EP1692231A2 - Particules a surface modifiee - Google Patents

Particules a surface modifiee

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Publication number
EP1692231A2
EP1692231A2 EP04797871A EP04797871A EP1692231A2 EP 1692231 A2 EP1692231 A2 EP 1692231A2 EP 04797871 A EP04797871 A EP 04797871A EP 04797871 A EP04797871 A EP 04797871A EP 1692231 A2 EP1692231 A2 EP 1692231A2
Authority
EP
European Patent Office
Prior art keywords
pigments
modified
pigment
substrates
polymer
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.)
Withdrawn
Application number
EP04797871A
Other languages
German (de)
English (en)
Inventor
Marc Entenmann
Adalbert Huber
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.)
Merck Patent GmbH
Original Assignee
Merck Patent GmbH
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 Merck Patent GmbH filed Critical Merck Patent GmbH
Publication of EP1692231A2 publication Critical patent/EP1692231A2/fr
Withdrawn legal-status Critical Current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
    • 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
    • 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
    • C01P2006/62—L* (lightness axis)
    • 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
    • C01P2006/63—Optical properties, e.g. expressed in CIELAB-values a* (red-green axis)
    • 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
    • C01P2006/64—Optical properties, e.g. expressed in CIELAB-values b* (yellow-blue axis)
    • 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
    • C09C2200/30—Interference pigments characterised by the thickness of the core or layers thereon or by the total thickness of the final pigment particle
    • C09C2200/307—Thickness of an outermost protective layer
    • 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
    • C09C2200/405—High molecular weight materials, e.g. polymers
    • 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
    • C09C2200/405—High molecular weight materials, e.g. polymers
    • C09C2200/406—High molecular weight materials, e.g. polymers comprising additional functional groups, e.g. -NH2, -C=C- or -SO3
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
    • Y10T428/264—Up to 3 mils
    • Y10T428/265—1 mil or less
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers

Definitions

  • the present invention relates to particles modified by colorants, which are characterized in that they are coated with one or more layers of immobilized LCST and / or UCST polymers.
  • the object of the present invention is to greatly change the color of existing colorants, in particular pigments, in a simple manner. This possibility of changing the color properties is particularly useful for effect pigments
  • Interference and metal pigments since it makes it possible to change the color properties that were originally only variable in a given frame and thus to expand this frame considerably. Since these pigments are preferably reflective or interfering pigments, in which the absorption of light often only plays a minor role, the color range of these pigments can be expanded considerably by immobilizing absorbent colorants. In the case of interference pigments in which there is a certain transparency, the opacity is additionally increased.
  • the invention therefore relates to particles which have been surface-modified by colorants and which are coated with one or more layers of immobilized LCST and / or UCST polymers.
  • the colorant is applied to the surface of the effect pigment more efficiently and homogeneously than if the polymer or generally the precipitant is formed only by in situ polymerization, the dye during the Precipitation process and immobilizes the dye on the surface.
  • Such methods are e.g. B. is known from US 4,323,554, RU 2133218 C1 and US 5,037,475.
  • the trial of dyes by improved adsorbent (DE 19933138 A1, US 6,113,683, EP 0919598 A2, US 6,022,911) or charge-controlled
  • an organic colorant when included in an inorganic matrix, poor immobilization is to be expected due to the less strong interaction between colorant and matrix, which is often noticeable in the bleeding / blooming of the organic pigment in the lacquer layer, such as, for example. B. from U.S. 4,323,554 and RU 2133218.
  • the present invention uses an organic polymer as the immobilization matrix of the colorant, bleeding / blooming effects are very strongly suppressed and can be excluded by special adaptation of the polymer to the colorant.
  • the UCST and LCST polymers used in the present invention also show a very good interaction with inorganic substances, so that even these can be fixed on the surface without problems, since these substances do not tend to migrate anyway.
  • the process according to the invention is easier to carry out (deposition only by changing the temperature, no charge control, in situ polymerization), more universal (not very dependent on surface properties) and more efficient (since the colorant is homogenized directly in the precipitant and often can also be better immobilized).
  • the invention furthermore relates to the production of the surface-modified substrates and their use, inter alia in lacquers, water-based lacquers, powder lacquers, paints, printing inks, security printing inks, plastics, concrete, as a pigment for corrosion protection, as a dopant for the laser marking of paper and plastics and laser welding and in cosmetic formulations.
  • the particles according to the invention are also suitable for the preparation of pigment preparations and for the preparation of dry preparations, such as, for. B. granules, pellets, briquettes, etc., suitable.
  • Suitable particles are effect pigments, but also inorganic and organic spherical pigments, e.g. Titanium dioxide pigments, iron oxide pigments and Cu phthalocyanine pigments.
  • a platelet-shaped substrate such as, for example, aluminum, Al 2 O 3 , SiO 2 platelets, graphite platelets, glass platelets and / or mica, directly with organic or inorganic colorants in order to produce a new color pigment ,
  • metallic effect pigments such as ChromaFlair pigments from Flex, coated or uncoated aluminum flakes, gold bronze pigments, eg from Eckart, coated iron oxide flakes, such as Paliochrom ® pigments from BASF, Sicopearl pigments, are preferably used as effect pigments from BASF and goni-chromatic pigments from BASF, as described, for example, in EP 0 753 545 A2, as well as pearlescent pigments and interference pigments - mica flake pigments coated with metal oxides - available, for example, from Merck, Darmstadt under the trade name Iriodin ® - used.
  • Pearlescent pigments based on platelet-shaped substrates are preferably used.
  • Particularly preferred effect pigments are holographic Pigments, conductive and magnetic pigments, metallic effect pigments, e.g. B. on the basis of aluminum and / or iron flakes and effect pigments such as pearlescent pigments, interference pigments, goniochromatic pigments and multilayer pigments.
  • the platelet-shaped substrates are preferably natural or synthetic mica, BiOCI, Al 2 O, TiO 2 , Si0 2 , Fe 2 O 3 , glass or graphite platelets.
  • Preferred effect pigments are substrates coated with TiO 2 (rutile or anatase), such as, for. B. with TiO 2 coated natural or synthetic mica, with TiO 2 coated SiO 2 -, AI2O 3 -, graphite, glass, Fe 2 ⁇ 3 - or metal platelets, especially aluminum platelets.
  • TiO 2 rutile or anatase
  • TiO 2 coated natural or synthetic mica with TiO 2 coated SiO 2 -, AI2O 3 -, graphite, glass, Fe 2 ⁇ 3 - or metal platelets, especially aluminum platelets.
  • natural or synthetic mica, SiO 2 platelets, Al 2 O 3 platelets, glass platelets, ceramic platelets or synthetic carrier-free platelets are used as the substrate.
  • Multilayer pigments with two, three or more layers which contain one or more Ti
  • Substrate + titanium suboxides substrate + TiO 2 + Fe 2 O 3
  • the substrate preferably being mica, Al 2 O 3 , SiO 2 glass or metal platelets and metal-coated inorganic platelets. Mixtures of different effect pigments can also be stabilized by the process according to the invention.
  • Suitable colorants are all dyes and organic and inorganic color pigments known to the person skilled in the art.
  • Particularly suitable organic pigments from the color index list are e.g. Monoazo pigments C.I. Pigments Brown 25, C.I. Pigment Orange 5, 13, 36, 67, C.I. Pigment Red 1, 2, 3, 5, 8, 9, 12, 17, 22, 23, 31, 48: 1, 48: 2, 48: 3, 48: 4, 49.49: 1.52: 1, 52: 2.53.53: 1.53: 3.57: 1.251, 112, 146, 170, 184, 210, and 245, Cl Pigment Yellow 1, 3, 73, 65, 97, 151 and 183;
  • the colorants are used in amounts of 0.001-150%, particularly preferably 5-50%, in particular 10-30% by weight, based on the polymer.
  • the installation of additional scattering particles can also be interesting if an effect is to be dampened.
  • the proportion of scattering particles is 0-150%, particularly preferably 5-50%, in particular 10-30% by weight, based on the polymer.
  • the present invention can also be used to significantly change the physical properties of the surface, in particular with respect to the refractive index, by including transparent substances, in particular nanoparticles.
  • the precipitation of luminescent dyes, fluorescent dyes or phosphorescent dyes using LCST / UCST polymers opens up a process which enables the often more expensive dyes to be applied efficiently as the top layer on the surface.
  • These dyes are often used as a pure substance, only the surface being effective, or methods for precipitation are used which result in severe secondary precipitation of the dye.
  • This secondary precipitation effect can be achieved in the present process by slow, controlled precipitation, by optimizing the ratio of the LCST or UCST polymer to the colorant, by premixing and homogenizing the polymer with the colorant, and by selecting one on the colorant LCST / UCST polymers with a good stabilizing effect can be achieved below the critical temperature of the polymer.
  • the colorant and, if appropriate, further additives can be deposited in such a way that the colorant with the corresponding
  • LCST / UCST polymers are mixed (lower solution temperature polymers, become insoluble when the temperature rises in the medium), or UCST polymers (upper solution temperature polymers, become insoluble when cooled in the medium).
  • this can be done by simply admixing the dye to the polymer with gentle stirring, in the case of color pigments it being necessary to disperse the color pigment in the polymer or in a corresponding polymer solution using a bead mill or shaker.
  • the colorant / LCST or UCST polymer mixture is then added to the liquid medium which contains the effect pigments to be coated.
  • Polymers and a polymer / colorant layer is deposited on the surface of the effect pigment, which is then only immobilized by an additional reaction.
  • LCST polymers or UCST polymers are polymers which are soluble in a solvent at low or higher temperatures and when the temperature is increased or decreased and the so-called LCST or UCST (Iower or upper critical solution temperature) is reached from the Solution to be separated as a separate phase.
  • Such polymers are e.g. in the literature in "Polymers", H.-G. Elias, Wegig and Wepf-Verlag, Switzerland, 1996 on pages 183 ff.
  • Suitable LCST polymers or UCST polymers for the present invention are, for example, those as described in WO 01/60926 A1 and WO 03/014229 A1.
  • Particularly suitable LCST polymers are polyalkylene oxide derivatives, preferably polyethylene oxide (PEO) derivatives, polypropylene oxide (PPO) derivatives, olefinically modified PPO-PEO block copolymers, with acrylate-modified PEO-PPO-PEO three-block copolymers, polymethyl vinyl ether , Poly-N-vinylcaproIactam, ethyl (hydroxyethyl) cellulose, poly (N-isopropylacrylamide) and polysiloxanes.
  • Particularly preferred LCST polymers are siloxane polymers or polyethers modified with olefinic groups.
  • Suitable UCST polymers are in particular polystyrene, polystyrene copolymers and polyethylene oxide copolymers.
  • LCST or UCST polymers with functional groups are preferably used which have strong interactions and / or chemical bonds with the effect pigment and the application medium, such as. B. the paint matrix.
  • All functional groups known to the person skilled in the art are suitable, in particular silanol, amino, hydroxyl, epoxy, acid anhydride and acid groups.
  • the LCST or UCST polymers preferably have molar masses in the range from 300 to 500,000 g / mol, in particular from 500 to 20,000 g / mol.
  • the polymer content, based on the end product, is generally 0.1-80% by weight, preferably 1-30% by weight, in particular 1-20% by weight.
  • the effect pigment is preferably mixed with an immobilizable LCST and / or UCST polymer or polymer mixture containing one or more colorants in the presence of a solvent.
  • the LCST polymer is dissolved at the temperature below the LCST, while the UCST polymer is dissolved above the UCST.
  • the LCST temperature is 0.5-90 ° C., preferably 35-80 ° C.
  • the UCST temperature is 5-90 ° C., in particular 35-60 ° C.
  • additives are added.
  • the temperature is generally increased by about 5 ° C. above the LCST or lowered below the UCST, the polymer precipitating and settles on the particle surface.
  • the immobilization takes place in the form of a crosslinking of the polymer on the particle surface, the polymer being irreversibly fixed on the particle surface.
  • the immobilization can take place, for example, free-radical, cationic, anionic or by a condensation reaction.
  • the LCST or UCST polymers are preferably crosslinked by free radicals or by a condensation reaction.
  • potassium peroxodisulfate for a radical crosslinking (immobilization) of the deposited layer in water, potassium peroxodisulfate or is preferably used
  • Ammonium peroxodisulfate is used in concentration ranges from 1 to 100% by weight, based on the olefinic LCST or UCST polymer used for the coating.
  • the crosslinking takes place depending on the LCST or UCST temperature of the polymer at 0 - 35 ° C using a catalyst, such as. B. a Fe (ll) salt, or at 40 - 100 ° C by direct thermal decomposition of the radical initiator.
  • the choice of solvent depends on the solubility of the polymer used.
  • the solvent is preferably water or a water-miscible organic solvent.
  • the water-miscible solvents also include those solvents which have gaps in the mixture with water. In these cases, the proportions are chosen so that there is miscibility.
  • Suitable solvents are mono- and polyalcohols such as methanol, ethanol, n-propanol, isopropanol, cyclohexanol, glycol, glycerin, propylene glycol, polyethylene glycol, polybutylene glycol and the mono- and diether with methanol, ethanol, propanol and butanol of the polyalkylene glycols; Ethers such as tetrahydrofuran, dioxane, 1, 2-propanediol propyl ether, 1, 2-butane-1-methyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether; Esters such as methyl acetate, monoesters of ethylene glycol or propylene glycols with acetic acid, butyrolactone; Ketones such as acetone or methyl ethyl ketone; Amides such as formamide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and
  • the LCST and / or UCST polymer coatings are preferably carried out as a complete coating of the particles.
  • Effect pigments which have an LCST polymer coating, in particular made of polysiloxanes, or alternately an LCST and a UCST polymer coating are particularly preferred.
  • the effect pigments can also be coated with two or more successive identical or different LCST or UCST polymers.
  • the effect pigments preferably contain no more than five polymer coatings.
  • the polymer layer thickness determines the settling behavior, the so-called seeding, of the effect pigments. Seeding can be suppressed by selecting the polymer sheath accordingly thick, so that the density of the pigments is influenced. The particles settle more slowly and mostly do not compress as much as untreated effect pigments so that they can be easily stirred up again.
  • the polymer coating also largely prevents the pigment from bleeding out in the application medium.
  • the individual LCST and / or UCST polymer layers can also contain additives which additionally increase or decrease the chemical and / or mechanical stability of the particles.
  • Suitable additives are e.g. Nanoparticles, such as B. barium sulfate, polymerizable monomers, plasticizers, antioxidants, soot particles, microtitanium or mixtures thereof.
  • the proportion of additives is preferably 0.001 to 150% by weight, in particular 0.05 to 100% by weight, based on the polymer used.
  • the additives are preferably mixed into the solution of the LCST or UCST polymer as a dispersion, the same solvent as that of the polymer solution preferably being used and the
  • the additives can also be directly dispersed in the LCST or UCST polymers if they are in liquid form.
  • the surface modification of the particles with an LCST and / or UCST polymer containing a colorant changes the physical parameters of the pigments, e.g. the refractive index. Furthermore, the hydrophilicity or hydrophobicity and thus also the surface tension and the interfacial tension of the effect pigments in different application media can be determined by a suitable one
  • Polymer assignment can be set specifically. This results in improved and faster wetting and improved compatibility of the effect pigments with the respective systems. Since the LCST and / or UCST polymer layer can also absorb mechanical loads, the aftertreated effect pigments are also opposite
  • Shear loads more stable This is particularly the case with corresponding applications of shear-sensitive effect pigments, e.g. Aluminum pigments, effect pigments based on mica, an advantage.
  • shear-sensitive effect pigments e.g. Aluminum pigments, effect pigments based on mica
  • the surface modification also serves as protection against corrosion.
  • the properties of the polymer layer can also be influenced. It is possible, for example, to deposit titanium dioxide nanoparticles with a crosslinkable LCST polymer and other monomers as a mixture by precipitation, the hardness, crosslinking density and hydrophilicity / hydrophobicity can be varied depending on the polymer mixture. This mixture is then crosslinked on the surface, the properties of the deposited polymer layer additionally being able to be influenced depending on the crosslinking reaction and the amount of crosslinker.
  • LCST polymers modified with acrylate groups are crosslinked with, for example, potassium peroxodisulfate on the surface, the hydrophilicity of the effect pigment is greatly increased not only by the polymer coating, but also by the amount of peroxodisulfate used.
  • the effect pigments according to the invention preferably have an isoelectric point (pH at which the zeta potential of the pigment becomes zero) in the range from 5 to 10, in particular from 6 to 8.
  • the surface-modified effect pigments also show very good weather resistance, very good dispersion behavior and, because of their stability, are very well suited for a wide variety of application systems, in particular for aqueous and organic paints, particularly preferably for powder paints.
  • Effect pigments based on platelet-shaped substrates are generally sensitive to shear.
  • the surface modification of the effect pigments with LCST and / or UCST polymers leads to an additional mechanical stabilization of the pigments under high shear loads or abrasive processing methods.
  • the stabilization can also be increased if nanoparticles are added to the LCST and / or UCST polymers. Effect pigments stabilized in this way can be exposed to significantly higher shear forces than the untreated effect pigments, without loss of the platelet structure.
  • effect pigments according to the invention show an improved orientation in the lacquer and greatly improved color values compared to pearlescent pigments which have been treated with a silane to improve the leafing behavior, such as, for example, B. described in EP 0 634 459 A2.
  • the effect pigments modified according to the invention are compatible with a large number of color systems, preferably from the field of paints, water-based paints, powder paints, paints, printing inks, security printing inks, plastics and cosmetic formulations.
  • the particles according to the invention are furthermore provided that they are obtained by the polymer aftertreatment have been appropriately functionalized, as functional pigments, among other things, for laser marking of paper and plastics, as light protection, as pigment for corrosion protection, for coloring concrete and for applications in agriculture, for example for greenhouse films, as well as for the coloring of tent tarpaulins ,
  • the particles according to the invention are also advantageously mixed with organic dyes, organic pigments or other pigments, such as e.g. transparent and opaque white, colored and
  • Black pigments and with platelet-shaped iron oxides, organic pigments, holographic pigments, LCPs (Liquid crystal polymers), and conventional transparent, colored and black gloss pigments based on metal oxide coated mica, glass, Al 2 O 3 -, graphite and SiO 2 - Platelets, etc. can be used.
  • the particles stabilized according to the invention can be mixed in any ratio with commercially available pigments and fillers.
  • the surface-modified effect pigments are also suitable for the production of flowable pigment preparations and dry preparations, such as Granules, chips, briquettes, sausages, pellets, etc.
  • the pigment preparations and dry preparations are distinguished by the fact that they contain at least one or more effect pigments, binders and, optionally, one or more additives.
  • the dry preparations do not have to be completely dry, but can be up to max. 8% by weight, preferably 3-6% by weight, of water and / or a solvent or solvent mixture.
  • the invention thus also relates to formulations which contain the pigment preparations and dry preparations according to the invention.
  • Example 1 Deposition of a Cu-Phthalocyanine Blue Pigment on a Pearlescent Pigment
  • Iriodin ® 7205 TiO microns 2 coated mica pigments of particle size 10-60, Fa. Merck KGaA
  • 3 of a Cu-phthalocyanine pigment / LCST polymer preparation 1 g Heliogen g of blue pigment, Fa BASF is used for 1 h using zircon beads on a bead mill in 10 g
  • Silicone polymer molar mass 5000 g / mol and 10 ml of water dispersed.
  • the mixture is heated to the LCST temperature of the silicone polymer of 62 ° C. with stirring, the temperature is held for 45 min and, by reheating at 85 ° C. with the addition of 1 g of an aminoalkyltethoxysilane and 1 g of an epoxyalkyltrimethylsilane, the polysiloxane-LCST- modified with amino groups Polymer immobilized, the trapped dye also being fixed in the deposited pigment layer. After filtering off, the pigment is freed of non-immobilized dye by washing with water and dried.
  • Example 2 Deposition of a Cu-Phthalocyanine Blue Pigment on a Pearlescent Pigment
  • the result is that the body color of the red Iriodin, ® 504 in the direction of blue / green, the interference color near the glancing angle has shifted in the direction of blue.
  • Example 3 Deposition of a Cu-Phthalocyanine Blue Pigment on a Pearlescent Pigment
  • Table 3 Color value change when immobilizing Heliogen Blue on Iriodin .® 307 Stargold according to Example 3

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Cosmetics (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

L'invention concerne des substrats dont la surface est modifiée par des teintures, qui se caractérisent en ce qu'ils sont enveloppés d'une ou plusieurs couches de polymères LCST et/ou UCST immobilisés. L'invention concerne en outre un procédé de production de ces substrats à surface modifiée et leur utilisation dans des peintures, des peintures à l'eau, des peintures en poudre, des encres, des encres d'impression, des encres d'impression de sécurité, des matières plastiques, le béton, des formulations cosmétiques, des films pour l'agriculture, des bâches, pour le marquage laser de papiers et de matières plastiques, pour le soudage laser, comme agent photoprotecteur, comme pigment pour la protection anticorrosion et également la production de préparations de pigments et de préparations sèches.
EP04797871A 2003-12-10 2004-11-13 Particules a surface modifiee Withdrawn EP1692231A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2003158092 DE10358092A1 (de) 2003-12-10 2003-12-10 Oberflächenmodifizierte Partikel
PCT/EP2004/012882 WO2005056696A2 (fr) 2003-12-10 2004-11-13 Particules a surface modifiee

Publications (1)

Publication Number Publication Date
EP1692231A2 true EP1692231A2 (fr) 2006-08-23

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EP04797871A Withdrawn EP1692231A2 (fr) 2003-12-10 2004-11-13 Particules a surface modifiee

Country Status (5)

Country Link
US (2) US20070166534A1 (fr)
EP (1) EP1692231A2 (fr)
JP (1) JP2007518841A (fr)
DE (1) DE10358092A1 (fr)
WO (1) WO2005056696A2 (fr)

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JP2007518841A (ja) 2007-07-12
US20080249210A1 (en) 2008-10-09
DE10358092A1 (de) 2005-07-14
WO2005056696A3 (fr) 2005-08-11
WO2005056696A2 (fr) 2005-06-23

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