CN1134963A - 有光乳胶漆 - Google Patents
有光乳胶漆 Download PDFInfo
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- CN1134963A CN1134963A CN96101010A CN96101010A CN1134963A CN 1134963 A CN1134963 A CN 1134963A CN 96101010 A CN96101010 A CN 96101010A CN 96101010 A CN96101010 A CN 96101010A CN 1134963 A CN1134963 A CN 1134963A
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- polymer beads
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- 239000003973 paint Substances 0.000 title claims abstract description 79
- 239000000839 emulsion Substances 0.000 title claims abstract description 40
- 229920000642 polymer Polymers 0.000 claims abstract description 87
- 239000006185 dispersion Substances 0.000 claims abstract description 74
- 239000011246 composite particle Substances 0.000 claims abstract description 58
- 239000001023 inorganic pigment Substances 0.000 claims abstract description 47
- 239000002245 particle Substances 0.000 claims abstract description 21
- 239000011324 bead Substances 0.000 claims description 72
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 53
- 239000008187 granular material Substances 0.000 claims description 53
- 238000000034 method Methods 0.000 claims description 34
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 26
- 239000011707 mineral Substances 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 239000004408 titanium dioxide Substances 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 17
- 239000000126 substance Substances 0.000 claims description 14
- 239000004816 latex Substances 0.000 claims description 9
- 229920000126 latex Polymers 0.000 claims description 9
- 239000012736 aqueous medium Substances 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- -1 acrylic ester Chemical class 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000002174 Styrene-butadiene Substances 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 2
- 239000011118 polyvinyl acetate Substances 0.000 claims description 2
- 239000011115 styrene butadiene Substances 0.000 claims description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 1
- 238000010422 painting Methods 0.000 claims 1
- 229920001577 copolymer Polymers 0.000 abstract description 3
- 239000000049 pigment Substances 0.000 description 48
- 239000002002 slurry Substances 0.000 description 16
- 239000002131 composite material Substances 0.000 description 15
- 239000000975 dye Substances 0.000 description 14
- 239000007787 solid Substances 0.000 description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 239000004922 lacquer Substances 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000000227 grinding Methods 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000013019 agitation Methods 0.000 description 4
- 239000013530 defoamer Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 230000001186 cumulative effect Effects 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N n-propyl alcohol Natural products CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000002562 thickening agent Substances 0.000 description 3
- 239000000080 wetting agent Substances 0.000 description 3
- NECRQCBKTGZNMH-UHFFFAOYSA-N 3,5-dimethylhex-1-yn-3-ol Chemical compound CC(C)CC(C)(O)C#C NECRQCBKTGZNMH-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-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
- 239000005083 Zinc sulfide Substances 0.000 description 2
- 238000005189 flocculation Methods 0.000 description 2
- 230000016615 flocculation Effects 0.000 description 2
- 239000010954 inorganic particle Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 2
- DAFHKNAQFPVRKR-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylpropanoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)C DAFHKNAQFPVRKR-UHFFFAOYSA-N 0.000 description 1
- BFHKYHMIVDBCPC-UHFFFAOYSA-N 1,3,5,7-tetrahydro-[1,3]oxazolo[3,4-c][1,3]oxazol-7a-ylmethanol Chemical compound C1OCN2COCC21CO BFHKYHMIVDBCPC-UHFFFAOYSA-N 0.000 description 1
- LXOFYPKXCSULTL-UHFFFAOYSA-N 2,4,7,9-tetramethyldec-5-yne-4,7-diol Chemical compound CC(C)CC(C)(O)C#CC(C)(O)CC(C)C LXOFYPKXCSULTL-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920013802 TRITON CF-10 Polymers 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 description 1
- 238000004630 atomic force microscopy Methods 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- PVEOYINWKBTPIZ-UHFFFAOYSA-N but-3-enoic acid Chemical class OC(=O)CC=C PVEOYINWKBTPIZ-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000001035 lead pigment Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 239000002345 surface coating layer Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- UMFCIIBZHQXRCJ-NSCUHMNNSA-N trans-anol Chemical compound C\C=C\C1=CC=C(O)C=C1 UMFCIIBZHQXRCJ-NSCUHMNNSA-N 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/02—Emulsion paints including aerosols
- C09D5/024—Emulsion paints including aerosols characterised by the additives
- C09D5/028—Pigments; Filters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
- C08J3/21—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase
- C08J3/215—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase at least one additive being also premixed with a liquid phase
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- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/0081—Composite particulate pigments or fillers, i.e. containing at least two solid phases, except those consisting of coated particles of one compound
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/0081—Composite particulate pigments or fillers, i.e. containing at least two solid phases, except those consisting of coated particles of one compound
- C09C1/0084—Composite particulate pigments or fillers, i.e. containing at least two solid phases, except those consisting of coated particles of one compound containing titanium dioxide
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/36—Compounds of titanium
- C09C1/3607—Titanium dioxide
- C09C1/3676—Treatment with macro-molecular organic compounds
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/10—Treatment with macromolecular organic compounds
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- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
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Abstract
一种包含结构性复合颗粒的分散体的水性有光乳胶漆,所述结构性复合颗粒包括无机颜料与聚合物颗粒的缔合,所述聚合物颗粒由最低成膜温度不超过50℃的聚合物或共聚物形成,组成复合颗粒的颗粒由于聚合物颗粒上的表面电荷与无机颜料上的表面电荷符号相反而缔合在一起。聚合物颗粒与无机颜料颗粒在结构性复合颗粒中的体积比为0.5∶1至6∶1。
Description
本发明涉及有光乳胶漆,尤其涉及含有结构性复合颜料的有光乳胶漆。
一般认为难以制得表面涂覆时可形成高光泽度漆膜的水性乳胶漆,与颜料分散于成膜聚合物中的溶剂基漆不同,在水性乳胶漆中成膜聚合物和颜料分别和不连续地分散于体系中。在水性漆颜料的干燥过程中,颜料颗粒往往絮凝形成足以使干燥漆膜表面凹凸不平的附聚物。这些表面凹凸增加了漆膜表面的光散射,从而降低了镜面反射率和光泽度。
本发明的目的是提供干燥漆膜的光泽度得到提高的有光乳胶漆。
本发明提供包含结构性复合颗粒的分散体的水性有光乳胶漆,所述结构性复合颗粒包括至少一种无机颜料与至少一种聚合物颗粒的缔合,所述聚合物颗粒由最低成膜温度不超过50℃的聚合物或共聚物形成,所述结构性复合颗粒的组成应使得聚合物颗粒与无机颜料的颗粒的体积比在0.5∶1至6∶1的范围内,无机颜料颗粒和聚合物颗粒均带有表面电荷,当无机颜料颗粒表面带有负电荷时,聚合物颗粒的表面电荷是正电荷;当无机颜料颗粒表面带有正电荷时,聚合物颗粒的表面电荷是负电荷,所述表面电荷的作用使得无机颜料颗粒和聚合物颗粒在结构性复合颗粒中缔合。
本发明还提供制备包含结构性复合颗粒的分散体的水性有光乳胶漆的方法,所述结构性复合颗粒包含至少一种无机颜料颗粒与至少一种聚合物颗粒的缔合,该方法包括在所述无机颜料颗粒可带有表面电荷的pH值下将所述无机颜料分散于水性介质中;并将所述聚合物颗粒分散于水性介质中,其中所述聚合物颗粒带有表面电荷;当分散的无机颜料颗粒的表面电荷是负电荷时,聚合物颗粒的表面电荷是正电荷;当分散的无机颜料颗粒的表面电荷是正电荷时,聚合物颗粒的表面电荷是负电荷;将分散的无机颜料颗粒与分散的聚合物颗粒在混合不会使粒状材料之一的表面电荷的符号发生反转的条件下进行混合,从而形成无机颜料颗粒和聚合物颗粒由于所述表面电荷而缔合的结构性复合颗粒,所述聚合物颗粒由最低成膜温度不超过50℃的聚合物或共聚物形成,并且结构性复合颗粒的组成应使得聚合物颗粒与无机颜料颗粒的体积比在0.5∶1至6∶1的范围内。
一般来说,制成的乳胶漆的pH值在6-10的范围内。但在制备本发明的复合颗粒分散体时常常优选pH值在该范围之外。因此,在一个优选的本发明方法中,在形成结构性复合颗粒后,将复合颗粒的分散体的pH值调节在6-10的范围内。
在形成结构性复合颗粒后pH被调节至6-10的范围内的该方法的产物是本发明的优选产物。
因此,本发明还提供包含结构性复合颗粒的分散体的水性有光乳胶漆,所述结构性复合颗粒包括至少一种无机颜料与至少一种聚合物颗粒的缔合,所述聚合物颗粒由最低成膜温度不超过50℃的聚合物或共聚物形成,所述结构性复合颗粒的组成应使得聚合物颗粒与无机颜料的颗粒的体积比在0.5∶1至6∶1的范围内,该结构性复合颗粒可通过下述方法制得:在所述无机颜料颗粒可带有表面电荷的pH值下将所述无机颜料分散于水性介质中;并将所述聚合物颗粒分散于水性介质中,其中聚合物颗粒带有表面电荷;当分散的无机颜料颗粒的表面电荷是负电荷时,聚合物颗粒的表面电荷是正电荷;当分散的无机颜料颗粒的表面电荷是正电荷时,聚合物颗粒的表面电荷是负电荷;将分散的无机颜料颗粒与分散的聚合物颗粒在混合不会使粒状材料之一的表面电荷的符号发生反转的条件下进行混合,从而形成无机颜料颗粒和聚合物颗粒由于所述表面电荷而缔合的结构性复合颗粒,随后,将如此形成的结构性复合颗粒的分散体的pH值调节至6-10的范围内。
本发明能够提供能形成具有极高光泽度的干燥漆膜的有光乳胶漆。用镜面光泽计测得的所述漆膜的60°光泽度一般大于70%,常常大于75%。
构成本发明的复合颗粒的一个成分的无机颜料是乳胶漆中常用的任何颜料。典型的颜料包括二氧化钛颜料、氧化锌颜料、氧化锑颜料、钡颜料、钙颜料、锆颜料、铬颜料、铁颜料、镁颜料、铅颜料、硫化锌和立德粉。优选的颜料是二氧化钛,最优选金红石二氧化钛。
构成本发明的复合颗粒的另一个成分的聚合物颗粒可由任何最低成膜温度如上所述的聚合物或共聚物构成。典型的聚合物和共聚物包括丙烯酸或取代的丙烯酸或丙烯酸酯或取代的丙烯酸酯的聚合物或共聚物、聚(苯乙烯-丙烯酸酯)、聚酯、聚氨酯、聚(氨基甲酸酯-丙烯酸酯)、聚(苯乙烯-丁二烯)、聚乙酸乙烯酯聚合物和共聚物和醇酸树脂或环氧树脂乳液。
所述复合颗粒是由至少一种无机颜料颗粒和至少一种聚合物材料颗粒构成的。由多种无机颜料和/或多种聚合物材料构成的复合颗粒也在本发明的范围之内。
我们认为,在本发明的复合颗粒中的聚合物颗粒在将有光漆涂覆到底材上以后进行的干燥过程中聚结并将无机颜料颗粒包裹。尽管本发明包括设计为加热干燥的有光漆,但常常都在通常的环境温度下进行干燥。因此,聚合物颗粒的最低成膜温度(MFFT)是一个重要的参数。颗粒的MFFT最好低于25℃,最优选在0-25℃的范围内。
在复合颗粒中聚合物颗粒与无机颜料颗粒的比率也影响将无机颜料包裹在聚合物中这一过程的效率。珠粒与颜料的比率优选在1∶1至4∶1(体积比)的范围内,最优选在1.5∶1至3∶1(体积比)的范围内。
当在优选的实施方案中使用二氧化钛时,其平均晶体尺寸最优选在大约0.05-0.5μm之间。对于金红石二氧化钛而言,平均晶体尺寸最优选在0.2-0.3μm之间,对于锐钛型二氧化钛而言,平均晶体尺寸最优选在0.1-0.35μm的范围内。
聚合物颗粒的优选的平均尺寸取决于与之缔合的无机颗粒的平均尺寸,因为重要的是获得具有在漆膜干燥时有助于形成平滑漆膜的结构的复合颗粒。当使用具有上述平均晶体尺寸的二氧化钛颜料时,聚合物颗粒的平均尺寸优选0.02-0.5μm,更优选0.05-0.2μm。
在本发明的方法中,将无机颜料颗粒的分散体与聚合物颗粒的分散体在各成分具有相反的表面电荷的条件下进行混合。在许多市售聚合物颗粒的分散体中,颗粒带有负的表面电荷。因此,在本发明的优选方法中,使用了具有正的表面电荷的无机颜料颗粒的分散体。
在这一优选的实施方案中,无机颜料颗粒的分散体在pH低于颗粒的等电点时形成。例如,典型的具有氧化铝表面包覆层的二氧化钛颜料在pH低于大约6时分散于水中时将带有正的表面电荷。一个优选的本发明方法使用在优选pH低于6、更优选在4-6之间的条件下制备的氧化铝包覆的二氧化钛分散体。如果所用的二氧化钛是未包覆的或者具有含二氧化硅的包覆层时,则最好在pH值在2-4之间的条件下制备该分散体。
可通过任何适当的方法来制备本发明方法所用的分散体。最好在无分散剂存在下将粒状无机颜料与水搅拌,但对于聚合物颗粒使用市售的分散体常常是方便的,这样的分散体往往含有分散剂。这些分散剂的存在通常不妨碍该分散剂在本发明方法中的使用。重要的是,分散剂的使用很可能会有效地改变被分散材料的等电点,并因而改变了出现正或负的表面电荷的pH值。
最好使无机颜料的分散体经过一个研磨步骤以粉碎任何存在的附聚物并使颗粒的分散度优化。研磨可以用例如高速叶轮式研磨机、球磨机、砂磨机或者用超声波进行。
可以制备任何适宜浓度的分散体,但需要考虑诸如各成分和复合材料的分散体的粘度和产物用于油漆的适用性之类的因素。一般来说,优选使用聚合物颗粒含量为40-65%(重量)的聚合物颗粒的分散体,所用的分散体常常含有40-60%(重量)聚合物颗粒。无机颜料的分散体的优选浓度是50-80%(重量)。
复合材料的两成分的各分散体可在不同的pH值下生产和使用,但是如果两分散体具有基本相似的pH值,则该过程可以得到简化。两分散体的pH值优选相差不超过1pH单位,更优选相差不超过0.5pH单位。
当两分散体的pH值基本相似时,便可通过将该两分散体混合同时用任何适宜的装置搅拌的方法容易地制得本发明的产物。两分散体的适当混合通过例如搅拌、循环混合来进行,或者通过将混合物暴露在超声波振动下进行。通常是将分散体之一缓慢地加到另一分散体中,或者将两种分散体同时引入一个搅拌混合区中。
有时必须在pH值差异很大的条件下制备该两种分散体,例如将在混合所选的pH值下稳定性差的分散体进行混合时便是如此。当必须使用pH值差异很大的分散体时,重要的是要在pH值的任何改变(混合时可能发生)都不会使得无机颗粒或聚合物颗粒上的表面电荷的符号反转的条件下将各分散体混合。例如,在混合步骤中有可能必须加入酸或碱以调节pH。
例如由氧化铝包覆的二氧化钛来生产复合材料的适宜的pH值是大约4-5。但是,市售的聚合物颗粒常常以pH值大约为7-9的分散体的形成提供。然而,由二氧化钛和聚合物颗粒通过在pH值为4-5的条件下将市售聚合物颗粒的分散体加入二氧化钛的分散体中,同时通过加入酸使所得混合物的pH值保持在4至5的范围内可制得本发明的产物。
一般来说,对于无机颜料与聚合物的任何特定组合,将有一个进行本发明方法的最佳pH值或pH值范围。然而,许多水性漆体系的pH值都在6至10的范围内,而本发明的范围内还包括这样一种如上所述的pH值在6至10的范围之外实施以生成结构性复合颗粒的方法,其中在结构性复合颗粒中一个或多个无机颜料颗粒和一个或多个聚合物颗粒由于颗粒所带的表面电荷相反而缔合在一起,并且随后将所得复合颗粒的分散体的pH值调节到6至10的范围内。
在形成复合颗粒的分散体之后调节pH时,将其值调节到7至9的范围内。
本发明的产物的一个特别优选的实例是上文定义的pH值在6-10、优选在7-9范围内的复合颗粒的分散体。该产物可这样制备:在上述范围之一的pH下,由分开的无机颜料颗粒的分散体和聚合物颗粒的分散体制备复合颗粒的分散体;或者在上述pH范围之外制备该产物,随后将pH调节至所述范围之一的值。
适当地选择无机颜料、聚合物颗粒和这些成分的浓度和比例可制得复合颗粒的分散体,可不经过进一步改性而直接用作有光乳胶漆。然而,该分散体常常被用作油漆的主要成分,向其中加入常规油漆添加剂以形成成品油漆组合物。例如,可以使用常规加工技术混入外加的颜料和外加的成膜聚合物胶乳(不一定与结构性复合材料中所用的相似)。还可以加入其它成分如染料、消泡剂、聚结性溶剂和增稠剂。
由本发明的油漆形成的漆膜通常具有高的光泽度,与用常规方法制成的油漆相比,漆膜的不透明性增加,这显然是由于复合颗粒的结构性质使颜料颗粒在涂覆的漆膜中产生了更均匀的分布。与使用相似的结构性颜料的、基于具有较高成膜温度的聚合物颗粒的油漆相反,漆膜的表面光泽度并不比常规油漆的有所降低。镜面光泽可以比常规方法制备的油漆的高得多,原子力显微镜(Atomic ForceMicroscopy)观察表明具有较高光泽度的漆膜含有较小和较少颜料引起的表面粗糙。
用下述实施例说明本发明。
实施例1
将194g二氧化钛(TIOXIDE TR92)分散于169g软化水中制得颜料浆。通过加入盐酸将浆液的pH值调节至4.5并将浆液进行高剪切研磨以充分分散。将平均粒径为0.075微米且最低成膜温度为8℃的实验级醋酸乙烯酯/VeoVa聚合物乳液(44%固体)调节至pH4.5,然后在高剪切搅拌条件下,将200g乳液与颜料浆混合。通过加入氨将所得复合颗粒的分散体调节至pH8.5。复合分散体的总干固体分为50.1%(重量),乳液颗粒与颜料颗粒的体积比为1.77∶1。
然后用外加的醋酸乙烯酯/VeoVa乳液作为粘合剂制备了含有复合颜料的有光漆,其总体积固体浓度为30.0%,颜料体积浓度为18.0%。按照常规的油漆制造方法制备含有相同量乳液和颜料的油漆,用它作为标样。各油漆的组成如下:
重量份
标准漆 试验漆水 80.00 80.00羟乙基纤维素 3.00 3.00(Cellosize QP44OOH)氨(0.88) 2.32 2.32多元羧酸的钠盐 1.00 1.00(Dispex N40)非离子性表面活性剂 0.24 0.24(Triton CF10)聚结性溶剂 10.96 10.96(Texanol)消泡剂 0.80 0.80(Foamaster E75C)杀菌剂(Nuosept 95) 0.80 0.80二氧化钛 142.36 -(TIOXIDE TR92)复合颜料 (干重) - 208.92醋酸乙烯酯/VeoVa乳液 176.97 110.00(干重)
试验结果
标准漆 试验漆对比率 @20m2/l 89.60 90.9360°光泽度 47 65涂布率 (m2/l)@对比率 98% 6.81 8.53
实施例2
将758.4g二氧化钛(TIOXIDE TR92)分散于295.0g软化水中制得颜料浆。通过加入盐酸将浆液的pH值调节至4.5并将浆液进行高剪切研磨以充分分散。将平均粒径为0.086微米且最低成膜温度为22℃的实验级甲基丙烯酸甲酯-丙烯酸丁酯共聚物胶乳调节至pH4.5,然后在高剪切搅拌条件下,将300g胶乳与395.1g颜料浆混合。通过加入氨将所得复合颗粒的分散体调节至pH10。复合分散体的总干固体分为60.3%(重量),乳液颗粒与颜料颗粒的体积比为1.96∶1。然后制备了含有复合颜料的高光泽漆,使得油漆的总体积固体分为39.5%,颜料体积浓度为19.2%。按照常规的高光泽漆制造方法制备含有相同体积固体分和颜料浓度的油漆,用它作为标样。
各油漆的组成如下:
重量份
标准漆 试验漆水 50.20 3.00丙二醇 24.00 24.00氨基甲基丙醇panol 2.00 2.00(AMP95-Angus Chemie)消泡剂 20.00 20.00(Dehydran 1293-Henkel)润湿剂(Surfynol 104E-Air Products) 4.00 4.00分散剂(Neocryl BT24- 31.00 31.00Zeneca Resins)二氧化钛(TIOXIDE TR92) 240.00 -复合颜料 - 1152.00丙烯酸乳液 592.00 592.00(Neocryl XK90-Zeneca Resins)乙二醇 43.00 43.00缔合性增稠剂 11.00 11.00(Tafigel PUR40-Munzig Chemie)
试验结果
标准漆 试验漆
对比率 @20μm 93.8 94.5
干膜厚度s
60°光泽度 80 78
絮凝梯度 0.70 0.42
比较例A
将189.3g二氧化钛(TIOXIDE TR92)分散于189.3g软化水中制得颜料浆。通过加入盐酸将浆液的pH值调节至4.5并将浆液进行高剪切研磨以充分分散。将平均粒径为0.065微米且最低成膜温度高于50℃的实验级聚苯乙烯胶乳调节至pH4.5,然后在高剪切搅拌条件下,将100g胶乳与颜料浆混合。通过加入氨将所得复合颗粒的分散体调节至pH8.5。复合分散体的总干固体分为49.8%(重量),乳液与颜料的体积比为1.06∶1。然后将该复合颜料混入高光泽漆制剂中,使得二氧化钛体积浓度为20.0%。按照常规的高光泽漆的制造方法制备含有相同量浓度二氧化钛的油漆,用它作为标样。各油漆的组成如下:
重量份
标准漆 试验漆水 33.00 33.00丙二醇 24.00 24.00氨基甲基丙醇 2.00 2.00(AMP95)消泡剂 20.00 20.00(Dehydran 1293)润湿剂(Surfynol 104E) 4.00 4.00分散剂(Neocryl BT24) 31.00 31.00二氧化钛(TIOXIDE TR92) 240.00 -复合颜料(干重) - 308.00丙烯酸乳液 596.90 447.20(Neocryl XK-90)乙二醇 43.00 43.00缔合性增稠剂 6.00 6.00(Coatex BR910)
试验结果
标准漆 试验漆
对比率 @20μm 93.7 94.1
干膜厚度
60°光泽度 80 61
实施例3
将184.2g二氧化钛(TIOXIDE TR92)分散于74.4g软化水中制得颜料浆。通过加入盐酸将浆液的pH值调节至4.5并将浆液进行高剪切研磨以充分分散。将平均粒径为0.109微米且最低成膜温度为18℃的实验级甲基丙烯酸甲酯-丙烯酸丁酯共聚物胶乳调节至pH4.5,然后在高剪切搅拌条件下,将200g胶乳与颜料浆混合。通过加入氨将所得复合颗粒的分散体调节至pH8.5。复合分散体的总干固体分为59.5%(重量),乳液颗粒与颜料颗粒的体积比为1.99∶1。然后制备了含有复合颜料的高光泽漆,使得油漆的总体积固体分为38.5%,颜料体积浓度为19.2%。按照常规的高光泽漆制造方法制备含有相同体积固体分和颜料浓度的油漆,用它作为标样。
各油漆的组成如下:
重量份
标准漆 试验漆水 71.20 30.50丙二醇 24.00 24.00氨基甲基丙醇 2.00 2.00(AMP95-Angus Chemie)消泡剂 20.00 20.00(Dehydran 1293-Henkel)润湿剂(Surfynol 104E-Air Products) 4.00 4.00分散剂(Neocryl BT24- 31.00 31.00Zeneca Resins)二氧化钛(TIOXIDE TR92) 240.00 -复合颜料 - 1189.00丙烯酸乳液 592.00 592.00(Neocryl XK-90-Zeneca Resins)乙二醇 43.00 43.00缔合性增稠剂 11.00 11.00(Tafigel PUR40-Munzig Chemie)
油漆性能
体积固体分 38.50%
颜料体积浓度 19.2%
试验结果
标准漆 试验漆
对比率 @20μm 93.3 94.2
干膜厚度
20°光泽度 44 62
60°光泽度 75 87
絮凝梯度 0.70 0.54
Claims (21)
1.包含结构性复合颗粒的分散体的水性有光乳胶漆,所述结构性复合颗粒包括至少一种无机颜料与至少一种聚合物颗粒的缔合,所述聚合物颗粒由最低成膜温度不超过50℃的聚合物或共聚物形成,所述结构性复合颗粒的组成应使得聚合物颗粒与无机颜料的颗粒的体积比在0.5∶1至6∶1的范围内,无机颜料颗粒和聚合物颗粒均带有表面电荷,当无机颜料颗粒表面带有负电荷时,聚合物颗粒的表面电荷是正电荷;当无机颜料颗粒表面带有正电荷时,聚合物颗粒的表面电荷是负电荷,所述表面电荷的作用使得无机颜料颗粒和聚合物颗粒在结构性复合颗粒中缔合。
2.根据权利要求1的水性有光乳胶漆,其特征在于无机颜料是金红石二氧化钛。
3.根据权利要求1或2的水性有光乳胶漆,其特征在于聚合物颗粒是由下述物质组成的:丙烯酸或取代的丙烯酸或丙烯酸酯或取代的丙烯酸酯的聚合物或共聚物、聚(苯乙烯-丙烯酸酯)、聚酯、聚氨酯、聚(氨基甲酸酯-丙烯酸酯)、聚(苯乙烯-丁二烯)、聚乙酸乙烯酯聚合物和共聚物和醇酸树脂乳液或环氧树脂乳液。
4.根据上述任何一项权利要求的水性有光乳胶漆,其特征在于所述复合颗粒是由多种无机颜料或多种聚合物材料构成的。
5.根据上述任何一项权利要求的水性有光乳胶漆,其特征在于所述聚合物或共聚物的最低成膜温度低于25℃。
6.根据上述任何一项权利要求的水性有光乳胶漆,其特征在于在复合颗粒中聚合物颗粒与无机颜料颗粒的体积比在1∶1至4∶1的范围内。
7.根据上述任何一项权利要求的水性有光乳胶漆,其特征在于无机颜料是平均晶体尺寸在0.05-0.5μm范围内的二氧化钛。
8.根据权利要求7的水性有光乳胶漆,其特征在于聚合物颗粒的平均粒径为0.02-0.5μm。
9.根据上述任何一项权利要求的水性有光乳胶漆,其特征在于油漆可形成在用镜面光泽计测定时60°光泽度大于70%的干燥漆膜。
10.制备包含结构性复合颗粒的分散体的水性有光乳胶漆的方法,所述结构性复合颗粒包含至少一种无机颜料颗粒与至少一种聚合物颗粒的缔合,该方法包括在所述无机颜料颗粒可带有表面电荷的pH值下将所述无机颜料分散于水性介质中;并将所述聚合物颗粒分散于水性介质中,其中所述聚合物颗粒带有表面电荷;当分散的无机颜料颗粒的表面电荷是负电荷时,聚合物颗粒的表面电荷是正电荷;当分散的无机颜料颗粒的表面电荷是正电荷时,聚合物颗粒的表面电荷是负电荷;将分散的无机颜料颗粒与分散的聚合物颗粒在混合不会使粒状材料之一的表面电荷的符号发生反转的条件下进行混合,从而形成无机颜料颗粒和聚合物颗粒由于所述表面电荷而缔合的结构性复合颗粒,所述聚合物颗粒由最低成膜温度不超过50℃的聚合物或共聚物形成,所述结构性复合颗粒的组成应使得聚合物颗粒与无机颜料的颗粒的体积比在0.5∶1至6∶1的范围内。
11.根据权利要求10的方法,其特征在于在形成复合颗粒后将结构性复合颗粒的分散体的pH值调节至6-10的范围内。
12.根据权利要求10或11的方法,其特征在于无机颜料颗粒具有正的表面电荷,而聚合物颗粒具有负的表面电荷。
13.根据权利要求10至12任何一项的方法,其特征在于无机颜料是表面涂覆有氧化铝的二氧化钛和在pH值小于6的条件下将二氧化钛颗粒分散。
14.根据权利要求10至13任何一项的方法,其特征在于无机颜料的分散体是在没有分散剂的条件下制备的。
15.根据权利要求10至14任何一项的方法,其特征在于聚合物颗粒分散的浓度在40-65%(重量)的范围内。
16.根据权利要求10至15任何一项的方法,其特征在于无机颜料颗粒分散的浓度在50-80%(重量)的范围内。
17.根据权利要求10至16任何一项的方法,其特征在于待混合的分散的无机颜料的颗粒和分散的聚合物颗粒的pH值相差不超过1pH单位。
18.根据权利要求10至16任何一项的方法,其特征在于在将分散的无机颜料颗粒与分散的聚合物混合的步骤中,加入酸或碱以调节形成的分散体的pH值。
19.根据权利要求18的方法,其特征在于将带有氧化铝包覆层的二氧化钛在pH值为4至5的条件下分散,并将其与pH值为7至9的聚合物颗粒的分散体混合,通过同时加入酸使所得混合物的pH值保持在4至5的范围内。
20.pH值在6-10范围内的、按照权利要求10-18任何一项的方法制备的水性有光乳胶漆。
21.一种包含结构性复合颗粒的分散体的水性有光乳胶漆,所述结构复合颗粒包括至少一种无机颜料与至少一种聚合物颗粒的缔合,所述聚合物颗粒由最低成膜温度不超过50℃的聚合物或共聚物形成,所述结构性复合颗粒的组成应使得聚合物颗粒与无机颜料的颗粒的体积比在0.5∶1至6∶1的范围内,该结构性复合颗粒可通过下述方法制得:在所述无机颜料颗粒可带有表面电荷的pH值下将所述无机颜料分散于水性介质中;并将所述聚合物颗粒分散于水性介质中,其中所述聚合物颗粒带有表面电荷;当分散的无机颜料颗粒的表面电荷是负电荷时,聚合物颗粒的表面电荷是正电荷;当分散的无机颜料颗粒的表面电荷是正电荷时,聚合物颗粒的表面电荷是负电荷;将分散的无机颜料颗粒与分散的聚合物颗粒在混合不会使粒状材料之一的表面电荷的符号发生反转的条件下进行混合,从而形成无机颜料颗粒和聚合物颗粒由于所述表面电荷而缔合的结构性复合颗粒,随后,将如此形成的结构性复合颗粒的分散体的pH值调节至6-10的范围内。
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GBGB9500497.4A GB9500497D0 (en) | 1995-01-11 | 1995-01-11 | Gloss emulsion paints |
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1995
- 1995-01-11 GB GBGB9500497.4A patent/GB9500497D0/en active Pending
- 1995-12-12 DK DK95309054T patent/DK0721966T3/da active
- 1995-12-12 AT AT95309054T patent/ATE197600T1/de not_active IP Right Cessation
- 1995-12-12 DE DE69519418T patent/DE69519418T2/de not_active Expired - Fee Related
- 1995-12-12 EP EP95309054A patent/EP0721966B1/en not_active Expired - Lifetime
- 1995-12-12 GB GB9525349A patent/GB2297758B/en not_active Expired - Fee Related
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- 1995-12-18 AU AU40497/95A patent/AU704674B2/en not_active Ceased
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- 1995-12-28 KR KR1019950060520A patent/KR960029422A/ko not_active Application Discontinuation
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1996
- 1996-01-09 NO NO960088A patent/NO960088L/no not_active Application Discontinuation
- 1996-01-09 AR AR33495996A patent/AR000642A1/es unknown
- 1996-01-09 BR BR9600077A patent/BR9600077A/pt active Search and Examination
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- 1996-01-10 CN CN96101010A patent/CN1134963A/zh active Pending
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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CN102826788A (zh) * | 2011-06-08 | 2012-12-19 | 罗门哈斯公司 | 基于微球体的墙壁修复配混物 |
CN102826788B (zh) * | 2011-06-08 | 2015-08-19 | 罗门哈斯公司 | 基于微球体的墙壁修复配混物 |
CN105121562A (zh) * | 2013-03-18 | 2015-12-02 | 可泰克斯公司 | 聚合物乳液用于无机材料颗粒的表面处理的用途 |
CN105121562B (zh) * | 2013-03-18 | 2017-05-31 | 可泰克斯公司 | 聚合物乳液用于无机材料颗粒的表面处理的用途 |
Also Published As
Publication number | Publication date |
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JPH08231890A (ja) | 1996-09-10 |
FI960117A (fi) | 1996-07-12 |
CA2165219A1 (en) | 1996-07-12 |
TW359682B (en) | 1999-06-01 |
US5952404A (en) | 1999-09-14 |
SK4096A3 (en) | 1997-08-06 |
AU704674B2 (en) | 1999-04-29 |
DK0721966T3 (da) | 2000-12-11 |
GB9525349D0 (en) | 1996-02-14 |
MX9600186A (es) | 1997-01-31 |
CZ7396A3 (en) | 1996-07-17 |
DE69519418D1 (de) | 2000-12-21 |
GB2297758A (en) | 1996-08-14 |
DE69519418T2 (de) | 2001-04-19 |
NO960088L (no) | 1996-07-12 |
GB2297758B (en) | 1998-11-25 |
FI960117A0 (fi) | 1996-01-10 |
GB9500497D0 (en) | 1995-03-01 |
NO960088D0 (no) | 1996-01-09 |
ATE197600T1 (de) | 2000-12-15 |
NZ280800A (en) | 1996-09-25 |
KR960029422A (ko) | 1996-08-17 |
AU4049795A (en) | 1996-07-18 |
EP0721966B1 (en) | 2000-11-15 |
BR9600077A (pt) | 1998-01-27 |
EP0721966A1 (en) | 1996-07-17 |
ZA96216B (en) | 1996-07-26 |
AR000642A1 (es) | 1997-07-10 |
PL312235A1 (en) | 1996-07-22 |
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