EP3380566A1 - Particules de pigment munies d'un enrobage superficiel et composition de revêtement contenant de telles particules de pigment - Google Patents

Particules de pigment munies d'un enrobage superficiel et composition de revêtement contenant de telles particules de pigment

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Publication number
EP3380566A1
EP3380566A1 EP16801999.0A EP16801999A EP3380566A1 EP 3380566 A1 EP3380566 A1 EP 3380566A1 EP 16801999 A EP16801999 A EP 16801999A EP 3380566 A1 EP3380566 A1 EP 3380566A1
Authority
EP
European Patent Office
Prior art keywords
pigment particles
coating
coating composition
mpas
amino
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP16801999.0A
Other languages
German (de)
English (en)
Inventor
Marc Entenmann
Irina ZIHAREVA
Heinz Greisiger
Rita Bitzer
Thadeus Schauer
Roman Maurer
Udo STÖCKLEIN
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Original Assignee
Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV filed Critical Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Publication of EP3380566A1 publication Critical patent/EP3380566A1/fr
Pending legal-status Critical Current

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Classifications

    • 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
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/36—Compounds of titanium
    • C09C1/3692—Combinations of treatments provided for in groups C09C1/3615 - C09C1/3684
    • 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
    • C09C1/0018—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings uncoated and unlayered plate-like particles
    • 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
    • C09C1/0051—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings comprising a stack of coating layers with alternating low and high refractive indices, wherein the first coating layer on the core surface has the low refractive index
    • C09C1/0057—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings comprising a stack of coating layers with alternating low and high refractive indices, wherein the first coating layer on the core surface has the low refractive index comprising at least one light-absorbing layer
    • C09C1/006—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings comprising a stack of coating layers with alternating low and high refractive indices, wherein the first coating layer on the core surface has the low refractive index comprising at least one light-absorbing layer consisting of a metal or an alloy
    • 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
    • C09C1/22—Compounds of iron
    • C09C1/24—Oxides of iron
    • 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
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C09C1/3081—Treatment with organo-silicon 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
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/36—Compounds of titanium
    • C09C1/3607—Titanium dioxide
    • C09C1/3684—Treatment with organo-silicon 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
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/40—Compounds of aluminium
    • C09C1/42—Clays
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C09D5/022—Emulsions, e.g. oil in water
    • 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
    • C09D7/20—Diluents or solvents
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general
    • 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
    • C08K9/06—Ingredients treated with organic substances with silicon-containing 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
    • 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

Definitions

  • the invention relates to pigment particles with a surface coating which are particularly suitable for use in stratifying coating compositions with which coatings can be achieved on a substrate with a surface-distant, substrate-near enrichment of the pigment particles.
  • the invention further relates to substrates having a coating produced using the aforementioned stratifying coating composition and to a process for producing an effect pigment lacquer layer in which the stratifying properties of the pigment particles according to the invention are utilized.
  • Patent 4,654,270 discloses a polysiloxane component-containing self-stratifying coating composition which additionally contains a polyester binder and preferably an aminoplast curing agent.
  • Another stratifying coating composition is known from British patent specification GB 631,245, which is based on a paraffinic binder, a polyvinyl binder, in particular formed from a copolymer of a vinyl halide and vinyl acetate, and a solvent for these components and which also for coating metals should be suitable.
  • the above self-stratifying coating compositions are always based on at least two mutually incompatible polymeric or oligomeric components which separate into a near-surface and a substrate-near layer having different physical and chemical properties.
  • these self-stratifying coating compositions include binder mixtures of incompatible polymeric or oligomeric olefinic or paraffinic components on the one hand and siloxane or fluoro-organic components on the other.
  • binder mixtures of incompatible polymeric or oligomeric olefinic or paraffinic components on the one hand and siloxane or fluoro-organic components on the other.
  • too little pronounced substrate and / or interlayer adhesion proves to be problematic in these, formed on the incompatibility of binder components, separate layers forming systems, so that these systems, if at all, only for special applications.
  • the object of the invention is therefore to propose pigment particles and coating compositions containing them, which are suitable for demanding industrial protective coatings and coatings in the automotive sector.
  • the pigment particles of the present invention are particularly suitable for use in self-stratifying coating compositions where stratification is a distribution gradient of the components of the composition within a coherent layer, as viewed across the thickness of the coating obtained. Differing from each other and thus in case of doubt also peeling layers within the coating can be avoided. Also, with these self-stratifying coating compositions, a coating with very good substrate liability, which also meets very high requirements. In particular, distribution gradients of the pigment particles of the present invention in the coating can also be achieved with increased concentrations in substrate-near and surface-distant areas of the coating, an effect which results in additional advantages in a number of applications.
  • Reactive silane-functional components for the purposes of the present invention are components which comprise a silane compound which can undergo a crosslinking reaction with an amino-functional component.
  • the crosslinking reaction is not fixed to a specific type of reaction.
  • the surface coating does not necessarily cover the entire surface of these particles.
  • the thickness of the surface coating does not need to be homogeneous.
  • pigment particles are preferred in which the surface coating covers substantially the entire surface of the pigment particles, with a substantially uniform thickness of the surface coating being more preferred.
  • the method according to the invention is based on the knowledge of the inventors that organic coating formulations containing amino-functional hardener components lead to a surface-distant and substrate-like Enrichment of polar, especially amino-functional, components can come.
  • the inventors were able to both use comparative IR-microscopic measurements on the top and bottom sides of lacquer films detached from a substrate, or before detachment of the lacquer films on their surface and their substrate-proximate area
  • a significant increase in polar, amino-functional and hydroxyl-functional coating components on the (former) substrate side of the coating films can be observed.
  • surface-coated pigment particles according to the invention often increase their viscosity less when added to clearcoat formulations than corresponding pigment particles which have been surface-modified according to the prior art only with silane-functional components. On the one hand, this has favorable effects on the course of the clearcoat formulations on the substrate surface and thus also on the formation of a high surface gloss and on the extent of pigment stratification.
  • the upper limit is preferably a weight fraction of about 7 wt .-%, preferably maintained at about 5 wt .-%.
  • a further preferred range for the weight fraction of the surface coating on the weight of the uncoated pigment particles is about 2 to about 3.5 wt .-%, most preferably about 2.1 to about 3.5 wt .-%.
  • the organic amino-functional component used in the formation of the surface coating of the pigment particles according to the invention preferably comprises an oligomeric, amino-functional polyether, an oligomeric polyethylenimine, an aliphatic, aromatic and / or heterocyclic amine or mixtures of two or more of the abovementioned components.
  • Heterocyclic amines having two or more nitrogen atoms qualify in the context of the present invention as an amino-functional component having two or more amino groups.
  • Particularly preferred amino-functional components having two or more amino groups are polyoxypropylenediamine, 1,2-diaminocyclohexane, 2,4,6-triaminopyramidine and 1H-benzotriazole.
  • a reactive, preferably epoxy- and / or amino-functional silane component is used as silane-functional component in the formation of Oberfiumbleenbe harshung the pigment particles of the invention.
  • Particularly preferred silane-functional components are N- (2-aminoethyl) -3-aminopropyltrimethoxysilane (DAMO), 3-aminopropyltrimethoxysilane (AMMO), 3-methacryloxypropyltrimethoxysilane (MEMO) and 3-glycidyl-oxypropyl- trimethoxysilane (GLYMO).
  • DAMO N- (2-aminoethyl) -3-aminopropyltrimethoxysilane
  • AMMO 3-aminopropyltrimethoxysilane
  • MEMO 3-methacryloxypropyltrimethoxysilane
  • GLYMO 3-glycidyl-oxypropyl- trimethoxysilane
  • the preferred silane-functional components may
  • the surface coating according to the invention is formed using an amino-functional and a silane-functional component, wherein the ratio of the weight proportions of the silane to the amino-functional component in the surface coating of the particles is in particular about 1: 2 to about 5.8: 1 Preferably, about 1.2: 1 to about 5.8: 1, more preferably about 1.5: 1 to about 4.8: 1, most preferably about 1.8: 1 to about 2 , 8: 1.
  • the present invention is suitable for the modification of pigment particles of different shape and size, in particular also of granular and substantially spherical pigment particles.
  • pigment particles which are spatially anisotropic in particular platelet-shaped pigment particles.
  • the average particle size D 50 of the pigment particles is preferably about 0.1 m to about 120 pm, more preferably about 1 pm to about 30 pm, wherein in the case of spatially anisotropic particles, the mean particle size determined by the largest dimension of the particles becomes.
  • the invention furthermore relates, as already mentioned, to stratifying coating compositions, in particular in the form of coating compositions, these comprising a first polar, oligomeric or polymeric component, a proportion of a polar solvent and a proportion of pigment particles of the invention.
  • the proportion of pigment particles on which the coating composition is composed tion-forming solids in the range of about 0.05 wt .-% to about
  • stratifying and non-stratifying particles can also be used in the coating compositions, the proportion of non-stratifying pigment particles here being rather low, typically about 30% by weight of the proportion of particles used or less.
  • the proportion of non-stratifying particles can be higher depending on the task and, for example, approx.
  • the coating composition of the invention has a viscosity at 20 ° C and a shear rate of 10 s "1 from about 50 mPas to about 500 mPas, more preferably about 100 mPas to about 400 mPas, most preferably about 100 mPas to about 350 mPas.
  • coating compositions having pronounced thixotropy in which a difference in the viscosities determined at 20 ° C at shear rates of 10 s -1 and 1000 s -1 is about 300 mPas or less, more preferably about 200 mPas or less, most preferably about 150 mPas or less.
  • the difference in preferred coating compositions is about 20 mPas or more.
  • the coating composition of the present invention comprises one or more volatile solvents, which are also preferably selected from polar and non-polar solvents, the polar solvents being selected in particular from alcohols, esters and ketones and the non-polar solvents from hydrocarbons.
  • Particularly preferred coating compositions according to the invention each contain at least one polar and one nonpolar solvent which together form a hydrophobic medium, the polar solvents in particular from propyl and butyl acetates and the non-polar solvents, in particular from solvent naphtha (DIN 51 633) (SN), toluene , Xylene and petroleum ether are selected.
  • the polar solvents in particular from propyl and butyl acetates
  • the non-polar solvents in particular from solvent naphtha (DIN 51 633) (SN), toluene , Xylene and petroleum ether are selected.
  • compositions in which all solvent portions are selected from highly volatile solvents.
  • coating compositions according to the invention can be formulated with great advantages as coating compositions, in particular also as non-hiding coating material, in particular also as clearcoat material.
  • the invention further relates to a substrate with a coating which is produced using one of the coating compositions according to the invention.
  • Substrates according to the invention are preferably characterized in that, due to a stratification effect, the coating has in its surface area with a thickness corresponding to 25% of the total thickness of the coating a proportion of pigment particles which is about 20% or less of the mass of pigment particles in the entire coating , preferably about 15 wt% or less, more preferably about 13 wt% or less.
  • This reduction in the proportion of the pigment particles according to the invention in the near-surface area of the coating due to a stratification effect has the result that the proportion of pigment particles in regions of the coating which are adjacent to the substrate surface is above the average content of pigment particles.
  • the coating according to the invention has its advantageous properties, in particular the optical properties, but also, for example, the improved corrosion resistance in a - optionally repeated - polishing of the surface, in which significant proportions of the coating can be removed, in a significant Maintains extent, while conventional coatings are expected to be significant losses.
  • substrates in which the coating has a 20 ° gloss value, measured in accordance with DIN 67 530 / ISO 2813, in the range from about 75 to about 98, more preferably in the range from about 78 to about 95, on most preferably in the range of about 80 to about 92.
  • Further preferred substrates have a coating in the form of a multilayer coating, wherein the uppermost layer of the coating is produced using the coating composition according to the invention.
  • substrates according to the invention may be mentioned in which one of the layers of the multilayer coating is formed below the uppermost layer as a primer and / or basecoat layer.
  • a particularly important field of application of the coating compositions according to the invention is the industry, in particular also the automotive industry, wherein the coating compositions according to the invention can also be used, in particular, alternatively to conventional clearcoat formulations for the coating of vehicle bodies.
  • the invention also relates to a process for producing an ef-effect pigment coating, wherein a primer or basecoat film and then a coating composition according to the invention are applied to a substrate first.
  • FIG. 1 IR-microscopic measurements on surface-near and substrate-near areas of coatings of commercially available automotive clearcoats ProGloss, iGloss (both BASF Coatings) and CeramiClear (PPG);
  • FIG. 2 Sedimentation analyzes for the Iriodin Pigment 1103 in MPA, surface-modified according to the prior art (formulation Bl) and surface-coated according to the invention (formulation B3-A1);
  • FIG. 3 shows sedimentation analyzes for the Iriodin Pigment 1103 in MPA / solvent naphtha 1: 1, surface-modified according to the prior art (formulation Bl) and surface-coated according to the invention (formulation B3-A1);
  • FIG. 4 Sedimentation analyzes for the Iriodin Pigment 1504 in MPA, surface-modified according to the prior art (formulation Bl) and surface-coated according to the invention (formulation B3-A1);
  • FIG. 5 Sedimentation analyzes for the Iriodin Pigment 1504 in MPA / solvent denaphtha 1: 1, surface-modified according to the prior art (formulation Bl) and surface-coated according to the invention (formulation B3-A1);
  • FIG. 7 dependence of the 20 ° surface gloss value on the type of surface modification / coating of the Iriodin 103 and Iriodin 504 pigment particles in the clearcoat formulation B;
  • FIG. 8 anticorrosive examination using impedance measurements of the hydrophilic clearcoat formulation B with in each case 3% by weight of unmodified and surface-coated talcum pigment particles LP30 according to the invention according to Example 1;
  • Pigment particles according to the prior art Iriodin 103 Bl on the du values of a clearcoat formulation A for different pigment particle concentrations
  • Pigment particles according to the prior art Iriodin 103 Bl on the DOI values of a clearcoat formulation A for different pigment concentrations.
  • Example 1 Carrying out the surface modifications according to the prior art and the surface coating according to the invention
  • this mixture is heated with gentle stirring to 70 ° C and the proportion of the reactive silane-functional component 2-aminoethyl-3-aminopropyltrimethoxysilane (Dynasylan DAMO; Evonik AG) and optionally additionally 3-glycidyl-oxypropyl-trimethoxysilane (Dynasylan GLYMO , Evonik AG) was added to the mixture. After stirring for 30 minutes at 70 ° C., the resulting surface-coated pigment is filtered off and purified by repeated rinsing with distilled water.
  • the proportions of the amino-functional and the silane-functional components (also referred to as amino component or silane component for short) used in the individual example formulations are given in the following Table 1.
  • the example formulation defined in the following Table 1 as Bl serves as a comparison formulation with DAMO as a silane-functional component.
  • An amino-functional component is not used in this comparative example.
  • the surface modification carried out here corresponds to the prior art (EP 0 492 223 A2).
  • Example formulations B2-A1 and B3-A1 use surface coatings according to the invention using DAMO as the silane component and polyoxypropylenediamines (obtainable as Jeffamine D-400 with a molecular weight of about 430 g / mol from Huntsman Corp.) as the amino component.
  • DAMO silane component
  • polyoxypropylenediamines obtainable as Jeffamine D-400 with a molecular weight of about 430 g / mol from Huntsman Corp.
  • the proportions of the respective silane and amino-functional components in the formulations used for the surface coating can be found again in Table 1, in each case as wt .-% based on the content of uncoated pigment particles.
  • Example 2 Characterization of the Compatibility of Pigments Obtained from Example 1 by Sedimentation Analyzes in the Solvent Mixture Methoxypropyl Acetate / Solvent Naphtha and in Pure MPA
  • sedimentation analyzes were carried out in the polar solvent methoxypropyl acetate (MPA) and in a performed by Solventnaphatha (SN) addition of hydrophobic set 1: 1 solvent mixture MPA / SN.
  • the sedimentation analyzes include transparency measurements as a function of the sedimentation time. The content of pigment particles was in each case 0.09% by weight, based on the solvent.
  • a strong increase in the transparency with respect to the sedimentation time characterizes a lower wetting and compatibility of the respective surface-modified / -coated pigment particles with the respective solvent or solvent mixture.
  • the iriodin pigment particles based on iriodin 103 and iriodin 504 with the surface coating of the formulation B3-A1 according to the invention have a somewhat improved compatibilization and flocculation stability in the more polar solvent MPA than pigment particles with the surface modification according to the prior art the technique (formulation Bl), which were modified only with the silane-functional component.
  • the more hydrophobic solvent mixture with solvent naphtha can be used detect a reverse effect on the sedimentation behavior of the pigment particles.
  • the surface-coated pigment particles according to the invention are particularly suitable for use in coating compositions with high proportions of polar solvents.
  • Example 3 incorporation of pigment particles from Example 1 in clearcoat formulation and characterization of the resulting stratification effect by measuring the surface gloss
  • Desmophen® A 665 BA / X 50.30% by weight of Desmophen® A 665 BA / X, 65% by weight in butyl acetate / xylene
  • the clearcoat formulation A has a viscosity of 320 mPas at a temperature of 20 ° C. and a shear rate of 10 s -1 and a viscosity of 319 mPas at a shear rate of 1000 s -1 .
  • Proportions of pigment particles from Example 1, which are each specified below, relate to the solid formed from Desmodur® and Desmophen®.
  • the clearcoat formulation B has a viscosity of 331 mPas at a temperature of 20 ° C. and a shear rate of 10 s -1 and a viscosity of 330 mPas at a shear rate of 1000 s -1 .
  • the clearcoat formulation A (with solvent mixture MPA / SN in the ratio 1: 1) represents the less polar
  • the clearcoat formulation B (with solvent MPA) the more polar formulation.
  • the clearcoat formulations with the differently surface-modified or surface-coated pigment particles were applied pneumatically to black Leneta sheets (manufacturer: Leneta Company Inc.) with a dry film thickness of about 35 m.
  • a coating of a substrate could be shown by laser scanning microscope (type VK-X of Keyence Corp.) that coated according to the invention Iriodin pigment particles 1103 B3-A1 from Example 1 in a 40 pm thick coating with a pigment content of about 1% by weight, based on the solids of the coating composition, in a composition based on paint formulation B due to the stratification effect achieved according to the invention in the near-surface 10 ⁇ m only with a proportion of about 12 %, instead of the statistical value of 25%, while the same pigment in uncoated form even accumulates to about 32% in this near-surface area.
  • the viscosity values of the clearcoat formulation B remain substantially unchanged after addition of the pigment particles 1103 B3-A1 in a proportion of 1% by weight within the scope of the measurement accuracy.
  • the stratification effect has the advantage that substrates coated according to the invention, even after a surface polishing in which a quarter of the coating is removed, substantially unchanged in their - especially optical - properties present, while in a coating with untreated pigment significant losses in the optical equity Shafts must be accepted. Also, the corrosion resistance is substantially retained in a coating according to the invention after such a polishing, while in coatings with untreated pigments is to be expected with a significant deterioration. In addition, corrosion resistance is further enhanced by the fact that not only the near surface area of the coatings is depleted due to the stratification effect on pigments, but also that an enrichment of the pigment particles according to the invention which exceeds the statistical value is achieved in the substrate-near area of the coatings ,
  • the 20 ° surface gloss value according to DIN 67 530 / ISO 2813 was used as another practically relevant measure for the quantification of the obtained stratification of the pigment particle fractions in the coating composition.
  • the viscosity of the coating composition with the pigment particles 1103 B3-A1 at 20 ° C. and a shear rate of 10 s -1 was 336 mPas, the viscosity measured at 20 ° C. and a shear rate of 1000 s -1
  • compositions with pigment particles according to the prior art 103 Bl viscosity values "1 s or 1.000" resulted at 20 ° C of 341 mPas and 340 mPas at shear rates of 10 s. 1
  • Example 2 If one now assumes that in the copolymerization of low molecular weight polyfunctional amino-functional component (s), the amino functionality and the polarity of the pigment surface coating increase significantly and that higher proportions of the silane-functional component (s) in the inventive Surface coating of the pigment particles rather adversely affect the pigment wetting and flocculation stability, the sedimentation results in Example 2 and the surface gloss values obtained in Example 3 can be interpreted to mean that a higher amino-functional surface coating compared to the exclusive use of silane-functional components as in stand The technique has a favorable effect on the pigment particle wetting and also allows the achievement of high surface gloss values.
  • silane-functional component predominantly performs the function of fixing the reaction product of the organic amino-functional component with the silane-functional component on the pigment particle surface, since only then are correspondingly high surface gloss values achieved, if a critical and Networking necessary amount of silane-functional component is not exceeded.
  • formulation B2-A1 not only the highest proportions of the silane-functional component but at the same time the lowest total amounts of components were used for the surface coating, so that ultimately both factors mentioned for the lower gloss values obtained in the case of the formula B2-A1 are responsible.
  • finely divided pigment particles having a higher specific surface area such as, for example, platelet-shaped effect pigments
  • silane-functional component based on the pigment particle mass, for their surface coating, in particular about 2.0% by weight or more.
  • the silane-functional component essentially plays the role of the crosslinking partner in the surface coating of the pigment particles and less important for the development of a high surface gloss in the substrate coatings. Therefore, it is also evident in these examples that, in particular, the organic multiply functional amino component used nents to achieve the highest possible surface gloss value.
  • pigment particles which have a polar and strongly amino-functional surface coating accumulate more strongly at a greater distance to the surface during a paint application on a substrate surface and the subsequent course than conventionally - ie. with the exclusive use of silane-functional components - surface-modified pigment particles.
  • sufficiently high pigment contents and not too strong and not too weakly viscous set clearcoat systems could also a trend to lower the viscosity at certain shear rates for the surface-coated pigment particles according to the invention compared to the surface-modified pigment particles which are conventionally surface-modified using only silane-functional components.
  • the non-pigmented coating formulations show the lowest viscosities and the corresponding coating formulations with the conventional surface-modified pigment particles have the highest viscosities.
  • the surface-coated pigment particles according to the invention have a viscosity lying between the two extremes.
  • the surface coating of the pigment particles according to the invention therefore additionally has a favorable effect on the course of pigmented coating formulations, which also influences the stratification of the proportions of the pigment particles in the coating composition according to the invention and the expression of a high surface gloss value.
  • Example 4 incorporation of talcum pigment particles according to the invention obtained from Example 1 into a clearcoat formulation and characterization of the corrosion protection effects obtained by impedance measurements
  • FIG. 8 shows the results of a corrosion protection investigation using impedance measurements of the hydrophilic clearcoat formulation B with MPA as solvent after incorporation of in each case 3% by weight of differently surface-modified talcum pigment particles LP30, applied at a dry layer thickness of about 35 ⁇ m to sandblasted steel sheets 200 mm x 100 mm x 2.0 mm DC 04 B Rz 20-30 pm (Franz Krüppel Industrie office, GmbH + Co. KG).
  • the samples were thermocycled with 5% by weight aqueous brine for the duration indicated in the abscissa of Figure 8 with directly consecutive one-hour cycles of 23 ° C to 70 ° C. In this case, the heating of 23 ° C to 70 ° C for half an hour and then directly followed by the cooling from 70 ° C back to 23 ° C per cycle.
  • the results shown in FIG. 8 show that the more polar and hydrophilic clearcoat formulation B with MPA and the talcum pigment particles (LP30) with the surface coating according to the invention according to formulation B3-A1 according to the invention compared to a formulation with the - as usual in the art non-surface-modified talc has greatly improved anti-corrosion properties.
  • the stratification of the proportions of the pigment particles according to the invention in the lacquer layer and their accumulation in the region near the substrate lead to the formation of a better water and oxygen barrier.
  • Example 5 Influence According to the Invention of Surface-Modified Effect Pigment Particles from Example 1 at Different Concentrations in Clearcoat Target Formulations on the Dullness D u Values and the Distinctness of Image DOI Values
  • FIG. 9 shows the influences of selected surface-coated pigment particles Iriodin 103 B4-A4 and Iriodin 103 Bl according to the prior art from Example 1 on the automotive-relevant Dullness du values for the weaker polar clearcoat formulation A, with 1: 1.
  • a lower Dullness du value represents a higher surface quality of the paint layer.
  • the Dullness du value represents the ratio of the scattered light intensity at the edge of a pinhole to the scattered light intensity in the center of the pinhole (Konrad Lex, progression evaluation of the coating structure with the wave-scan dual, rl-press, reprint World of Colors, 3, 2006, 14 -19).
  • the differences in the du values are also strongly influenced by the level of the proportions of the pigment particles. At low pigment concentrations of 0.25% by weight, the differences in the Dullness du values between the formulations with surface-coated pigment particles according to the invention and surface-modified pigment particles according to the prior art are significantly lower.
  • FIG. 10 shows the effects of the pigment particles Iriodin 103 B4-A4 according to the invention and the pigment particles Iriodin 103 Bl according to the prior art from Example 1 on the Distinctness of Image DOI values (ASTM E 284), which are likewise significant in the automotive sector, for the weaker polar clearcoat Feed formulation A with a 1: 1 solvent mixture MPA / SN for the pigment concentrations of 0.25% by weight; 0.50 wt%, 1.00 wt% and 3.00 wt%. In contrast to the du values, a higher DOI value represents a higher surface quality of the lacquer layer.
  • Iriodin 103 in accordance with formulation Bl, is more favorable for the surface-coated pigment particles Iriodin 103 according to the invention when using the formulation B4-A4 compared to surface-modified pigment particles according to the prior art. give higher DOI values for pigmented clearcoat formulations. Concentrations of the pigment particles in the formulations in the range from 0.5% by weight to 1% by weight show the greatest differences in terms of the DOI value between the surface-coated pigment particles according to the invention and the surface-modified pigment particles according to the prior art.
  • Examples 2 to 5 show that the inventive surface coating according to Example 1 different pigment particles for various applications in different paint systems can be optimally optimized with regard to optimum wetting, compatibility and flocculation stability.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Dispersion Chemistry (AREA)
  • Metallurgy (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Paints Or Removers (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)

Abstract

Le but de l'invention est de fournir des particules de pigment et des compositions de revêtement les contenant, qui conviennent aux revêtements de protection industriels et aux peintures du secteur automobile exigeants. A cet effet, l'invention concerne des particules de pigment munies d'un enrobage superficiel et destinées à être utilisées dans une composition de revêtement stratifiante, l'enrobage superficiel des particules de pigment étant formé au moyen d'un constituant organique à fonction amino, qui comprend en particulier deux groupes amino ou plus, et d'un constituant réactif à fonction silane différent de ce dernier.
EP16801999.0A 2015-11-26 2016-11-17 Particules de pigment munies d'un enrobage superficiel et composition de revêtement contenant de telles particules de pigment Pending EP3380566A1 (fr)

Applications Claiming Priority (2)

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DE102015120557.2A DE102015120557A1 (de) 2015-11-26 2015-11-26 Pigmentpartikel mit einer Oberflächenbeschichtung und Beschichtungszusammensetzung mit solchen Pigmentpartikeln
PCT/EP2016/078022 WO2017089225A1 (fr) 2015-11-26 2016-11-17 Particules de pigment munies d'un enrobage superficiel et composition de revêtement contenant de telles particules de pigment

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EP (1) EP3380566A1 (fr)
JP (1) JP2019501991A (fr)
CN (1) CN109874328A (fr)
DE (1) DE102015120557A1 (fr)
WO (1) WO2017089225A1 (fr)

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EP3794077A4 (fr) * 2018-05-16 2022-03-16 Burgess Pigment Company Kaolin anhydre et autres minéraux traités au silane

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GB631245A (en) 1946-10-04 1949-10-31 Continental Can Co Improvements in or relating to coating compositions
US4618657A (en) 1985-03-11 1986-10-21 Desoto, Inc. Heat curable polysiloxane release coatings which stratify when baked and paper coated therewith
DE4041663A1 (de) 1990-12-22 1992-06-25 Merck Patent Gmbh Silanisierte pigmente und deren verwendung zu vergilbungsinhibierung von pigmentierten kunststoffen
US5912283A (en) * 1995-07-19 1999-06-15 Toyo Aluminium Kabushiki Kaisha Surface-treated color pigment, colored substrate particles and production process thereof
DE19820112A1 (de) * 1998-05-06 1999-11-11 Eckart Standard Bronzepulver Mit reaktiven Orientierungshilfsmitteln beschichtete Effektpigmente
DE10006538C2 (de) 2000-02-15 2002-11-28 Forsch Pigmente Und Lacke E V Verfahren zur Beschichtung von Partikeln mit LCST-Polymeren
JP2002256173A (ja) * 2000-12-26 2002-09-11 Nippon Aerosil Co Ltd 表面改質無機酸化物粉末とその用途
DE10245201A1 (de) 2002-09-27 2004-04-15 Daimlerchrysler Ag Beschichtungszusammensetzung zur Bildung selbstschichtbildender oder selbstschichtender Lacksysteme
JP2005171208A (ja) * 2003-12-15 2005-06-30 Toyota Motor Corp フィラー及び樹脂組成物
CN101316901A (zh) * 2005-08-09 2008-12-03 索恩实验室公司 经染料附着的和/或经表面改性的颜料
DE102006009130A1 (de) * 2006-02-24 2007-08-30 Eckart Gmbh & Co. Kg Wetterstabile Perlglanzpigmente auf Basis dünner Glasplättchen und Verfahren zu deren Herstellung
US8299170B2 (en) 2008-10-08 2012-10-30 Toyota Motor Engineering & Manufacturing North America, Inc. Self-stratifying coating
DE102008060228A1 (de) * 2008-12-04 2010-06-10 Merck Patent Gmbh Oberflächenmodifizierte Pigmente
US8044140B2 (en) * 2009-06-12 2011-10-25 Toyota Motor Engineering & Manufacturing North America, Inc Methods and compositions for pigmented self-stratifying coatings
EP2604247A1 (fr) * 2011-12-15 2013-06-19 Dentsply DeTrey GmbH Particules de charge composite et procédé de préparation associé
DE102012103505A1 (de) * 2012-04-20 2013-10-24 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verfahren zur Oberflächenmodifizierung von Partikeln
BR112014032285B1 (pt) * 2012-06-21 2021-04-20 Tesla Nanocoatings, Inc. materiais ajustáveis
DE102012109407A1 (de) * 2012-10-02 2014-03-27 Eckart Gmbh Wetterstabile Perlglanzpigmente, Verfahren zu ihrer Herstellung und Verwendung
EP2727966A1 (fr) * 2012-11-06 2014-05-07 Eckart GmbH Pigment à activité photocatalytique, son procédé de fabrication et moyen de revêtement
JP6415104B2 (ja) * 2014-05-16 2018-10-31 ナミックス株式会社 液状封止材、それを用いた電子部品
JP2018052997A (ja) * 2015-02-12 2018-04-05 関西ペイント株式会社 表面被覆光輝性顔料及びこれを含む光輝性塗料組成物

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CN109874328A (zh) 2019-06-11
US20180265709A1 (en) 2018-09-20
DE102015120557A1 (de) 2017-06-01
WO2017089225A1 (fr) 2017-06-01
JP2019501991A (ja) 2019-01-24

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