CA2127814C - Coating composition which is applied to a substrate and contains ultra fine tio2 - Google Patents
Coating composition which is applied to a substrate and contains ultra fine tio2 Download PDFInfo
- Publication number
- CA2127814C CA2127814C CA002127814A CA2127814A CA2127814C CA 2127814 C CA2127814 C CA 2127814C CA 002127814 A CA002127814 A CA 002127814A CA 2127814 A CA2127814 A CA 2127814A CA 2127814 C CA2127814 C CA 2127814C
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- coating composition
- pigment
- ultra fine
- coating
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- 239000008199 coating composition Substances 0.000 title claims abstract description 57
- 239000000758 substrate Substances 0.000 title claims abstract description 12
- 239000000049 pigment Substances 0.000 claims abstract description 54
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000002245 particle Substances 0.000 claims abstract description 17
- 238000000576 coating method Methods 0.000 claims abstract description 16
- 239000011230 binding agent Substances 0.000 claims abstract description 11
- 239000011248 coating agent Substances 0.000 claims abstract description 11
- 239000003973 paint Substances 0.000 claims abstract description 11
- 239000006229 carbon black Substances 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 239000002966 varnish Substances 0.000 claims abstract description 4
- 239000006115 industrial coating Substances 0.000 claims abstract description 3
- 239000004922 lacquer Substances 0.000 claims abstract description 3
- 239000006223 plastic coating Substances 0.000 claims abstract description 3
- 239000000470 constituent Substances 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 15
- 229920005989 resin Polymers 0.000 claims description 14
- 239000011347 resin Substances 0.000 claims description 14
- 229920000180 alkyd Polymers 0.000 claims description 6
- 239000004925 Acrylic resin Substances 0.000 claims description 2
- 229920000178 Acrylic resin Polymers 0.000 claims description 2
- 239000004640 Melamine resin Substances 0.000 claims description 2
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- 235000019241 carbon black Nutrition 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000000985 reflectance spectrum Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000009471 action Effects 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Inorganic materials [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- 241000557626 Corvus corax Species 0.000 description 2
- 238000005169 Debye-Scherrer Methods 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000001055 blue pigment Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 2
- 239000001054 red pigment Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 235000010215 titanium dioxide Nutrition 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 241001274189 Pomatomus saltatrix Species 0.000 description 1
- 229920004482 WACKER® Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000001045 blue dye Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- VVOLVFOSOPJKED-UHFFFAOYSA-N copper phthalocyanine Chemical compound [Cu].N=1C2=NC(C3=CC=CC=C33)=NC3=NC(C3=CC=CC=C33)=NC3=NC(C3=CC=CC=C33)=NC3=NC=1C1=CC=CC=C12 VVOLVFOSOPJKED-UHFFFAOYSA-N 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 230000019612 pigmentation Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 235000020354 squash Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/08—Homopolymers or copolymers of acrylic acid esters
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
A coating composition is described, which is applied to a substrate and contains ultra fine TiO2. This coating composition consists of 0.5 to 30.0% by volume colored pigment and/or carbon black, 55.0 to 98.5% by volume binder solids content and 0.3 to 15% by volume ultra fine TiO2 having a particle size of 5 to 40 nm. It has a high total reflectance and is of intensive depth of color. The production of this coating composition is also described.
This coating composition is useful as a finishing lacquer for motor vehicles, industrial coating, printing ink, coil coating, package coating, plastic coating and decorative paint. It is also useful as varnish.
This coating composition is useful as a finishing lacquer for motor vehicles, industrial coating, printing ink, coil coating, package coating, plastic coating and decorative paint. It is also useful as varnish.
Description
2i2~~~4 The present invention relates to a coating composition which is applied to a substrate and contains ultra fine Ti02, to a method for the production of the coating composition and to the use thereof.
A coat composition is known from EP 0 270 472 Bl which contains 24.0 to 35.0% by weight of a thermoplastic or duroplastic resin, 1.1 to 10.5% by weight of a metallic or metal-like pigment and 1.1 to 10.5% by weight transparent Ti02, which has a particle size of 20 to 30 nm. The coat composition is intended for use as a base coating for a metallic paint for car bodies in the automobile industry. At least one layer of an unpigmented varnish is applied to this base paint.
Several layers of a pigmented base paint may also be applied. However, the pigmented coat composition is not used as a top coat. In addition to the metallic effect, the coating composition exhibits the frast effect. The frost effect can be noted when observing coat compositions which contain metallic or metal-like pigments in combination with finely-divided Ti02. The frost effect depends on the direction of incidence of the light relative to the sample and to the observer.
If the samples are observed from a vertical direction, the coating seems yellowish to golden in color, and if observed from a horizontal direction, the sample looks b~ueish.
It can be inferred from the publication by J. G. Balfour in J. Oil Colour Chem. Assoc. (lj, 1992, page 21 ff. that in the case of paints which contain exclusively ultra fine Ti02, the total reflectance of the paints increases with the increase in the pigment volume concentration from o.1 to 1.0% of 2~,2~81.4 ultra fine TiOZ. The increase in the reflectance of the paints is greater in the range of blue light at a relatively short wavelength. With the increase in ultra. fine 'fiOZ in the pigment volume concentration, , the paints appear to be increasingly milky to the observer.
In conventional coating compositions which are applied to a substrate, an improvement in the total reflectance and depth of color is always desired. An improvement in the unsatisfactory stabilization of colored pigments is likewise always desired. This is particularly so when it is necessary to apply preferably only one coating composition as top coat to a substrate, and therefore the total reflectance and the depth of color only result from the one top coat.
It is an object of the present invention to provide a coating composition which has a high total reflectance, intensive depth of color and long storage stability, and also good flocculation stabilization of colored pigments.
This object is achieved by a coating composition which consists of o.5 to 30.0% by volume colored pigment and/or carbon black, with the proviso that it is not a metallic pigment or metal-like pigment, 55.0 to 98.50 by volume binder solids content and 0.3 to 15% by volume ultra fine Ti02 having a particle size of 5 to 40 nm and has a high total reflectance and intensive depth of color. The crystallite size is determined according to Debye-Scherrer. The crystallite size thus determined is approximately identical to the particle size. The term "coating composition" refers to the hardened coating.
2~2~~8~.4 The proportions of the coating composition are given in pigment volume concentration (PVC), and therefore in %
by volume or, in simplified manner, in %. The pigment volume concentration designates the proportion by ~ volume of one or more pigments, relative to the total solids volume of the hardened coating.
The ultra fine TiOz may be in the form of the crystal modifications rutile, anatase or in X-amorphous form. For reasons of weathering-resistance, a ultra fine Ti02 in the rutile modification is preferably used. Subsequent inorganic and/or organic treatment of the ultra fine Ti02 produced has no effect on the suitability thereof in the coating compositions according to the invention. The production process for the ultra fine Ti02 or the particle morphology of the ultra fine Ti02 do not impair the action of the ultra fine Ti02 in the coating composition according to the invention. Ultra fine Tio2 can therefore be used in coating compositions according to the invention independently of the method of production or particle morphology thereof.
The coating compositions according to the invention have a surprisingly strong blue-tone shift of the respective color. The color does not change with the angle of observation. The color impression is identical for a steep-angled and for a shallow-angled top view of the coatings. The total reflectance of the coating composition according to the .invention increases owing to the addition of ultra fine TiOZ, which does not reduce the brightness. This action can be demonstrated by measured reflectance spectra in the UV-VIS range. According to conventional processes, optical brighteners are used in order.to shift the reflectance spectra of coatings into the blue range.
The optical brighteners are blue-colored pigments or :- , 212'7814 blue dyes which are soluble in the medium being used, which absorb long-wave light and thus shift the intensity distribution of the remitted radiation towards the blue range. The great disadvantage of this ~ is however that the total reflectance decreases.
In the coating compositions according to the invention, the blue shift of the reflectance spectra takes place in that an additional reflectance is produced in the wave range of the blue color, namely in the range of about 290 to 440 nm.
Surprisingly, blue-colored coating compositions according to the invention can be produced by combining carbon blacks with ultra fine Tio2. Conventional titanium dioxides in combination with carbon blacks result in coating compositions of grey color.
Coating compositions according to the invention with a surprisingly intensive depth of color and brilliance can be produced with highly-colored blue pigments, such as copper phthalocyanine blue, in combination with ultra fine . TiOZ. A combination of these blue pigments with conventional titanium dioxides results in light blue coating compositions having a comparatively greyish-yellowish appearance. If bluefish red pigments are combined with ultra finev TiOZ, the blue tinge of the coating compositions according to the invention is increased, which means that the color magenta with an intensive depth of color is obtained.
With the coating compositions according to the invention, it. was surprisingly possible to establish that the ultra fine. TiOZ has a flocculation-stabilizing effect on the colored pigments.
212'~~~.~:
The ultra fine Tioz demonstrates a surprisingly great strength, which is expressed in that finished coating compositions are not destroyed by photo-degradation even after a long period of application.
'5 According to a preferred embodiment of the invention, at least one colored pigment, selected from blue, red or orange colored pigments, is contained in the coating composition as the colored pigment. Those colored pigments which preferably reflect light in the wave range of 400 nm to 550 nm and of 700 nm to 780 nm are designated as blue colored pigments. Those colored pigments which preferably reflect light in the wave range of 600 nm to 680 nm are designated as red colored pigments.
According to another preferred embodiment of the invention, at least one binder selected from the group consisting of alkyd resin, melamine resin, acrylic resin and other resins, is contained in the coating composition as binder solids content. The binders may be dilutable both with water and with organic solvents. They are also used as dispersions for formulating the coating composition. The binders react physically or chemically with a cross-linking action. According to the invention, multi-constituent reactive resins are also used.
According to a further preferred embodiment of the 'invention, the ultra fine Tio2 has a specific surface area of 30 to 150 m2/g. For conventional Tioz having a particle size of 150 to 350 nm (particle size determined by photo-centrifuge measurements), the specific surface area is 7 to 22 mz/g.
According to still another preferred embodiment of the invention, the total pigment volume concentration of all 212''784 the pigment constituents is from 1.0 to 20.0%. The coating compositions according to the invention show that with a low pigment volume concentration surprisingly a very good coverage is obtained far the total pigment, which makes them particularly suitable as top coats. This can be ascribed to the flocculation-stabilization action of the ultra fine Tioz on the other pigmentation constituents.
According to a further preferred embodiment of the invention the pigment volume concentration for the colored pigment is 0.5 to 15.0%.
Another object of the invention is a substrate which is coated with a coating composition according to the invention. Suitable substrates are any conventional commercially-available materials which can be coated on their surface with a top coat.
The coating composition according to the invention is produced in that colored pigment and/or carbon black, binder solids content, ultra fine TiOZ and solvent are dispersed in known manner and are applied to a substrate.
High-speed microelement mixer mills or roller mills and other dispersing apparatus are used for dispersing. The ultra fine Ti02 is added to the grinding paste of the colored pigment. Alternatively, a paste of the ultra fine ., ~Ti02 is d~.spersed and is added to the coating composition.
In this case, homogenization of the coating composition according to the invention using a dispersing apparatus with a lesser dispersing action, such as a dissolver, is sufficient.
A further object of the invention is the use of the coating composition according to the invention as a finishing lacquer for motor vehicles, industrial coating, printing ink, coil coating, package coating, plastic coating and decorative paint, and also as a varnish.
A special use of the coating composition according to the invention is in the decorative field, in which coatings with intensive depth of color and brilliance with high total reflectance are required.
The invention will be explained with reference to Examples 1 to 6 and the accompanying drawings in which:
Figure 1 shows the reflectance spectra of various coatings in the UV-VIS range in the wave range of 190 to 690 nm; and Figure 2 shows a section of the reflectance spectra represented in Figure 1 in the wavelength range of 25o to 450 nm.
In Examples 1 to 6, coating compositions before application to a substrate are illustrated in table form. The dispersed coating compositions, in addition to the constituents according to the invention, contain one or more solvents, which evaporate after application to a substrate. Some dispersed coating compositions additionally contain additives and catalysts. The coating compositions represented have all the constituents present in the coating compositions before application to a substrate. The contents of the constituents of the dispersed coating compositions are therefore given in percent by weight. "Dry substance" (%) defines the percentage of solid of the respective constituent which does not evaporate.
y___, 22'781.4 examples example 1 , Color: blue Constituent Ports by Density Density Dry Weighs wet g/cm3 dry g/cm3 substance wt.x x Alkyd Alkydal~ F 55.4201.000 1.100 65.0 resin 3001) Solvent Xylene 10.4650.870 0.000 0.0 Solvent Solvessos 3.223 0.950 0.000 0.0 Melamine10010) 21.8321.100 1.100 55.0 resin HaprenaleMF 2.522 1.800 1.800 100.0 Cas black8002) Ravens 11706) Ti02 ultra fine 6.538 4.000 4.000 100.0 Tit ilk ~
100,000 1.067 1.223 Pigment PVC Particle Specific surface area VoI.X size nm m2/g Total , , ~ 6.5 ultra Eirie T102 ~1) 3~S 20~30a~ 113.o0a~
Carbon blackb) 3.0 24b) 120.OOb) i v_ , 212~g~,4 Example 2 COIOr:royal ' blue Constituent PortsDensity Density Dry by weightwet dry substonce X
Wt / 3 . cm e/cm X
AlkydalAlkydaleF26111s1)60 1 1 resin 278 140 200 . . . 79.0 Resin Cymele3017) 12.0721.200 1.200 98.0 PhthalocyanineNeliogen Blue blue 1.6989 F3) 6.1511.600 1.600 100.0 TiOZ ultra fine 5.4924.000 4.000 10p.0 Ti0211) PTSS p-toluenesul(onic0.2780.950 1.050 50.0 acid AdditiveBYKe344g) 0.0620.940 1.050 50.0 Additive8YKe1415) 0.1240.890 1.000 3.0 Solvent8utanol 2.2330.800 0.000 0.0 SolventEthylglycol 2.1060.930 0.000 0.0 SolventEthylglycol 7.6940.970 0.000 0.0 acetate SolventButyl acetate3.5100.890 0.000 0.0 100.0001.168 1.298 PigmentPVC Particle Specific area surface Vol.-X size rm m2/g Total 9.5 -ultra Ti0211) 2.5 20-30) 113.00) fine Colored3) 7Ø 44.OOb) pigment ~..., 21281.4 Example 3 Color: mngento Constituent Perts by Donsity Density Ory weight wet dry substnnce ut.X g/em3 9/em3 X
Alkyd AlkydaleF3001~52.744 1.000 1.100 65.0 resin PigmentCinquasias-Red Red YRT759D4~ 6.788 1.550 1.550 100.0 254 Solvessoa1001013.Ob7 0.950 0.000 0.0 Solvent , SolventI(ylene 9.959 0.870 0.000 0.0 HelamineHaprenale(1T8002120.778 1.100 1.100 55.0 resin ultra fine 6.664 4.000 4.000 100.0 Ti02 Tio211) 100.0001.083 1.243 Pigment PVC Particle Specific surface area Vol.-X size ~m m2/g Total 12.7 - .
ultra fine 3.5 Z O-30a1 113.ooa~
Ti0211) Colored pigment9,2 50-110b1 44.OOb1 4~
..', example 4 Color: magenta Constituent Parts by Density Density Ory Weight uet dry substance Nt.X
9/cm3 9/cm3 X
Acrylic MacrynaleSM510n2T49.4021.000 1.100 60.0 resin DOTI Irgastab eODTl.410.010 1.000 1.000 100.0 Amine Dimethylethanolamine0.141 1.000 1.000 100.0 SiliconeSilicone oil 0.006 1.000 1.000 100.0 oil L 0508 Solvent Solvessos10010T3.167 0.950 0.000 0.0 Solvent Xylene 4.359 0.870 0.000 0.0 Solvent Methoxypropyl5.100 0.900 0.000 0.0 acetate Pig. Pioment red 2.714 1.650 1.650 100.0 Red 20297 T 102 ultra fine 13.1594.000 4.000 100.0 ' T 10211 ) PolyisocyanateOesmodur N 21.9421.070 1.100 75.0 100.000 1.123 1.322 Pigment PVC Particle Specific surface area Vol,-X site rm m2/g Total tU.S
ultra fine ~710211) 7.0 20-30°~ 113.OOa1 Colored pigment 9T 3.5 53.OOc1 a ., ~, ~ 21~'~~~.4 1. 2 Example 5 Nnter-tensed vnrnish: blue Constituent Parts by Density Density Dry weight Not dry substonco Nt.X g/ca~3 9/cm3 %
Alkyd Ileso-Alkyd 44.1381.000 1.100 00.0 resin 359 1f1121 HelamineNaprennle 12.3901.200 1.200 95.0 resin HF 90021 Amine Triethylamine4.394 0.900 0.900 100.0 Solvent Isobutanol 7.784 0.900 0.000 0.0 Solvent Nater 19.3341.000 0.000 0.0 Carbon Ravens 1170612.420 1.800 1.800 100.0 black AdditiveSolingen 2n13~0.502 0.900 1.000 35.0 AdditiveBYKs32051 0.126 0.850 1.000 52.0 AdditiveOorchigerr~ 0.126 1.100 1.100 100.0 AdditiveNopcos 80341410.628 0.920 0.920 100.0 Solvent 8utylglycol 2.510 0.980 0.000 0.0 Ti02 ultra fine 5.64113.600 3.600 100.0 Ti02 100.000 1.180 1.231 Pigment FvC Particle Specific surface 9o1.-X site nn area - m2/g Total 5.7 ultra fine Ti021113.1 20-30a1 113.OOa1 Carbon black6l 2,6 24b1 120,DOb1 ~~,~~4 example 6 Con blue coating:
Constituent Parts Density DensityDry by weight uet dry substance Wt 3 3 X /
. cm g/cm X
g SaturatedOynapole 58.700 1.000 1.100 60.0 polyester Solvent Solvessos 21.290 0.990 0.000 0.0 CatalystVestoritkat.2.914 0.950 1.050 50.0 Solvent Butyldiglycol0.953 0.950 0.000 0.0 Resin Cymele30371 9.279 1.100 1.100 100.0 Solvent Dibasic ester2.719 0.900 0.000 0.0 Special Special Black0.698 1.800 1.800 100.0 carbon 5161 black TiOZ ultra fine 3.447 4.000 4.000 100.0 TiOZ
100.000 1.031 1.163 Pigment pVC Particle Specific surface area Vol.-X size rm m2/g Total 1.9 -ultra fine 2.0 20-3081 113.OOa1 Ti0211T
Carbon black1610.9 20b1 240.OOb1 212' 8~.4 a) measured according to Debye-Scherrer b) details of manufacturer c) measured according to DIN 66 132 List of Manufacturers 1) Bayer AG
2) Hoechst AG
3) BASF AG
4) CIBA-GEIGY AG
A coat composition is known from EP 0 270 472 Bl which contains 24.0 to 35.0% by weight of a thermoplastic or duroplastic resin, 1.1 to 10.5% by weight of a metallic or metal-like pigment and 1.1 to 10.5% by weight transparent Ti02, which has a particle size of 20 to 30 nm. The coat composition is intended for use as a base coating for a metallic paint for car bodies in the automobile industry. At least one layer of an unpigmented varnish is applied to this base paint.
Several layers of a pigmented base paint may also be applied. However, the pigmented coat composition is not used as a top coat. In addition to the metallic effect, the coating composition exhibits the frast effect. The frost effect can be noted when observing coat compositions which contain metallic or metal-like pigments in combination with finely-divided Ti02. The frost effect depends on the direction of incidence of the light relative to the sample and to the observer.
If the samples are observed from a vertical direction, the coating seems yellowish to golden in color, and if observed from a horizontal direction, the sample looks b~ueish.
It can be inferred from the publication by J. G. Balfour in J. Oil Colour Chem. Assoc. (lj, 1992, page 21 ff. that in the case of paints which contain exclusively ultra fine Ti02, the total reflectance of the paints increases with the increase in the pigment volume concentration from o.1 to 1.0% of 2~,2~81.4 ultra fine TiOZ. The increase in the reflectance of the paints is greater in the range of blue light at a relatively short wavelength. With the increase in ultra. fine 'fiOZ in the pigment volume concentration, , the paints appear to be increasingly milky to the observer.
In conventional coating compositions which are applied to a substrate, an improvement in the total reflectance and depth of color is always desired. An improvement in the unsatisfactory stabilization of colored pigments is likewise always desired. This is particularly so when it is necessary to apply preferably only one coating composition as top coat to a substrate, and therefore the total reflectance and the depth of color only result from the one top coat.
It is an object of the present invention to provide a coating composition which has a high total reflectance, intensive depth of color and long storage stability, and also good flocculation stabilization of colored pigments.
This object is achieved by a coating composition which consists of o.5 to 30.0% by volume colored pigment and/or carbon black, with the proviso that it is not a metallic pigment or metal-like pigment, 55.0 to 98.50 by volume binder solids content and 0.3 to 15% by volume ultra fine Ti02 having a particle size of 5 to 40 nm and has a high total reflectance and intensive depth of color. The crystallite size is determined according to Debye-Scherrer. The crystallite size thus determined is approximately identical to the particle size. The term "coating composition" refers to the hardened coating.
2~2~~8~.4 The proportions of the coating composition are given in pigment volume concentration (PVC), and therefore in %
by volume or, in simplified manner, in %. The pigment volume concentration designates the proportion by ~ volume of one or more pigments, relative to the total solids volume of the hardened coating.
The ultra fine TiOz may be in the form of the crystal modifications rutile, anatase or in X-amorphous form. For reasons of weathering-resistance, a ultra fine Ti02 in the rutile modification is preferably used. Subsequent inorganic and/or organic treatment of the ultra fine Ti02 produced has no effect on the suitability thereof in the coating compositions according to the invention. The production process for the ultra fine Ti02 or the particle morphology of the ultra fine Ti02 do not impair the action of the ultra fine Ti02 in the coating composition according to the invention. Ultra fine Tio2 can therefore be used in coating compositions according to the invention independently of the method of production or particle morphology thereof.
The coating compositions according to the invention have a surprisingly strong blue-tone shift of the respective color. The color does not change with the angle of observation. The color impression is identical for a steep-angled and for a shallow-angled top view of the coatings. The total reflectance of the coating composition according to the .invention increases owing to the addition of ultra fine TiOZ, which does not reduce the brightness. This action can be demonstrated by measured reflectance spectra in the UV-VIS range. According to conventional processes, optical brighteners are used in order.to shift the reflectance spectra of coatings into the blue range.
The optical brighteners are blue-colored pigments or :- , 212'7814 blue dyes which are soluble in the medium being used, which absorb long-wave light and thus shift the intensity distribution of the remitted radiation towards the blue range. The great disadvantage of this ~ is however that the total reflectance decreases.
In the coating compositions according to the invention, the blue shift of the reflectance spectra takes place in that an additional reflectance is produced in the wave range of the blue color, namely in the range of about 290 to 440 nm.
Surprisingly, blue-colored coating compositions according to the invention can be produced by combining carbon blacks with ultra fine Tio2. Conventional titanium dioxides in combination with carbon blacks result in coating compositions of grey color.
Coating compositions according to the invention with a surprisingly intensive depth of color and brilliance can be produced with highly-colored blue pigments, such as copper phthalocyanine blue, in combination with ultra fine . TiOZ. A combination of these blue pigments with conventional titanium dioxides results in light blue coating compositions having a comparatively greyish-yellowish appearance. If bluefish red pigments are combined with ultra finev TiOZ, the blue tinge of the coating compositions according to the invention is increased, which means that the color magenta with an intensive depth of color is obtained.
With the coating compositions according to the invention, it. was surprisingly possible to establish that the ultra fine. TiOZ has a flocculation-stabilizing effect on the colored pigments.
212'~~~.~:
The ultra fine Tioz demonstrates a surprisingly great strength, which is expressed in that finished coating compositions are not destroyed by photo-degradation even after a long period of application.
'5 According to a preferred embodiment of the invention, at least one colored pigment, selected from blue, red or orange colored pigments, is contained in the coating composition as the colored pigment. Those colored pigments which preferably reflect light in the wave range of 400 nm to 550 nm and of 700 nm to 780 nm are designated as blue colored pigments. Those colored pigments which preferably reflect light in the wave range of 600 nm to 680 nm are designated as red colored pigments.
According to another preferred embodiment of the invention, at least one binder selected from the group consisting of alkyd resin, melamine resin, acrylic resin and other resins, is contained in the coating composition as binder solids content. The binders may be dilutable both with water and with organic solvents. They are also used as dispersions for formulating the coating composition. The binders react physically or chemically with a cross-linking action. According to the invention, multi-constituent reactive resins are also used.
According to a further preferred embodiment of the 'invention, the ultra fine Tio2 has a specific surface area of 30 to 150 m2/g. For conventional Tioz having a particle size of 150 to 350 nm (particle size determined by photo-centrifuge measurements), the specific surface area is 7 to 22 mz/g.
According to still another preferred embodiment of the invention, the total pigment volume concentration of all 212''784 the pigment constituents is from 1.0 to 20.0%. The coating compositions according to the invention show that with a low pigment volume concentration surprisingly a very good coverage is obtained far the total pigment, which makes them particularly suitable as top coats. This can be ascribed to the flocculation-stabilization action of the ultra fine Tioz on the other pigmentation constituents.
According to a further preferred embodiment of the invention the pigment volume concentration for the colored pigment is 0.5 to 15.0%.
Another object of the invention is a substrate which is coated with a coating composition according to the invention. Suitable substrates are any conventional commercially-available materials which can be coated on their surface with a top coat.
The coating composition according to the invention is produced in that colored pigment and/or carbon black, binder solids content, ultra fine TiOZ and solvent are dispersed in known manner and are applied to a substrate.
High-speed microelement mixer mills or roller mills and other dispersing apparatus are used for dispersing. The ultra fine Ti02 is added to the grinding paste of the colored pigment. Alternatively, a paste of the ultra fine ., ~Ti02 is d~.spersed and is added to the coating composition.
In this case, homogenization of the coating composition according to the invention using a dispersing apparatus with a lesser dispersing action, such as a dissolver, is sufficient.
A further object of the invention is the use of the coating composition according to the invention as a finishing lacquer for motor vehicles, industrial coating, printing ink, coil coating, package coating, plastic coating and decorative paint, and also as a varnish.
A special use of the coating composition according to the invention is in the decorative field, in which coatings with intensive depth of color and brilliance with high total reflectance are required.
The invention will be explained with reference to Examples 1 to 6 and the accompanying drawings in which:
Figure 1 shows the reflectance spectra of various coatings in the UV-VIS range in the wave range of 190 to 690 nm; and Figure 2 shows a section of the reflectance spectra represented in Figure 1 in the wavelength range of 25o to 450 nm.
In Examples 1 to 6, coating compositions before application to a substrate are illustrated in table form. The dispersed coating compositions, in addition to the constituents according to the invention, contain one or more solvents, which evaporate after application to a substrate. Some dispersed coating compositions additionally contain additives and catalysts. The coating compositions represented have all the constituents present in the coating compositions before application to a substrate. The contents of the constituents of the dispersed coating compositions are therefore given in percent by weight. "Dry substance" (%) defines the percentage of solid of the respective constituent which does not evaporate.
y___, 22'781.4 examples example 1 , Color: blue Constituent Ports by Density Density Dry Weighs wet g/cm3 dry g/cm3 substance wt.x x Alkyd Alkydal~ F 55.4201.000 1.100 65.0 resin 3001) Solvent Xylene 10.4650.870 0.000 0.0 Solvent Solvessos 3.223 0.950 0.000 0.0 Melamine10010) 21.8321.100 1.100 55.0 resin HaprenaleMF 2.522 1.800 1.800 100.0 Cas black8002) Ravens 11706) Ti02 ultra fine 6.538 4.000 4.000 100.0 Tit ilk ~
100,000 1.067 1.223 Pigment PVC Particle Specific surface area VoI.X size nm m2/g Total , , ~ 6.5 ultra Eirie T102 ~1) 3~S 20~30a~ 113.o0a~
Carbon blackb) 3.0 24b) 120.OOb) i v_ , 212~g~,4 Example 2 COIOr:royal ' blue Constituent PortsDensity Density Dry by weightwet dry substonce X
Wt / 3 . cm e/cm X
AlkydalAlkydaleF26111s1)60 1 1 resin 278 140 200 . . . 79.0 Resin Cymele3017) 12.0721.200 1.200 98.0 PhthalocyanineNeliogen Blue blue 1.6989 F3) 6.1511.600 1.600 100.0 TiOZ ultra fine 5.4924.000 4.000 10p.0 Ti0211) PTSS p-toluenesul(onic0.2780.950 1.050 50.0 acid AdditiveBYKe344g) 0.0620.940 1.050 50.0 Additive8YKe1415) 0.1240.890 1.000 3.0 Solvent8utanol 2.2330.800 0.000 0.0 SolventEthylglycol 2.1060.930 0.000 0.0 SolventEthylglycol 7.6940.970 0.000 0.0 acetate SolventButyl acetate3.5100.890 0.000 0.0 100.0001.168 1.298 PigmentPVC Particle Specific area surface Vol.-X size rm m2/g Total 9.5 -ultra Ti0211) 2.5 20-30) 113.00) fine Colored3) 7Ø 44.OOb) pigment ~..., 21281.4 Example 3 Color: mngento Constituent Perts by Donsity Density Ory weight wet dry substnnce ut.X g/em3 9/em3 X
Alkyd AlkydaleF3001~52.744 1.000 1.100 65.0 resin PigmentCinquasias-Red Red YRT759D4~ 6.788 1.550 1.550 100.0 254 Solvessoa1001013.Ob7 0.950 0.000 0.0 Solvent , SolventI(ylene 9.959 0.870 0.000 0.0 HelamineHaprenale(1T8002120.778 1.100 1.100 55.0 resin ultra fine 6.664 4.000 4.000 100.0 Ti02 Tio211) 100.0001.083 1.243 Pigment PVC Particle Specific surface area Vol.-X size ~m m2/g Total 12.7 - .
ultra fine 3.5 Z O-30a1 113.ooa~
Ti0211) Colored pigment9,2 50-110b1 44.OOb1 4~
..', example 4 Color: magenta Constituent Parts by Density Density Ory Weight uet dry substance Nt.X
9/cm3 9/cm3 X
Acrylic MacrynaleSM510n2T49.4021.000 1.100 60.0 resin DOTI Irgastab eODTl.410.010 1.000 1.000 100.0 Amine Dimethylethanolamine0.141 1.000 1.000 100.0 SiliconeSilicone oil 0.006 1.000 1.000 100.0 oil L 0508 Solvent Solvessos10010T3.167 0.950 0.000 0.0 Solvent Xylene 4.359 0.870 0.000 0.0 Solvent Methoxypropyl5.100 0.900 0.000 0.0 acetate Pig. Pioment red 2.714 1.650 1.650 100.0 Red 20297 T 102 ultra fine 13.1594.000 4.000 100.0 ' T 10211 ) PolyisocyanateOesmodur N 21.9421.070 1.100 75.0 100.000 1.123 1.322 Pigment PVC Particle Specific surface area Vol,-X site rm m2/g Total tU.S
ultra fine ~710211) 7.0 20-30°~ 113.OOa1 Colored pigment 9T 3.5 53.OOc1 a ., ~, ~ 21~'~~~.4 1. 2 Example 5 Nnter-tensed vnrnish: blue Constituent Parts by Density Density Dry weight Not dry substonco Nt.X g/ca~3 9/cm3 %
Alkyd Ileso-Alkyd 44.1381.000 1.100 00.0 resin 359 1f1121 HelamineNaprennle 12.3901.200 1.200 95.0 resin HF 90021 Amine Triethylamine4.394 0.900 0.900 100.0 Solvent Isobutanol 7.784 0.900 0.000 0.0 Solvent Nater 19.3341.000 0.000 0.0 Carbon Ravens 1170612.420 1.800 1.800 100.0 black AdditiveSolingen 2n13~0.502 0.900 1.000 35.0 AdditiveBYKs32051 0.126 0.850 1.000 52.0 AdditiveOorchigerr~ 0.126 1.100 1.100 100.0 AdditiveNopcos 80341410.628 0.920 0.920 100.0 Solvent 8utylglycol 2.510 0.980 0.000 0.0 Ti02 ultra fine 5.64113.600 3.600 100.0 Ti02 100.000 1.180 1.231 Pigment FvC Particle Specific surface 9o1.-X site nn area - m2/g Total 5.7 ultra fine Ti021113.1 20-30a1 113.OOa1 Carbon black6l 2,6 24b1 120,DOb1 ~~,~~4 example 6 Con blue coating:
Constituent Parts Density DensityDry by weight uet dry substance Wt 3 3 X /
. cm g/cm X
g SaturatedOynapole 58.700 1.000 1.100 60.0 polyester Solvent Solvessos 21.290 0.990 0.000 0.0 CatalystVestoritkat.2.914 0.950 1.050 50.0 Solvent Butyldiglycol0.953 0.950 0.000 0.0 Resin Cymele30371 9.279 1.100 1.100 100.0 Solvent Dibasic ester2.719 0.900 0.000 0.0 Special Special Black0.698 1.800 1.800 100.0 carbon 5161 black TiOZ ultra fine 3.447 4.000 4.000 100.0 TiOZ
100.000 1.031 1.163 Pigment pVC Particle Specific surface area Vol.-X size rm m2/g Total 1.9 -ultra fine 2.0 20-3081 113.OOa1 Ti0211T
Carbon black1610.9 20b1 240.OOb1 212' 8~.4 a) measured according to Debye-Scherrer b) details of manufacturer c) measured according to DIN 66 132 List of Manufacturers 1) Bayer AG
2) Hoechst AG
3) BASF AG
4) CIBA-GEIGY AG
5) BYK Chemie AG
6) Columbian Chemical 7) American Cyanamid Co.
8) Wacker Chemie 9) Sun Chemical 10) Texaco AG
11) Sachtleben Chemie GmbH
12j Cray Valley 13) Gebr. Borchers AG
14) Munzing Chemie 15) Hiils AG , 16) Degussa AG
Description of Figures 1 and 2 Figure 1 shows the reflectance spectra of various coatings in the UV-VIS range in the wave range of 190 to 690 nm. The reflection is measured at a given wavelength. The reflection is given on the ordinate in percent. The reflection measurements are measured with the Ulbrich-Kugel (System: Phillips PU 8800) at a wavelength advance of 1 nms'~ with BaS04 as reference.
Figure 2 shows a section of the reflectance spectra , represented in Figure 1 in the wa~relength range of 250 to 450 nm.
212'78~.~
Samples (1) to (5) are paints having the pigments listed below:
Vol.-% Vol.-% Sample '5 3.0 carbon black (1) 3.0 carbon black 3.5 ultra fine Ti02i~~ (2) 3 . carbon black + 7 . 0 ultra fine Ti.02~~~( ) 9 . Irgazin Red-DPPB04~+ 7 . 0 ultra fine $aS0411)( ) 10 9 Irgazin Red-DPPB04~+ 3 . 5 ultra fine Ti02~~~( . 2 5 ) In samples (2), (3) and (5), Ti02 having a particle size of to 3o nm was used. In sample (4), BaS04 having a particle size of 150 nm to 25o nm was used.
Samples ( 1 ) and ( 4 ) contain no ultra fine TiOz. The spectra of samples (1) and (4) in Figures 1 and 2 do not exhibit any increase in the reflection in the blue range of 30o to 400 nm. Samples ( 2 ) , ( 3 ) and ( 5 ) contain ultra fine Ti02 in different pigment volume concentrations. Samples (2) and (3) differ in the pigment volume concentration of ultra fine TiOz. Sample (2) contains 3.5% by volume ultra fine Ti02, and sample (3) contains 7.0% by volume ultra fine Ti02. As a result of this, sample ( 3 ) in the wavelength range of 330 to 400 nm exhibits an increase in reflection of on average i%. The reflection of samples (4) and (5) in the range of red light above 570 nm with a maximum at 650 !nm can be ascribed to the red pigment used in these samples.
Samples (4) and (5) differ in that sample (5) contains 3.5%
by volume ultra fine TiOz, whereas sample ( 4 ) contains 7% by volume ultra fine BaS04. Even in the red range, sample j5) shows an increase in reflection by 5% compared with sample (4), which is further proof that the total reflectance of .. ;~12~'~8~.4 the coating compositions according to the invention is increased by the addition of ultra fine TiOz, which is a surprising result of the present invention. E'urthermore, it was surprisingly discovered that when the coating compositions according to the invention are irradiated with a blue light source of fluorescence-like effect is observed.
12j Cray Valley 13) Gebr. Borchers AG
14) Munzing Chemie 15) Hiils AG , 16) Degussa AG
Description of Figures 1 and 2 Figure 1 shows the reflectance spectra of various coatings in the UV-VIS range in the wave range of 190 to 690 nm. The reflection is measured at a given wavelength. The reflection is given on the ordinate in percent. The reflection measurements are measured with the Ulbrich-Kugel (System: Phillips PU 8800) at a wavelength advance of 1 nms'~ with BaS04 as reference.
Figure 2 shows a section of the reflectance spectra , represented in Figure 1 in the wa~relength range of 250 to 450 nm.
212'78~.~
Samples (1) to (5) are paints having the pigments listed below:
Vol.-% Vol.-% Sample '5 3.0 carbon black (1) 3.0 carbon black 3.5 ultra fine Ti02i~~ (2) 3 . carbon black + 7 . 0 ultra fine Ti.02~~~( ) 9 . Irgazin Red-DPPB04~+ 7 . 0 ultra fine $aS0411)( ) 10 9 Irgazin Red-DPPB04~+ 3 . 5 ultra fine Ti02~~~( . 2 5 ) In samples (2), (3) and (5), Ti02 having a particle size of to 3o nm was used. In sample (4), BaS04 having a particle size of 150 nm to 25o nm was used.
Samples ( 1 ) and ( 4 ) contain no ultra fine TiOz. The spectra of samples (1) and (4) in Figures 1 and 2 do not exhibit any increase in the reflection in the blue range of 30o to 400 nm. Samples ( 2 ) , ( 3 ) and ( 5 ) contain ultra fine Ti02 in different pigment volume concentrations. Samples (2) and (3) differ in the pigment volume concentration of ultra fine TiOz. Sample (2) contains 3.5% by volume ultra fine Ti02, and sample (3) contains 7.0% by volume ultra fine Ti02. As a result of this, sample ( 3 ) in the wavelength range of 330 to 400 nm exhibits an increase in reflection of on average i%. The reflection of samples (4) and (5) in the range of red light above 570 nm with a maximum at 650 !nm can be ascribed to the red pigment used in these samples.
Samples (4) and (5) differ in that sample (5) contains 3.5%
by volume ultra fine TiOz, whereas sample ( 4 ) contains 7% by volume ultra fine BaS04. Even in the red range, sample j5) shows an increase in reflection by 5% compared with sample (4), which is further proof that the total reflectance of .. ;~12~'~8~.4 the coating compositions according to the invention is increased by the addition of ultra fine TiOz, which is a surprising result of the present invention. E'urthermore, it was surprisingly discovered that when the coating compositions according to the invention are irradiated with a blue light source of fluorescence-like effect is observed.
Claims (10)
1. A coating composition which is intended to be applied to a substrate and contains ultra fine TiO2, characterized in that said coating composition consists of:
0.5 to 30.0% by volume colored pigment, carbon black or both of them, with the proviso that said pigment is not a metallic pigment or metal-like pigment;
55.0 to 98.5% by volume binder solids content; and 0.3 to 15% by volume ultra fine TiO2 having a particle size of 5 to 40 nm.
0.5 to 30.0% by volume colored pigment, carbon black or both of them, with the proviso that said pigment is not a metallic pigment or metal-like pigment;
55.0 to 98.5% by volume binder solids content; and 0.3 to 15% by volume ultra fine TiO2 having a particle size of 5 to 40 nm.
2. A coating composition according to claim 1, characterized in that at least one colored pigment, selected from blue or red colored pigments, is contained in the coating composition as the colored pigment.
3. A coating composition according to claim 1 or 2, characterized in that at least one binder selected from the group consisting of alkyd resin, melamine resin, acrylic resin and other resins, is contained as binder solids content.
4. A coating composition according to claim 1 or 2, characterized in that the ultra fine TiO2 has a specific surface area of 30 to 150 m2/g.
5. A coating composition according to claim 3, characterized in that the ultra fine TiO2 has a specific surface area of 30 to 150 m2/g.
6. A coating composition according to claim 1, 2 or 5, characterized in that the total pigment volume concentration of all the pigment constituents is from 1.0 to 20.0%.
7. ~A coating composition according to claim 3, characterized in that the total pigment volume concentration of all the pigment constituents is from 1.0 to 20Ø
8. ~A coating composition according to claim 1, 2, 5 or 7, characterized in that the pigment volume concentration for the colored pigment is 0.5 to 15.0%.
9. ~A method for producing a coating composition according to claim 1, 2, 5 or 7, characterized in that the colored pigment and/or carbon black, binder solids content, ultra fine TiO2 and solvent are dispersed.
10. The use of a coating composition according to claim 1, 2, 5 or 7, as a finishing lacquer for motor vehicles, industrial coating, printing ink, coil coating, package coating, plastic coating and decorative paint, or as a varnish.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4323372.4 | 1993-07-13 | ||
| DE4323372A DE4323372C2 (en) | 1993-07-13 | 1993-07-13 | Coating composition that is applied to a substrate and contains finely divided TiO¶2¶ |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2127814A1 CA2127814A1 (en) | 1995-01-14 |
| CA2127814C true CA2127814C (en) | 2004-10-19 |
Family
ID=6492656
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002127814A Expired - Fee Related CA2127814C (en) | 1993-07-13 | 1994-07-12 | Coating composition which is applied to a substrate and contains ultra fine tio2 |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0634462B1 (en) |
| JP (1) | JPH07150080A (en) |
| CA (1) | CA2127814C (en) |
| DE (2) | DE4323372C2 (en) |
| ZA (1) | ZA945091B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19540623A1 (en) * | 1995-10-31 | 1997-05-07 | Inst Neue Mat Gemein Gmbh | Process for the production of composite materials with a high proportion of interfaces and thus obtainable composite materials |
| US6770705B2 (en) * | 2002-02-20 | 2004-08-03 | Ppg Industries Ohio, Inc. | Curable film-forming composition exhibiting improved impact strength and chip resistance |
| DE10358488A1 (en) * | 2003-12-13 | 2005-07-14 | Basf Coatings Ag | Coating material, process for its preparation and its use for the production of transparent, corrosion-inhibiting coatings |
| DE102004054048A1 (en) * | 2004-11-05 | 2006-05-11 | Basf Ag | coating materials |
| WO2023227600A1 (en) | 2022-05-25 | 2023-11-30 | Omya International Ag | Process for producing a white uv-absorbing surface-reacted calcium carbonate doped with a titanium species, a white uv-absorbing surface-reacted calcium carbonate and use thereof |
| WO2023227585A1 (en) | 2022-05-25 | 2023-11-30 | Omya International Ag | White uv-absorbing surface-reacted calcium carbonate doped with a titanium species |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4753829A (en) * | 1986-11-19 | 1988-06-28 | Basf Corporation | Opalescent automotive paint compositions containing microtitanium dioxide pigment |
| JPS63247032A (en) * | 1987-04-03 | 1988-10-13 | 日本ペイント株式会社 | Surface-treated metallic blank |
-
1993
- 1993-07-13 DE DE4323372A patent/DE4323372C2/en not_active Expired - Fee Related
-
1994
- 1994-06-17 EP EP94109347A patent/EP0634462B1/en not_active Revoked
- 1994-06-17 DE DE59407862T patent/DE59407862D1/en not_active Revoked
- 1994-07-12 CA CA002127814A patent/CA2127814C/en not_active Expired - Fee Related
- 1994-07-13 ZA ZA945091A patent/ZA945091B/en unknown
- 1994-07-13 JP JP6183912A patent/JPH07150080A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| DE59407862D1 (en) | 1999-04-08 |
| DE4323372C1 (en) | 1994-12-15 |
| JPH07150080A (en) | 1995-06-13 |
| ZA945091B (en) | 1996-01-15 |
| CA2127814A1 (en) | 1995-01-14 |
| EP0634462A2 (en) | 1995-01-18 |
| EP0634462B1 (en) | 1999-03-03 |
| EP0634462A3 (en) | 1996-06-05 |
| DE4323372C2 (en) | 2003-07-31 |
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