CA2024486A1 - Platelet-like, surface-modified substrates - Google Patents
Platelet-like, surface-modified substratesInfo
- Publication number
- CA2024486A1 CA2024486A1 CA002024486A CA2024486A CA2024486A1 CA 2024486 A1 CA2024486 A1 CA 2024486A1 CA 002024486 A CA002024486 A CA 002024486A CA 2024486 A CA2024486 A CA 2024486A CA 2024486 A1 CA2024486 A1 CA 2024486A1
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- Prior art keywords
- coupling
- platelet
- substrates
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- low molecular
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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
- 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
- C09C1/0015—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0001—Post-treatment of organic pigments or dyes
- C09B67/0004—Coated particulate pigments or dyes
-
- C—CHEMISTRY; METALLURGY
- 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
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
-
- C—CHEMISTRY; METALLURGY
- 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
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/12—Treatment with organosilicon compounds
-
- 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
- C09D5/36—Pearl essence, e.g. coatings containing platelet-like pigments for pearl lustre
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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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
- 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
- C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
- C09C2200/10—Interference pigments characterized by the core material
- C09C2200/102—Interference pigments characterized by the core material the core consisting of glass or silicate material like mica or clays, e.g. kaolin
-
- C—CHEMISTRY; METALLURGY
- 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
- C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
- C09C2200/40—Interference pigments comprising an outermost surface coating
- C09C2200/402—Organic protective coating
- C09C2200/403—Low molecular weight materials, e.g. fatty acids
- C09C2200/404—Low molecular weight materials, e.g. fatty acids comprising additional functional groups, e.g. -NH2, -C=C- or -SO3
-
- C—CHEMISTRY; METALLURGY
- 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
- C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
- C09C2200/40—Interference pigments comprising an outermost surface coating
- C09C2200/402—Organic protective coating
- C09C2200/407—Organosilicon materials, e.g. silanes, silicones
- C09C2200/408—Organosilicon materials, e.g. silanes, silicones comprising additional functional groups, e.g. –NH2, -C=C- or -SO3
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Cosmetics (AREA)
- Paints Or Removers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
Abstract
Abstract Plate-like, surface-modified substrates, obtainable by treating platelet-like substrates using at least dye-functional organic coupling agents and then coupling a low molecular weight organic radical to a second functional group of the agent which has been coupled to the substrate, are eminently suitable for use in formulations such as paints, dye compositions, plastics and cosmetics.
Description
q,~
Merck Patent Gesellschaft mit beschrankter Haftung 6100 Darmstadt Platelet-like, surface-modified substrates The invention relates to platelet-like, surface-modified substrates, obtainable by treating platelet-like substrates using at least di~functional organic coupling agents and ~hen coupling a low molecular weight organic radical to a second functional group of the ag nt which has been coupled to the substrate.
Platelet-like substrates, i.e. materials having a rel~-tively small thickness in relation to length and width are used in many fields of technology. For instance, platelet-like minerals such as, for example, kaolin, mica lS or talc are used in finely divided form a~ fillers for plastics. Platelet-like pi~ments such as, for example, s metal oxide-coated mica pla$elets or platelet-like iron oxide or bismuth oxychloride are used not only in ~he pigmenting of, for example, paints, ~olorants, pla8tic5 and the like but also in cosmetic preparations.
The ever increasing utility of platele~-liXe substrates in different industrial field~ increasingly requires the development of surface-modified substrates ultimately to ensure the compatibility of the substrates with further component3 presa~t in industrial compositions.
A fundamental problem i8 the ~trong tendency of platelet-like substrates of this type to form agglomerates in which the substrates are present lying on top of one another like a deck of cards and can only be separated again with difficulty owing to strong adhesion. Thi~ is all the more troublesome ~inca, on incorporating platelet-like substrates in for~ulations, high shear force~ cannot be applied owing to the fragility of the thin substrat~s.
Merck Patent Gesellschaft mit beschrankter Haftung 6100 Darmstadt Platelet-like, surface-modified substrates The invention relates to platelet-like, surface-modified substrates, obtainable by treating platelet-like substrates using at least di~functional organic coupling agents and ~hen coupling a low molecular weight organic radical to a second functional group of the ag nt which has been coupled to the substrate.
Platelet-like substrates, i.e. materials having a rel~-tively small thickness in relation to length and width are used in many fields of technology. For instance, platelet-like minerals such as, for example, kaolin, mica lS or talc are used in finely divided form a~ fillers for plastics. Platelet-like pi~ments such as, for example, s metal oxide-coated mica pla$elets or platelet-like iron oxide or bismuth oxychloride are used not only in ~he pigmenting of, for example, paints, ~olorants, pla8tic5 and the like but also in cosmetic preparations.
The ever increasing utility of platele~-liXe substrates in different industrial field~ increasingly requires the development of surface-modified substrates ultimately to ensure the compatibility of the substrates with further component3 presa~t in industrial compositions.
A fundamental problem i8 the ~trong tendency of platelet-like substrates of this type to form agglomerates in which the substrates are present lying on top of one another like a deck of cards and can only be separated again with difficulty owing to strong adhesion. Thi~ is all the more troublesome ~inca, on incorporating platelet-like substrates in for~ulations, high shear force~ cannot be applied owing to the fragility of the thin substrat~s.
2 ~
Numerous mathods have therefore been developed, inter alia, to solve the prohlem of incorporating platelet-like pigments, in particular, in-to thermoplastic materials (DE-A-2,603,211, DE-A-3,221,044, DE-A-3,627,329).
5 Furthermore, coatings employing polysiloxanes for improved weathering resistance have been disclosed (DE 3,334,598), and also treatment with coupling agents such as organotitanates to give improved dispersibility in cosmetic preparations (EP 0,306,056), and with organosilanes to give improved water resistance (~P 0,268,918).
The object of the present invention is to develop other and better processes for surface modification of platel~t-like substrates. In particular, the substra~es must be compatible with a great many di~ferent industrial formulations without the typical properties of platelet-like substrates being lost. There is a need, inter alia, for platelet-like, surface-modi~ied pigments which can be incorporated in formulations without losing their pigme~t properties. Examples of frequently encountered disadvantages from pigment incorporation ar~ pigment shock, ie. the formation of agglomerates on incorporation owing to incompatibilities, and pigment migration.
Thi~ object is achieved by the present invention. In particula~, it has been found that the trea~ment of platelet-like sub~trates with organic coupling agents which have at least one other functional group for coupling to a low molecular weight organic radical allows the preparation of ~urface-modified substrates having virtually any de~ired functional propertieY, depending on the type of low molecular weight organic radical.
The present invention accordingly provides platelet-like ~urface-modiied sub~trates, obtainable by txeating platelet-like substrates with at least di-functional organic coupling agent~ and then coupling a low molecular weight organic radical to a second functional group of the agent which has been coupled to the substrate.
The invention also provides platelet-like surface-modified substrates, obtainable by treating platelet-like substrates with organo~Ti, organo-Zr or organo-Zr/organo-Al coupling agents, characterized in that after the coupling reaction to the coupled agent, a second functional group is available for coupling to a low molecular weight organic radical.
Furthermore, the present invention provides a process for the preparation of substrate according to ClaLm 1, characterized in that platelet-like substrates are reacted in an aqueous or an organic medium or in a mixture thereof with the coupling agent and then the low molecular weight organic radical is coupled, or in that initially a coupling agent containing the low molecular weight organic radical is prepared and is then r~ac$ed with the substrate.
Finally, the inventisn provide~ the use of the ~urface-modified substratQs according to ClaLm 1 in formulations such as paints, dye compositions, plaætics and cosmetics.
The invention ultimately provides formulation~ which contain the substrates according to the invention.
Prefarred platelet-like sub~trates for surface modifica-tion according to the invention are, in particular, layer-~tructured ~ilicates and oxides or oxide-coated materials, ~ince these have reactive OH groups on their surface. Examplas of the~e ar , on the one hand, mica, talc, kaolin or other comparable mineral~ and, on the other hand, also platelet-like iron oxide, bismuth oxychloride and the metal oxide-coated micas known as pearl lustre pigments, and also aluminium platelets or metal oxide-coated metal platelets, in particular metal oxide-coated aluminium platelets. All conventional pearl lustre pigments can be used, for example mica coatings ~2~8~
~, containing coloured or colourless me~al oxides such as TiO2, Fe2O3, SnO2, Cr2O3, ZnO and other metal oxides as such or mixed in a uniform layer or in successive layer~.
These pigments have been disclosed, for example, in the S German Patents and Patent Applications 1,467,468, 1,959,998, 2,009,566, 2,214,545, 2,215,191, 2,244,298, 2,313,331, 2,522,572, 3,137,808, 3,137,809, 3,151,343, 3,151,354, 3,151,355, 3,211,~02 and 3,~35,017.
The surface-modified substrates according to the invention are prepared by reacting th~ substrates, for example with at least di functional organic coupling agents. Then a remaining functional group of the coupled agen~ is reacted with a low molecular weight organic radical. However, it is also possible fir~t to prepare the coupling agents which have been linked to the low molecular weight organic radical and then to react these coupling agents with the platelet-like substrate.
Depending on the structure of this radical, this gives platelet~like, surface-modified substrates having various pro~erties.
Suitable compounds for uqe as coupling agents which have not thems~lves yet been further modified are described, for example, in the following publications:
Edwin P. Plueddemann; Silane Coupling Agents; Plenum Pres~; ~e~w ~ork, London (1982) an~ the literature referred to ~hexein. Sal~atore J. Monte, Gerald Su~erman;
Ren-React Reference Manual - Titanate, Zirconate and Aluminate Coupling Agents (1987) and the literature - referred to therein. Dynasilan Haftvermit~ler, Organo-funktionelle Silane, Technische Information Dynamit Nobel (1985~. Lawrence B. Cohen, The Chemistry of Zircon-aluminate Coupling Agents and their ~pplication in ~igh Solids Coatings, Water-borne and Higher-Solids Coatings Symposium, New Orleans, 1986. Lawrence B. Cohen, Corrosion Reduction in High Solids and Water-bc^ne Coatings using 2irconaluminate Adhesion Promoters, Water-g ~
borne and Higher-Solids Coatings Symposiumr New Orleans, 1988. Peter Z. Moles, The Application of Zirconium Compounds in Surface Coatings, Water-~orne and Higher-Solids Coatings Symposium, New Orleans, 1987.
As a rule, suitable compounds contain one or more metal centres such as Si, Ti, Zr or Al to which functional organic groups are bonded. Exampl~s of suitable silanes are the commercially available polyfunctionalizPd DYNASYLAN0 agents (Dynamik Nobel). These are alkoxysilane derivatives having two or three alkoxy radicals and one or two alkyl radicals to which functional group~ have additionally been bonded, for example amino, mercapto or a nitrile group or a halogen radical such as chlorine.
Examples o~ suitable titanate coupling agents are the commercially available "KR~ materials (Kenrich Pe~ro-chemicals, Inc.). Like the abovementioned silanes, these agents are compounds having alkoxy radicals and radicals additionally substituted by functional groups, the radicals of the said compounds being bonded via oxygen to the metal centre~ Examplex of the functional groups are amino, mercapto or hydroxyl groups.
~xamples of suitable zirconate coupling agents are the neoalko~y ~irconate~ havi~g amino or mercapto groups obtainable from Renri~h Petrochemicals, Inc. under the designation "hZ n agents. Furthermore, the substrates according~ to the invention can be prepared using zirconium aluminate~ such as, for example, the appropriate "Cavco Mod" agents obtainable from Cavedon Chemical Co., Inc. Platelet-like metal ~ubstrates, for example platelets of Al, Cu, Zn or alloys thereof, are also suitable for coatings using zirconium aluminates.
The coupling agents are applied either directly or by intensive mixing of substrate and coupling agent~ prefer-ably, however, in organic solvents or in aqueous medium.
The concentration of the coupling agent in these procedures is in the range from about 0.01 to 20, preferably 0~1 to 10% by weight, relative to the substrate.
Then a still intact functional group of the agent which has been applied to the substrate is coupled to a low molecular weight organic radical. It is possible, for example, to react a chromophore-containing radical with the modified substrate. By virtue of the high degree of variation, excess is thus available to virtually colours which t as surface colours, by interaction with the surface colours of the substrates themselves and in : particular with the interference colours of the pearl lustre pigments give any desired colour effect.
Primary aromatic amines are particularly suitable functional groups for coupling a chromophore-conferring organic radical. The complete colour spect:~Lm from yellow through orange, red/ boxdeaux, blue to brown and black i8 accessible by direct azo-coupling uæing the coupling agents known from azo dye and pigment chemistry ~W. Herbst, R. Hunger, Indu~trielle Organische Pigmente, published by Y~H Verlagsgesellschaft mbH, Weinheim (1987) and P. Ry~, H. Zollin~er, Leitfaden der Farbstofchemie, published by Verlag Chemie, Weinheim (197633.
The preparation of the preferred chromophore-containing substrates according to the invention iæ accordingly carried ~ut by first reacting the substrate with an organic coupling ag~nt containing an aromatic prLmary amine and, if desired, after isolating the modified substrate, by diazotizing the amine and reacting this functional group with a coupling component by convQntional methods.
ExAmples of sui~able coupling agents are:
I s o p r o p y l 4 - a m i n o p h e n y l s u l p h o n y l di(dodecylphenylsulphonyl) titanate (KR 26S), 4-aminophenylsulphonyl dodecylphenylsulphonyl e~hylene--- 7 _ titanate ~KR 226S), isopropyl tri~2-aminobenzoyl~
titana~e (KR 52S), isopropyl di(4-aminobenzoyl) isostearoyl titanate (KR 37BS) and neopentyldiallyloxy tri(m-aminophenyl) zirconate (LZ 97). However, it is also possible to use other coupling agents in which one functional group, after reaction with the substrate, is suitably transformed so that a couplable amino group is available. Alternatively, it is also possible to carry out the azo coupling on the coupling agent itself and, 2S
the final process step, to couple the modified coupling agent to the platelet-like substrate. Fur~hermore, it is possible first to prepare an azo-dye compound and to convert this into a coupling agent.
Moreover, it is possible to couple low molecular weight organic radicals to one function~l group of the agent which has been coupled to the substrate, these organic radicals containing a free-radical initiator function or to form a f?:~ction of this type only after the coupling has taken place. Similarly to the abovementioned azo dyes, it is possible, on the one hand, to form ~ypical azo initiator groups which can be prepared from primary aromatic amines ~azo components originating from the coupling agsnt). On the other hand, aliphatic azo initiator groups are also ~ccesæible.
For instance, an initiator such as 4,4'-azo bis(4-cyanopentanoic acid) (Fluka A&) can be converted into an acid derivative using a functional group of a coupling agent, such a~ -MH2 ~ ~OH or -SH. The corresponding reaction are preferably carried out under mild condition~.
Moreover, it i~ po3sible by the process according to the invention to bond photoinitiators via a coupling agent to platelet-like substxates by reacting compound~ of the general formula RG-A-IN
with a functional group of the coupling agent which may already have been coupled to the substrate. RG is a reactive group such as -OH, -SH, -NH2, -halogen, -COOH or -CONH2; A, a spacer group, normally an alkylene chain which is optionally interrupted by hetero atoms such as -o-, -S-, -NH- or carbonyl, carboxyl, carboxamide groups or sLmilar groups; and IN is a photoinitiator ~ase structure.
Suitable compounds for this purpose whose mode of preparation and reactions of the group RG can give covalent linkage to matrix systems without loss of initiator activity, are descrihed in detail in DE-A-3,738,567 and are similarly wholly applicable to the present invention. This gives access to all well known-and currently used photoinitiator structures of the hydroxy- or amino-alkylphenone type, and also to derivatives of benzoin ethers, benzyl ketals, dialcoxyacetophenones, thioxanthones, and acylphosphine oxides for the purpo~es of surface-modification according to the invention.
~0 In a similar manner to the ~bovementioned formation of chromophore group3, it is also usually possible in thi~
case first to introduce a free-radical initiator group by covalent bonding to the coupling agent itself. Then the modified coupling agent is reacted with the platelet-like substrate.
Depending on the intended use of the platelet-like, surface-modified substrate which has been prepared according to the invention, other low molecular weight organic radicals can be covalently bonded tol one ~un~tional group of the coupling agent.
The type of surface-modification according to the invention gives a number of advantages. For instance, it has been observed that the covalent linking of chromophores to the pigment matrix within the scope of the process according to the invention ensures a permanent coating of the pigments with the chromophore.
~2~
,, .
This is often not the case according to the prior art, particularly with regard to purely physical coating.
However, it is even more surprising that in the case of pearl lustre pigments, modification according to the invention allows the propertie~ typical of these pigments to be retained. This is true, in particular, of the pearl lustre effect, which with the substrates according to the invention by interaction with the intrinsic colours of the chromophore, allows virtually any colour effect to be achieved.
The particular combination of permanent coating and a high degree of variability of colour shades and ef~ects is of exceptionally great practical use in numerous formula~ions such as paints, for example car body lS finishes, cosmetics, plastics and dye compositions.
Substrates according to the invention in which free-radical initiator groups have bPen covalently bonded have surprising advantages on incorporation in polymer systems~ For instance, polymers ha~ing Lmproved pigment dispersion are obtained if a monomer system containing finely dispersed initiator pigment i8 polymerized. Since the polymerization is initiated at the pigment surface, the degree of dispersion in the polymer is ~irtually unaltered.
This reaction sequence has particular utility in emulsion polymerizatîons.
The modified platelet-like substrate is finely dispersed, or example in an aqueous solution containing an emulsifier. The emulsifier molecules then become pref~rentially attached to the hydrophobic pigment particle~ so that ultLmately the hydrophilic emulsifier molecules are directed into the aquQous phase. This gives micelle-like structures which fill up with monomer.
Polymerization then occurs almost without exception in the pigment micelles (C.H.M. Caris et al., 2~2~
I~Polymerization at the surface of inorganic submicron particles'~, XIX FATIPEX Kongre~, Aachen 1988). The application of this process principle allows all polymer reactions which are feasible in emulsion, for example the polymerization and copolymerization of styrene, vinyl acetate, butadiene, isoprene, acrylonitrile or vinyl chloride, to be carried out on platelet-like substrates which bear initiator groups. The reaction co~ditions are known to a person skilled in the are and can bs taken, for example, from: D.B. Braun et al. in "Praktikum der makromolekularen organischen Chemie", published by Huthig-Verlag, Heidelberg 19790 The polymer-encapsulated pigments which have been prepared in this manner can be significantly better incorporated in polymer systems and also have improved weathering resistance There is virtually no loss of lustre or formation of agglomerates.
Furthermore, it is not necessary to isolate the polymer-encapsulated substrate particles~ The substrate~polymer particles formed a~ pigment latices in the emulsion polymerization c~n be mixed directly with the component~
of a waterborne paint system by latex-intermixing. In this procedure, the polymer coating of the platelet-like substrates can be optimally adapted to the paint ~ystem by the appropriate selectlon of the monomers. The mixing of the har~onized latice~ allows any incompatibilities and any imperfections in the paint system caused by pigment addition (pigment shock) to be for the greatest part or even completely eliminated.
Example 1 100 g of Iriodin~ 103 (~itanium dioxide-coated mica flake pigment from E. Merck, ~arm~tadt) are treated to activate the calcined titanium dioxide surface by coating with approximately 7.3% of freshly precipitated titanium hydroxide oxide in aqueous solution (pH 2.2). This is 2 ~
achieved by metering an aqueous ~olution of titanium tetrachloride (350 g/l~ into the aqueous suspension of the pigment which has bee~ adjusted to a pH of 2.2 using 10~ hydrochloric acid, and keeping the pH value constant meanwhile using 10% sodium hydroxide solution. The pigment is then filtered, washed with water and dried.
100 g of the pre-treated pigment are suspended in 500 ml of toluene. Then a solution of 10 g of KR26S (isopropyl 4-aminophenylsulphonyl di(dodecylphenylsulphonyl) titanate from Renrich Petrocehmicals, Inc., Bayonne, New Jersey) in 75 ml of toluene is added. After stirring for 2 h at room temperature, the pigment is filtered off, washed with toluene and dried in vacuo.
100 g oi the KR26S-modified pigment are suspended in 150 ml of completely deionized water. To the pigment ~uspension are then added 11.8 ml of 5% hydrochloric acid and the mixture i~ cooled to -2~C. To the coole~, acidic pi~ment suspension is then added in the course of 20 min a solution at -5C of 0.94 g (0.27 mol~ of sodium ni~rite in 50 ml of deionized water. During this operation, the temperature increases to +2C. Potassium iodide/starch paper is used to test for nitrite and hence for the completion of the reaction. Excess nitrite is destroyed using urea.
After the diazonium salt forma~ion has ceased, the fiuspension of the pigment/diazonium salt is slowly run in, with stirring, to a solution at 5C of 0.98 g (5.5 mmol) of acetoacetanilide in 170 ml of 5~
hydrochloric acid. During this operation, the temperature increases to 10C and a light yellow pigment su pension i~ obtained. After addition to the acetoacetanilide ha~
ceased, stirring with cooling is maintained for a further 2 h. Then the pigment i~ filtered off under suction, washed with water and dried.
If the co-lpling i8 carried out in alkaline medium at a pH
2~2~
of about 10, a reddish-orange pigment suspension is obtained.
A similar procedure is used with the following coupling components:
2-Hydroxynaphthalene (~-naphthol) 2-Hydroxy-3-naphthoic acid and also the 2'-hydroxy-3'-naphthoylanilines Naphtol AS~, Naphtol AS-O and Naphtol AS-OL, known as the Naphtol AS~ agents (Hoechst AG).
All of the modified platelet-like substrates have high weathering resistance, can be very readily incorporated in industrial formulations with high migration resistance and colour stability without loss of lustre.
Example 2 The procedure of Example 1 is used to modify Iriodin~ 103.
The organic coupling agent used is LZ97 (neopentyl-diallyloxy tri(m-aminophenyl) zirconate from Kenrich Petrochemicals, Inc.).
To a solution of 10 g of LZ97 in 500 ml of acetone are added in portio~s 100 g of activated Iriodin~ 103. The solid is ~hen filtered off~ washed with acetone and dried in vacuo.
In thQ subsequent diazotization and coupling, the amounts given in Example 1 are trebled in accordance with the stoi~hiometry of-the coupling agent. ~his gives a reddish brown pigment suspension.
The coupling components given in Example 1 are similarly used.
All of the modified platelet-like substrates have high weathering resistance~ can be very readily incorporated in industrial formulations with high migration resistance and colour stability without loss of lustre.
Example 3 200 g of Iriodin9 504 (iron(III) oxide-coated mica flake pigment from E. Merck, Darmstadt) are suspended in 4 1 of deionized water. The suspension is heated to 75C with vigorous stirring. The pH is adjusted to 6.5 using 15~
aqueous sodium hydroxide solution. Then, in the course of 10 min, a solution of 10 mmol of 4-[2-(3-triethoxysilylpropoxy)-ethoxy]-phenyl (2-hydroxy-2-propyl~ ketone (preferable in accordance withDE-A-3,738~567) in 200 ml of ethanol is added dropwise to the pigment sllspen~ion. During this operation, the pH is kept con~tant using 5~ aqueous sodium hydroxide solution~
After the addition has ceased, the mixture is stirred for a further 30 min at 75C. Then the product is filtered off under suction thxough a filter funnel, washed with deionized water and dried in vacuo.
Surface-modified substràte~ are sLmilarly prepared using:
4-[3-tTriethogysilyl)propoxy]-phenyl (2-hydroxy-2-propyl) ketone 4-[2-(3-Triethoxy~ilylprop~lthio)-ethyl]-phenyl (2-hydroxy-2-propyl) ketone
Numerous mathods have therefore been developed, inter alia, to solve the prohlem of incorporating platelet-like pigments, in particular, in-to thermoplastic materials (DE-A-2,603,211, DE-A-3,221,044, DE-A-3,627,329).
5 Furthermore, coatings employing polysiloxanes for improved weathering resistance have been disclosed (DE 3,334,598), and also treatment with coupling agents such as organotitanates to give improved dispersibility in cosmetic preparations (EP 0,306,056), and with organosilanes to give improved water resistance (~P 0,268,918).
The object of the present invention is to develop other and better processes for surface modification of platel~t-like substrates. In particular, the substra~es must be compatible with a great many di~ferent industrial formulations without the typical properties of platelet-like substrates being lost. There is a need, inter alia, for platelet-like, surface-modi~ied pigments which can be incorporated in formulations without losing their pigme~t properties. Examples of frequently encountered disadvantages from pigment incorporation ar~ pigment shock, ie. the formation of agglomerates on incorporation owing to incompatibilities, and pigment migration.
Thi~ object is achieved by the present invention. In particula~, it has been found that the trea~ment of platelet-like sub~trates with organic coupling agents which have at least one other functional group for coupling to a low molecular weight organic radical allows the preparation of ~urface-modified substrates having virtually any de~ired functional propertieY, depending on the type of low molecular weight organic radical.
The present invention accordingly provides platelet-like ~urface-modiied sub~trates, obtainable by txeating platelet-like substrates with at least di-functional organic coupling agent~ and then coupling a low molecular weight organic radical to a second functional group of the agent which has been coupled to the substrate.
The invention also provides platelet-like surface-modified substrates, obtainable by treating platelet-like substrates with organo~Ti, organo-Zr or organo-Zr/organo-Al coupling agents, characterized in that after the coupling reaction to the coupled agent, a second functional group is available for coupling to a low molecular weight organic radical.
Furthermore, the present invention provides a process for the preparation of substrate according to ClaLm 1, characterized in that platelet-like substrates are reacted in an aqueous or an organic medium or in a mixture thereof with the coupling agent and then the low molecular weight organic radical is coupled, or in that initially a coupling agent containing the low molecular weight organic radical is prepared and is then r~ac$ed with the substrate.
Finally, the inventisn provide~ the use of the ~urface-modified substratQs according to ClaLm 1 in formulations such as paints, dye compositions, plaætics and cosmetics.
The invention ultimately provides formulation~ which contain the substrates according to the invention.
Prefarred platelet-like sub~trates for surface modifica-tion according to the invention are, in particular, layer-~tructured ~ilicates and oxides or oxide-coated materials, ~ince these have reactive OH groups on their surface. Examplas of the~e ar , on the one hand, mica, talc, kaolin or other comparable mineral~ and, on the other hand, also platelet-like iron oxide, bismuth oxychloride and the metal oxide-coated micas known as pearl lustre pigments, and also aluminium platelets or metal oxide-coated metal platelets, in particular metal oxide-coated aluminium platelets. All conventional pearl lustre pigments can be used, for example mica coatings ~2~8~
~, containing coloured or colourless me~al oxides such as TiO2, Fe2O3, SnO2, Cr2O3, ZnO and other metal oxides as such or mixed in a uniform layer or in successive layer~.
These pigments have been disclosed, for example, in the S German Patents and Patent Applications 1,467,468, 1,959,998, 2,009,566, 2,214,545, 2,215,191, 2,244,298, 2,313,331, 2,522,572, 3,137,808, 3,137,809, 3,151,343, 3,151,354, 3,151,355, 3,211,~02 and 3,~35,017.
The surface-modified substrates according to the invention are prepared by reacting th~ substrates, for example with at least di functional organic coupling agents. Then a remaining functional group of the coupled agen~ is reacted with a low molecular weight organic radical. However, it is also possible fir~t to prepare the coupling agents which have been linked to the low molecular weight organic radical and then to react these coupling agents with the platelet-like substrate.
Depending on the structure of this radical, this gives platelet~like, surface-modified substrates having various pro~erties.
Suitable compounds for uqe as coupling agents which have not thems~lves yet been further modified are described, for example, in the following publications:
Edwin P. Plueddemann; Silane Coupling Agents; Plenum Pres~; ~e~w ~ork, London (1982) an~ the literature referred to ~hexein. Sal~atore J. Monte, Gerald Su~erman;
Ren-React Reference Manual - Titanate, Zirconate and Aluminate Coupling Agents (1987) and the literature - referred to therein. Dynasilan Haftvermit~ler, Organo-funktionelle Silane, Technische Information Dynamit Nobel (1985~. Lawrence B. Cohen, The Chemistry of Zircon-aluminate Coupling Agents and their ~pplication in ~igh Solids Coatings, Water-borne and Higher-Solids Coatings Symposium, New Orleans, 1986. Lawrence B. Cohen, Corrosion Reduction in High Solids and Water-bc^ne Coatings using 2irconaluminate Adhesion Promoters, Water-g ~
borne and Higher-Solids Coatings Symposiumr New Orleans, 1988. Peter Z. Moles, The Application of Zirconium Compounds in Surface Coatings, Water-~orne and Higher-Solids Coatings Symposium, New Orleans, 1987.
As a rule, suitable compounds contain one or more metal centres such as Si, Ti, Zr or Al to which functional organic groups are bonded. Exampl~s of suitable silanes are the commercially available polyfunctionalizPd DYNASYLAN0 agents (Dynamik Nobel). These are alkoxysilane derivatives having two or three alkoxy radicals and one or two alkyl radicals to which functional group~ have additionally been bonded, for example amino, mercapto or a nitrile group or a halogen radical such as chlorine.
Examples o~ suitable titanate coupling agents are the commercially available "KR~ materials (Kenrich Pe~ro-chemicals, Inc.). Like the abovementioned silanes, these agents are compounds having alkoxy radicals and radicals additionally substituted by functional groups, the radicals of the said compounds being bonded via oxygen to the metal centre~ Examplex of the functional groups are amino, mercapto or hydroxyl groups.
~xamples of suitable zirconate coupling agents are the neoalko~y ~irconate~ havi~g amino or mercapto groups obtainable from Renri~h Petrochemicals, Inc. under the designation "hZ n agents. Furthermore, the substrates according~ to the invention can be prepared using zirconium aluminate~ such as, for example, the appropriate "Cavco Mod" agents obtainable from Cavedon Chemical Co., Inc. Platelet-like metal ~ubstrates, for example platelets of Al, Cu, Zn or alloys thereof, are also suitable for coatings using zirconium aluminates.
The coupling agents are applied either directly or by intensive mixing of substrate and coupling agent~ prefer-ably, however, in organic solvents or in aqueous medium.
The concentration of the coupling agent in these procedures is in the range from about 0.01 to 20, preferably 0~1 to 10% by weight, relative to the substrate.
Then a still intact functional group of the agent which has been applied to the substrate is coupled to a low molecular weight organic radical. It is possible, for example, to react a chromophore-containing radical with the modified substrate. By virtue of the high degree of variation, excess is thus available to virtually colours which t as surface colours, by interaction with the surface colours of the substrates themselves and in : particular with the interference colours of the pearl lustre pigments give any desired colour effect.
Primary aromatic amines are particularly suitable functional groups for coupling a chromophore-conferring organic radical. The complete colour spect:~Lm from yellow through orange, red/ boxdeaux, blue to brown and black i8 accessible by direct azo-coupling uæing the coupling agents known from azo dye and pigment chemistry ~W. Herbst, R. Hunger, Indu~trielle Organische Pigmente, published by Y~H Verlagsgesellschaft mbH, Weinheim (1987) and P. Ry~, H. Zollin~er, Leitfaden der Farbstofchemie, published by Verlag Chemie, Weinheim (197633.
The preparation of the preferred chromophore-containing substrates according to the invention iæ accordingly carried ~ut by first reacting the substrate with an organic coupling ag~nt containing an aromatic prLmary amine and, if desired, after isolating the modified substrate, by diazotizing the amine and reacting this functional group with a coupling component by convQntional methods.
ExAmples of sui~able coupling agents are:
I s o p r o p y l 4 - a m i n o p h e n y l s u l p h o n y l di(dodecylphenylsulphonyl) titanate (KR 26S), 4-aminophenylsulphonyl dodecylphenylsulphonyl e~hylene--- 7 _ titanate ~KR 226S), isopropyl tri~2-aminobenzoyl~
titana~e (KR 52S), isopropyl di(4-aminobenzoyl) isostearoyl titanate (KR 37BS) and neopentyldiallyloxy tri(m-aminophenyl) zirconate (LZ 97). However, it is also possible to use other coupling agents in which one functional group, after reaction with the substrate, is suitably transformed so that a couplable amino group is available. Alternatively, it is also possible to carry out the azo coupling on the coupling agent itself and, 2S
the final process step, to couple the modified coupling agent to the platelet-like substrate. Fur~hermore, it is possible first to prepare an azo-dye compound and to convert this into a coupling agent.
Moreover, it is possible to couple low molecular weight organic radicals to one function~l group of the agent which has been coupled to the substrate, these organic radicals containing a free-radical initiator function or to form a f?:~ction of this type only after the coupling has taken place. Similarly to the abovementioned azo dyes, it is possible, on the one hand, to form ~ypical azo initiator groups which can be prepared from primary aromatic amines ~azo components originating from the coupling agsnt). On the other hand, aliphatic azo initiator groups are also ~ccesæible.
For instance, an initiator such as 4,4'-azo bis(4-cyanopentanoic acid) (Fluka A&) can be converted into an acid derivative using a functional group of a coupling agent, such a~ -MH2 ~ ~OH or -SH. The corresponding reaction are preferably carried out under mild condition~.
Moreover, it i~ po3sible by the process according to the invention to bond photoinitiators via a coupling agent to platelet-like substxates by reacting compound~ of the general formula RG-A-IN
with a functional group of the coupling agent which may already have been coupled to the substrate. RG is a reactive group such as -OH, -SH, -NH2, -halogen, -COOH or -CONH2; A, a spacer group, normally an alkylene chain which is optionally interrupted by hetero atoms such as -o-, -S-, -NH- or carbonyl, carboxyl, carboxamide groups or sLmilar groups; and IN is a photoinitiator ~ase structure.
Suitable compounds for this purpose whose mode of preparation and reactions of the group RG can give covalent linkage to matrix systems without loss of initiator activity, are descrihed in detail in DE-A-3,738,567 and are similarly wholly applicable to the present invention. This gives access to all well known-and currently used photoinitiator structures of the hydroxy- or amino-alkylphenone type, and also to derivatives of benzoin ethers, benzyl ketals, dialcoxyacetophenones, thioxanthones, and acylphosphine oxides for the purpo~es of surface-modification according to the invention.
~0 In a similar manner to the ~bovementioned formation of chromophore group3, it is also usually possible in thi~
case first to introduce a free-radical initiator group by covalent bonding to the coupling agent itself. Then the modified coupling agent is reacted with the platelet-like substrate.
Depending on the intended use of the platelet-like, surface-modified substrate which has been prepared according to the invention, other low molecular weight organic radicals can be covalently bonded tol one ~un~tional group of the coupling agent.
The type of surface-modification according to the invention gives a number of advantages. For instance, it has been observed that the covalent linking of chromophores to the pigment matrix within the scope of the process according to the invention ensures a permanent coating of the pigments with the chromophore.
~2~
,, .
This is often not the case according to the prior art, particularly with regard to purely physical coating.
However, it is even more surprising that in the case of pearl lustre pigments, modification according to the invention allows the propertie~ typical of these pigments to be retained. This is true, in particular, of the pearl lustre effect, which with the substrates according to the invention by interaction with the intrinsic colours of the chromophore, allows virtually any colour effect to be achieved.
The particular combination of permanent coating and a high degree of variability of colour shades and ef~ects is of exceptionally great practical use in numerous formula~ions such as paints, for example car body lS finishes, cosmetics, plastics and dye compositions.
Substrates according to the invention in which free-radical initiator groups have bPen covalently bonded have surprising advantages on incorporation in polymer systems~ For instance, polymers ha~ing Lmproved pigment dispersion are obtained if a monomer system containing finely dispersed initiator pigment i8 polymerized. Since the polymerization is initiated at the pigment surface, the degree of dispersion in the polymer is ~irtually unaltered.
This reaction sequence has particular utility in emulsion polymerizatîons.
The modified platelet-like substrate is finely dispersed, or example in an aqueous solution containing an emulsifier. The emulsifier molecules then become pref~rentially attached to the hydrophobic pigment particle~ so that ultLmately the hydrophilic emulsifier molecules are directed into the aquQous phase. This gives micelle-like structures which fill up with monomer.
Polymerization then occurs almost without exception in the pigment micelles (C.H.M. Caris et al., 2~2~
I~Polymerization at the surface of inorganic submicron particles'~, XIX FATIPEX Kongre~, Aachen 1988). The application of this process principle allows all polymer reactions which are feasible in emulsion, for example the polymerization and copolymerization of styrene, vinyl acetate, butadiene, isoprene, acrylonitrile or vinyl chloride, to be carried out on platelet-like substrates which bear initiator groups. The reaction co~ditions are known to a person skilled in the are and can bs taken, for example, from: D.B. Braun et al. in "Praktikum der makromolekularen organischen Chemie", published by Huthig-Verlag, Heidelberg 19790 The polymer-encapsulated pigments which have been prepared in this manner can be significantly better incorporated in polymer systems and also have improved weathering resistance There is virtually no loss of lustre or formation of agglomerates.
Furthermore, it is not necessary to isolate the polymer-encapsulated substrate particles~ The substrate~polymer particles formed a~ pigment latices in the emulsion polymerization c~n be mixed directly with the component~
of a waterborne paint system by latex-intermixing. In this procedure, the polymer coating of the platelet-like substrates can be optimally adapted to the paint ~ystem by the appropriate selectlon of the monomers. The mixing of the har~onized latice~ allows any incompatibilities and any imperfections in the paint system caused by pigment addition (pigment shock) to be for the greatest part or even completely eliminated.
Example 1 100 g of Iriodin~ 103 (~itanium dioxide-coated mica flake pigment from E. Merck, ~arm~tadt) are treated to activate the calcined titanium dioxide surface by coating with approximately 7.3% of freshly precipitated titanium hydroxide oxide in aqueous solution (pH 2.2). This is 2 ~
achieved by metering an aqueous ~olution of titanium tetrachloride (350 g/l~ into the aqueous suspension of the pigment which has bee~ adjusted to a pH of 2.2 using 10~ hydrochloric acid, and keeping the pH value constant meanwhile using 10% sodium hydroxide solution. The pigment is then filtered, washed with water and dried.
100 g of the pre-treated pigment are suspended in 500 ml of toluene. Then a solution of 10 g of KR26S (isopropyl 4-aminophenylsulphonyl di(dodecylphenylsulphonyl) titanate from Renrich Petrocehmicals, Inc., Bayonne, New Jersey) in 75 ml of toluene is added. After stirring for 2 h at room temperature, the pigment is filtered off, washed with toluene and dried in vacuo.
100 g oi the KR26S-modified pigment are suspended in 150 ml of completely deionized water. To the pigment ~uspension are then added 11.8 ml of 5% hydrochloric acid and the mixture i~ cooled to -2~C. To the coole~, acidic pi~ment suspension is then added in the course of 20 min a solution at -5C of 0.94 g (0.27 mol~ of sodium ni~rite in 50 ml of deionized water. During this operation, the temperature increases to +2C. Potassium iodide/starch paper is used to test for nitrite and hence for the completion of the reaction. Excess nitrite is destroyed using urea.
After the diazonium salt forma~ion has ceased, the fiuspension of the pigment/diazonium salt is slowly run in, with stirring, to a solution at 5C of 0.98 g (5.5 mmol) of acetoacetanilide in 170 ml of 5~
hydrochloric acid. During this operation, the temperature increases to 10C and a light yellow pigment su pension i~ obtained. After addition to the acetoacetanilide ha~
ceased, stirring with cooling is maintained for a further 2 h. Then the pigment i~ filtered off under suction, washed with water and dried.
If the co-lpling i8 carried out in alkaline medium at a pH
2~2~
of about 10, a reddish-orange pigment suspension is obtained.
A similar procedure is used with the following coupling components:
2-Hydroxynaphthalene (~-naphthol) 2-Hydroxy-3-naphthoic acid and also the 2'-hydroxy-3'-naphthoylanilines Naphtol AS~, Naphtol AS-O and Naphtol AS-OL, known as the Naphtol AS~ agents (Hoechst AG).
All of the modified platelet-like substrates have high weathering resistance, can be very readily incorporated in industrial formulations with high migration resistance and colour stability without loss of lustre.
Example 2 The procedure of Example 1 is used to modify Iriodin~ 103.
The organic coupling agent used is LZ97 (neopentyl-diallyloxy tri(m-aminophenyl) zirconate from Kenrich Petrochemicals, Inc.).
To a solution of 10 g of LZ97 in 500 ml of acetone are added in portio~s 100 g of activated Iriodin~ 103. The solid is ~hen filtered off~ washed with acetone and dried in vacuo.
In thQ subsequent diazotization and coupling, the amounts given in Example 1 are trebled in accordance with the stoi~hiometry of-the coupling agent. ~his gives a reddish brown pigment suspension.
The coupling components given in Example 1 are similarly used.
All of the modified platelet-like substrates have high weathering resistance~ can be very readily incorporated in industrial formulations with high migration resistance and colour stability without loss of lustre.
Example 3 200 g of Iriodin9 504 (iron(III) oxide-coated mica flake pigment from E. Merck, Darmstadt) are suspended in 4 1 of deionized water. The suspension is heated to 75C with vigorous stirring. The pH is adjusted to 6.5 using 15~
aqueous sodium hydroxide solution. Then, in the course of 10 min, a solution of 10 mmol of 4-[2-(3-triethoxysilylpropoxy)-ethoxy]-phenyl (2-hydroxy-2-propyl~ ketone (preferable in accordance withDE-A-3,738~567) in 200 ml of ethanol is added dropwise to the pigment sllspen~ion. During this operation, the pH is kept con~tant using 5~ aqueous sodium hydroxide solution~
After the addition has ceased, the mixture is stirred for a further 30 min at 75C. Then the product is filtered off under suction thxough a filter funnel, washed with deionized water and dried in vacuo.
Surface-modified substràte~ are sLmilarly prepared using:
4-[3-tTriethogysilyl)propoxy]-phenyl (2-hydroxy-2-propyl) ketone 4-[2-(3-Triethoxy~ilylprop~lthio)-ethyl]-phenyl (2-hydroxy-2-propyl) ketone
Claims (7)
1. Platelet-like, surface-modified substrates obtainable by treating platelet-like substrates using at least di-functional organic coupling agents and then coupling a low molecular weight organic radical to a second functional group of the agent which has been coupled to the substrate.
2. Substrates according to Claim 1, characterized in that the low molecular weight organic radical contains a chromophore group or forms a chromophore group by coupling.
3. Substrates according to Claim 1, characterized in that the low molecular weight organic radical contains a free-radical initiator group or forms a free-radical initiator group by coupling.
4. Platelet-like, surface-modified substrates, obtainable by treating platelet-like substrate with organo-Ti-, organo-Zr or organo-Zr/organo-Al coupling agents, characterized in that after the coupling reaction to the coupled agent, a second functional group is available for coupling to a low molecular weight organic radical.
5. Process for the preparation of substrates according to Claim 1, characterized in that platelet-like substrates are reacted in an aqueous or an organic medium or in a mixture thereof with the coupling agent and then the low molecular weight organic radical is coupled, or that initially a coupling agent containing the low molecular weight organic radical is prepared and is then reacted with the substrate.
6. The use of substrates according to at least one of Claims 1, 2 and 3 in formulations such as paints, dye compositions, plastics and cosmetics.
7. Formulations containing substrates according to at least one of Claims 1, 2 and 3.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3929423A DE3929423A1 (en) | 1989-09-05 | 1989-09-05 | PLATE-SHAPED, SURFACE-MODIFIED SUBSTRATES |
| DEP3929423.4 | 1989-09-05 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2024486A1 true CA2024486A1 (en) | 1991-03-06 |
Family
ID=6388649
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002024486A Abandoned CA2024486A1 (en) | 1989-09-05 | 1990-08-31 | Platelet-like, surface-modified substrates |
Country Status (10)
| Country | Link |
|---|---|
| EP (1) | EP0416395B1 (en) |
| JP (1) | JPH0393863A (en) |
| KR (1) | KR910006426A (en) |
| CN (1) | CN1050033A (en) |
| AU (1) | AU6216890A (en) |
| BR (1) | BR9004383A (en) |
| CA (1) | CA2024486A1 (en) |
| DE (2) | DE3929423A1 (en) |
| ES (1) | ES2063878T3 (en) |
| FI (1) | FI904354A7 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7745003B2 (en) | 2004-02-07 | 2010-06-29 | Merck Patent Gmbh | Particles having a functional multilayered structure |
Families Citing this family (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4321005A1 (en) | 1993-06-24 | 1995-01-05 | Merck Patent Gmbh | Pearlescent pigment for water-based paint systems |
| US5648408A (en) * | 1995-06-07 | 1997-07-15 | Ciba-Geigy Corporation | Organic stir-in pigments |
| US5584922A (en) * | 1994-09-14 | 1996-12-17 | Ciba-Geigy Corporation | Stir-in organic pigments |
| DE19820112A1 (en) | 1998-05-06 | 1999-11-11 | Eckart Standard Bronzepulver | Effect pigments coated with reactive orientation aids |
| ES2200894T3 (en) * | 1999-07-13 | 2004-03-16 | Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno | COLORING PIGMENT. |
| DE10054980C2 (en) * | 2000-11-06 | 2003-02-06 | Merck Patent Gmbh | Stabilization of pearlescent pigments |
| DE10348174B4 (en) * | 2002-11-06 | 2017-02-09 | Merck Patent Gmbh | Surface stabilization of pearlescent pigments |
| DE102004035769A1 (en) | 2004-07-27 | 2006-03-23 | Merck Patent Gmbh | Multilayer interference pigments |
| WO2006041658A1 (en) * | 2004-10-08 | 2006-04-20 | Dow Global Technologies Inc. | Encapsulated metallic-look pigment |
| DE102004049203A1 (en) | 2004-10-08 | 2006-04-20 | Merck Patent Gmbh | Coated silicon dioxide effect pigments with improved optical properties are made using silicon dioxide platelets of 50-150 nm thickness |
| DE102005001997A1 (en) | 2005-01-17 | 2006-07-20 | Merck Patent Gmbh | Effect pigments with colour flop comprising SiO2 laminars coated with metal oxides, useful in e.g. cosmetics and coating for pharmaceuticals, has colour flop extending through all four quadrants of a,b-colour coordinate system |
| DE102005002124A1 (en) | 2005-01-17 | 2006-07-27 | Merck Patent Gmbh | Strong color effect pigments |
| DE102005037611A1 (en) * | 2005-08-05 | 2007-02-15 | Eckart Gmbh & Co. Kg | Metallic effect pigments with an inorganic / organic mixed layer, process for the preparation of such metallic effect pigments and their use |
| DE102008050924A1 (en) | 2008-10-10 | 2010-04-15 | Merck Patent Gmbh | pigments |
| DE102009016089A1 (en) | 2009-03-20 | 2010-09-23 | Merck Patent Gmbh | coating composition |
| DE102010009239A1 (en) | 2009-03-20 | 2010-09-23 | Merck Patent Gmbh | Aqueous composition, useful for coating optionally precoated flat substrates e.g. glass, ceramic, metal, polymer films, leather, textiles and wood or stone, comprises an effect pigment e.g. an opaque or transparent effect pigment |
| JP6008867B2 (en) | 2010-12-09 | 2016-10-19 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツングＭｅｒｃｋ Ｐａｔｅｎｔ Ｇｅｓｅｌｌｓｃｈａｆｔ ｍｉｔ ｂｅｓｃｈｒａｅｎｋｔｅｒ Ｈａｆｔｕｎｇ | Magnetic pigment |
| US9657185B2 (en) | 2010-12-09 | 2017-05-23 | Merck Patent Gmbh | Brilliant black pigments |
| DE102012005754A1 (en) | 2012-03-23 | 2013-09-26 | Merck Patent Gmbh | pigment |
| TW202045631A (en) | 2019-03-15 | 2020-12-16 | 德商麥克專利有限公司 | Deep bluish-black effect pigments |
| DE102019006869A1 (en) | 2019-10-02 | 2021-04-08 | Merck Patent Gmbh | Interference pigments |
| EP4121291A1 (en) | 2020-03-16 | 2023-01-25 | Merck Patent GmbH | Use of colored effect pigments for enhancing the infrared absorption capacity of colored polymers |
| EP4389828A1 (en) | 2022-12-19 | 2024-06-26 | Merck Patent GmbH | Effect pigments with at least one tio2 layer, in which the tio2 is doped with ti(3+) and fluoride |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3799799A (en) * | 1971-04-01 | 1974-03-26 | Fiberglas Canada Ltd | Coating of mica reinforcement for composite materials |
| DE3334598A1 (en) * | 1983-09-24 | 1985-04-18 | Merck Patent Gmbh | WEATHER-RESISTANT PEARL PIGMENT |
| FR2590583B1 (en) * | 1985-11-28 | 1988-01-29 | Saint Gobain Rech | METHOD FOR GRAFTING UNSATURATED ORGANIC COMPOUNDS ON GLASS FIBERS |
| US4877604A (en) * | 1987-09-04 | 1989-10-31 | Schlossman Mitchell L | Method of incorporating cosmetic pigments and bases into products containing oil and water phases |
-
1989
- 1989-09-05 DE DE3929423A patent/DE3929423A1/en not_active Withdrawn
-
1990
- 1990-08-24 EP EP90116230A patent/EP0416395B1/en not_active Expired - Lifetime
- 1990-08-24 ES ES90116230T patent/ES2063878T3/en not_active Expired - Lifetime
- 1990-08-24 DE DE59007552T patent/DE59007552D1/en not_active Expired - Fee Related
- 1990-08-31 CA CA002024486A patent/CA2024486A1/en not_active Abandoned
- 1990-09-04 KR KR1019900013922A patent/KR910006426A/en not_active Withdrawn
- 1990-09-04 CN CN90107465A patent/CN1050033A/en active Pending
- 1990-09-04 AU AU62168/90A patent/AU6216890A/en not_active Abandoned
- 1990-09-04 BR BR909004383A patent/BR9004383A/en unknown
- 1990-09-04 FI FI904354A patent/FI904354A7/en not_active IP Right Cessation
- 1990-09-05 JP JP2233435A patent/JPH0393863A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7745003B2 (en) | 2004-02-07 | 2010-06-29 | Merck Patent Gmbh | Particles having a functional multilayered structure |
Also Published As
| Publication number | Publication date |
|---|---|
| DE59007552D1 (en) | 1994-12-01 |
| EP0416395A2 (en) | 1991-03-13 |
| CN1050033A (en) | 1991-03-20 |
| KR910006426A (en) | 1991-04-29 |
| BR9004383A (en) | 1991-09-03 |
| FI904354A0 (en) | 1990-09-04 |
| EP0416395A3 (en) | 1991-11-21 |
| DE3929423A1 (en) | 1991-03-07 |
| ES2063878T3 (en) | 1995-01-16 |
| JPH0393863A (en) | 1991-04-18 |
| FI904354A7 (en) | 1991-03-06 |
| EP0416395B1 (en) | 1994-10-26 |
| AU6216890A (en) | 1991-03-14 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |