-01-24 | 2003-08-07 | Basf Coatings Ag | Gehärtete Materialien, Verfahren zu ihrer Herstellung und ihre Verwendung |
US20060052539A1 (en) | 2002-08-22 | 2006-03-09 | Mitsubishi Rayon Co., Ltd. | Primer composition for coating |
US20040254257A1 (en) | 2003-06-10 | 2004-12-16 | Laginess Thomas J. | Coating composition curable with ultraviolet radiation |
US7399793B2 (en) * | 2003-10-31 | 2008-07-15 | Basf Corporation | Coating composition curable with ultraviolet radiation |
US20050096427A1 (en) * | 2003-10-31 | 2005-05-05 | Basf Ag, | Ultraviolet radiation curable clearcoat composition with low color and good durability |
US7294656B2 (en) * | 2004-01-09 | 2007-11-13 | Bayer Materialscience Llc | UV curable coating composition |
US20050238815A1 (en) * | 2004-04-27 | 2005-10-27 | Dvorchak Michael J | UV curable coating composition |
US20060025522A1 (en) * | 2004-07-30 | 2006-02-02 | Johnson Jeffery W | High solids primer composition based on thermal initiated free-radical polymerization |
US7268172B2 (en) * | 2004-10-15 | 2007-09-11 | Bayer Materialscience Llc | Radiation curable compositions |
GB2432839B (en) * | 2004-10-18 | 2009-10-14 | New Lake Internat Ltd | A coating composition |
US7956098B2 (en) * | 2005-04-12 | 2011-06-07 | Bayer Materialscience Llc | Coating compositions containing ethylenically unsaturated polyurethanes as binders |
US7816418B2 (en) * | 2006-08-31 | 2010-10-19 | Ppg Industries Ohio, Inc. | Universal primer |
US7745010B2 (en) * | 2005-08-26 | 2010-06-29 | Prc Desoto International, Inc. | Coating compositions exhibiting corrosion resistance properties, related coated substrates, and methods |
US8231970B2 (en) * | 2005-08-26 | 2012-07-31 | Ppg Industries Ohio, Inc | Coating compositions exhibiting corrosion resistance properties and related coated substrates |
US8227050B1 (en) * | 2005-10-31 | 2012-07-24 | E I Du Pont De Nemours And Company | Coating composition and method for coating substrates |
US20070116866A1 (en) * | 2005-11-18 | 2007-05-24 | Basf Corporation | Quick method for repairing damage to a finish on a substrate |
US20090087671A1 (en) * | 2007-09-27 | 2009-04-02 | Ppg Industries Ohio, Inc. | Coating compositions exhibiting corrosion resistance properties and methods of coil coating |
PL2058343T3 (pl) * | 2007-11-08 | 2012-05-31 | Arkema Coatings Resins S A U | Kompozycja bezstyrenowej nienasyconej żywicy poliestrowej |
US20090176907A1 (en) * | 2008-01-08 | 2009-07-09 | Ramesh Subramanian | Direct-to-metal radiation curable compositions |
CA2644766C (en) | 2008-11-21 | 2016-01-12 | Honda Motor Co., Ltd. | Photoactivatable paint curing device and method |
US9701802B2 (en) * | 2009-04-08 | 2017-07-11 | Allnex Ip S.A.R.L. | Reinforced UV-A curable composite compositions and methods |
CA2672413C (en) | 2009-06-30 | 2012-11-20 | Honda Motor Co., Ltd. | Uv photoactivatable curable paint formulations and cured coatings thereof |
IN2012DN01796A (zh) * | 2009-08-31 | 2015-06-05 | Asahi Glass Co Ltd | |
CN102906206B (zh) | 2010-05-21 | 2016-06-22 | 湛新Ip有限公司 | 低光泽度的可辐射固化的组合物 |
CA2755151C (en) * | 2010-10-18 | 2014-06-17 | Valspar Sourcing, Inc. | Anti-graffiti coatings |
CN102101100A (zh) * | 2010-11-24 | 2011-06-22 | 李永霞 | 聚氯乙烯装饰片材制品表层的制作方法 |
US20160082473A1 (en) * | 2013-05-29 | 2016-03-24 | Cima Nanotech Israel Ltd. | Substrate pre-treating using photoinitiators |
CN104130674A (zh) * | 2014-07-29 | 2014-11-05 | 广西梧州龙鱼漆业有限公司 | 车用底漆 |
US10259010B2 (en) | 2014-08-29 | 2019-04-16 | Carmax Business Services, Llc | Devices, systems, and methods for curing a coating |
AU2017264964B2 (en) | 2016-05-13 | 2021-11-25 | MSI Coatings Inc. | System and method for using a VOC free low radiant flux LED UV curable composition |
US11338320B1 (en) * | 2018-02-03 | 2022-05-24 | MSI Coatings Inc. | Composition for aerosol cans, method of making and using the same |
WO2020131185A2 (en) | 2018-09-26 | 2020-06-25 | Dvorchak Enterprises Llc | One component uv curable compositions and methods for making same |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4668529A (en) * | 1985-04-12 | 1987-05-26 | Ronald L. Berry | Filler composition and method |
US4747013A (en) * | 1986-02-15 | 1988-05-24 | Licentia Patent-Verwaltungs Gmbh | Electrical capacitor with tearoff interrupter |
DE4336748A1 (de) * | 1992-11-17 | 1994-06-16 | Jordan Hch Lackfab Gmbh | Verfahren zur Blitztrocknung und Blitzhärtung und dafür geeignete Einrichtungen und strahlungshärtbare Produkte |
US5534559A (en) * | 1993-03-18 | 1996-07-09 | Ciba-Geigy Corporation | Daylight curing compositions containing bisacylphosphine oxide photoinitiators |
US5559163A (en) * | 1991-01-28 | 1996-09-24 | The Sherwin-Williams Company | UV curable coatings having improved weatherability |
US5747115A (en) * | 1993-09-30 | 1998-05-05 | The United States Of America As Represented By The Secretary Of The Navy | UV-curable and non-volatile pigmented coatings |
WO1999026732A1 (de) * | 1997-11-20 | 1999-06-03 | E.I. Du Pont De Nemours And Company, Inc. | Verfahren zur mehrschichtigen lackierung von substraten |
-
2000
- 2000-03-31 GB GBGB0007728.9A patent/GB0007728D0/en active Pending
-
2001
- 2001-02-27 DE DE60110775T patent/DE60110775T2/de not_active Expired - Lifetime
- 2001-02-27 US US10/239,604 patent/US6838177B2/en not_active Expired - Lifetime
- 2001-02-27 BR BRPI0109520-0A patent/BR0109520B1/pt not_active IP Right Cessation
- 2001-02-27 WO PCT/GB2001/000820 patent/WO2001074499A1/en active IP Right Grant
- 2001-02-27 EP EP01906016A patent/EP1274516B1/en not_active Expired - Lifetime
- 2001-02-27 CA CA002399381A patent/CA2399381C/en not_active Expired - Lifetime
- 2001-02-27 CN CNB018068456A patent/CN100413601C/zh not_active Expired - Fee Related
- 2001-02-27 ES ES01906016T patent/ES2241788T3/es not_active Expired - Lifetime
- 2001-02-27 AU AU2001233974A patent/AU2001233974A1/en not_active Abandoned
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4668529A (en) * | 1985-04-12 | 1987-05-26 | Ronald L. Berry | Filler composition and method |
US4747013A (en) * | 1986-02-15 | 1988-05-24 | Licentia Patent-Verwaltungs Gmbh | Electrical capacitor with tearoff interrupter |
US5559163A (en) * | 1991-01-28 | 1996-09-24 | The Sherwin-Williams Company | UV curable coatings having improved weatherability |
DE4336748A1 (de) * | 1992-11-17 | 1994-06-16 | Jordan Hch Lackfab Gmbh | Verfahren zur Blitztrocknung und Blitzhärtung und dafür geeignete Einrichtungen und strahlungshärtbare Produkte |
US5534559A (en) * | 1993-03-18 | 1996-07-09 | Ciba-Geigy Corporation | Daylight curing compositions containing bisacylphosphine oxide photoinitiators |
US5747115A (en) * | 1993-09-30 | 1998-05-05 | The United States Of America As Represented By The Secretary Of The Navy | UV-curable and non-volatile pigmented coatings |
WO1999026732A1 (de) * | 1997-11-20 | 1999-06-03 | E.I. Du Pont De Nemours And Company, Inc. | Verfahren zur mehrschichtigen lackierung von substraten |
Also Published As
Publication number | Publication date |
---|---|
CN1424945A (zh) | 2003-06-18 |
EP1274516A1 (en) | 2003-01-15 |
WO2001074499A1 (en) | 2001-10-11 |
BR0109520B1 (pt) | 2012-09-18 |
CA2399381C (en) | 2009-06-09 |
DE60110775T2 (de) | 2006-02-02 |
ES2241788T3 (es) | 2005-11-01 |
CA2399381A1 (en) | 2001-10-11 |
US20030059555A1 (en) | 2003-03-27 |
AU2001233974A1 (en) | 2001-10-15 |
DE60110775D1 (de) | 2005-06-16 |
US6838177B2 (en) | 2005-01-04 |
GB0007728D0 (en) | 2000-05-17 |
EP1274516B1 (en) | 2005-05-11 |
BR0109520A (pt) | 2003-06-10 |
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