EP3596170A1 - Pigments à effets - Google Patents

Pigments à effets

Info

Publication number
EP3596170A1
EP3596170A1 EP18712176.9A EP18712176A EP3596170A1 EP 3596170 A1 EP3596170 A1 EP 3596170A1 EP 18712176 A EP18712176 A EP 18712176A EP 3596170 A1 EP3596170 A1 EP 3596170A1
Authority
EP
European Patent Office
Prior art keywords
tio
effect pigment
platelets
pigments
effect
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Withdrawn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
EP18712176.9A
Other languages
German (de)
English (en)
Inventor
Nicole Nelischer
Lukas Hamm
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 EP3596170A1 publication Critical patent/EP3596170A1/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Withdrawn legal-status Critical Current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
    • 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
    • C09C1/0024—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 high and low refractive indices, wherein the first coating layer on the core surface has the high refractive index
    • 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
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
    • 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
    • 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
    • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
    • 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
    • C08K9/02—Ingredients treated with inorganic substances
    • 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
    • C09C2200/1004—Interference pigments characterized by the core material the core comprising at least one inorganic oxide, e.g. Al2O3, TiO2 or SiO2
    • 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
    • C09C2200/30—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
    • C09C2200/30—Interference pigments characterised by the thickness of the core or layers thereon or by the total thickness of the final pigment particle
    • C09C2200/308—Total thickness of the pigment particle
    • 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
    • C09C2200/401—Inorganic protective coating
    • 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
    • C09C2220/00—Methods of preparing the interference pigments
    • C09C2220/10—Wet methods, e.g. co-precipitation
    • C09C2220/106—Wet methods, e.g. co-precipitation comprising only a drying or calcination step of the finally coated pigment

Definitions

  • the invention relates to glaze- and email-stable effect pigments with a top layer of antimony oxide, which have an improved stability,
  • Pearlescent effect must be expected. In order to avoid this, these pigments must either be encapsulated in additional protective layers, or else the use of pearlescent pigments in this high-temperature field of application is limited to iron oxide-coated pearlescent pigments in specially modified engobes or rivers.
  • CN 101462895A discloses the use of 10-60% by weight of golden pearlescent pigments in glazes at 1, 000-1.200 ° C. The inserted frit consists of this together
  • the disadvantage here is that the use is limited exclusively to special gold-colored pearlescent pigments based on mica, wherein the layer structure of the gold-colored pearlescent pigments is not disclosed.
  • the number and color selection of the pigments which can be used is thus very limited in CN 101462895A.
  • the modified engobes achieve better adhesion of the engobe on the fired or unfired bricks, clay and ceramics.
  • the engobe contains a frit for the firing range of 600-1200 ° C and one or more
  • Effect pigments e.g. Pearlescent pigments, for example in glazes, enamels, ceramic or glassy materials, where at
  • Object of the present invention is therefore to stabilize effect pigments in such a way that they are stable at temperatures> 1000 ° C and thus, for example, in decorative glazes, enamels, etc., can be used without difficulty and at the same time the optical properties of the effect pigments not or only insignificantly be affected by the stabilization.
  • a stabilization should be achieved here exclusively by the protective layer, without having to perform any modifications to the frit or the manufacturing process of the workpiece.
  • effect pigments for example pearlescent pigments, based on platelet-shaped substrates containing at least one layer of TiO 2 and / or titanium oxynitride and / or other titanium-containing mixed oxides known to the person skilled in the art and optionally further layers, are stabilized when they have a surface Cover layer of antimony oxide have. Due to this cover layer, the effect pigment is stable against temperatures> 1000 ° C and can easily be incorporated without loss of optical properties in enamels, glazes, clay and ceramic goods, etc.
  • Antimony oxide mixture are coated.
  • Ceramic ware containing the stabilized effect pigment according to the invention.
  • Antimony oxides leads to a significantly improved stability of the
  • the cover layer of antimony oxide may consist of different modifications of the antimony oxide.
  • the cover layer of antimony oxide may consist of different modifications of the antimony oxide.
  • the cover layer of antimony oxide may consist of different modifications of the antimony oxide.
  • Preferred mixtures consist of Sb 2 O 3 and Sb 2 O 4, Sb 2 O 4 and Sb 2 O5 and from Sb 2 O 3, Sb 2 O 4 and Sb 2 Os.
  • the antimony oxide layer from only one antimony oxide, in particular of Sb 2 O 3 or Sb 2 O 4 or Sb 2 O.
  • a cover layer of Sb 2 O 4 is particularly preferred.
  • Modifications of the Sb 2 O 4 is particularly the alpha-cervantite (alpha-Sb 2 O 4 ) to name as particularly preferred because it provides the effect pigments the greatest protection against temperatures> 1000 ° C and at the same time in addition to the stabilizing effect from a toxicological point of view also rated less critically than, for example, the Sb 2 O 3 .
  • alpha-Sb 2 O 4 alpha-cervantite
  • Effect pigments on the surface preferably with 5 to 50 wt.%, In particular 5 to 30 wt.% And very particularly preferably 10 to 15 wt.%, Based on the effect pigment, are coated with antimony oxide or an antimony oxide mixture. Particularly preferred is the occupancy of 10-15 wt.% Sb 2 O 4 , in particular alpha-Sb 2 O 4 .
  • the cover layer on the effect pigment generally has a thickness of 1 to 100 nm, in particular 2 to 70 nm and most preferably 5 to 50 nm. Under cover layer is understood in this patent application, the complete coating of the surface of an effect pigment.
  • the application of the topcoat to the effect pigment is simple and easy to handle.
  • the antimony oxide or antimony oxide mixture used for the stabilization is preferably made of one or more soluble antimony salts by wet-chemical precipitation reaction on the
  • coated effect pigments at temperatures of 400-1000 ° C, depending on the annealing temperature various modifications of antimony oxide, such as Sb2O3, Sb 2 O 4 or Sb 2 O5.
  • Sb2O3, Sb 2 O 4 or Sb 2 O5. The respective modifications can be easily verified by means of XRD.
  • the effect pigments are suspended in water and reacted with one or more hydrolyzable antimony salts, preferably antimony-III salts, e.g. SbCU, at a suitable pH for the hydrolysis, which is chosen so that the antimony oxide or antimony oxide hydrate is precipitated directly on the effect pigments, without causing precipitation.
  • a suitable pH for the hydrolysis which is chosen so that the antimony oxide or antimony oxide hydrate is precipitated directly on the effect pigments, without causing precipitation.
  • the pH is usually kept constant by simultaneous addition of a base and / or acid.
  • the effect pigments are separated, washed and dried and optionally annealed. In general, the annealing temperatures are in the range of 250-1000 ° C, preferably 350-900 ° C. If desired, the pigments can finally be sieved to adjust the corresponding particle size.
  • the coating with the antimony oxide according to the invention takes place without calcining the effect pigment beforehand.
  • the coating can also be effected in a fluidized-bed reactor by gas-phase coating, wherein, for example, the methods proposed in EP 0 045 851 and EP 0 106 235 for the preparation of pearlescent pigments can be used correspondingly.
  • the following Sb-containing precursors can be used, which hydrolyze with H 2 O vapor: SbCU, SbF 3 , Sb (III) n-butoxide, Sb (III) ethoxide or tris (dimethylamino) antimony.
  • the present invention also provides a process for the preparation of the stabilized effect pigments according to the invention.
  • the effect pigments to be stabilized are preferably pearlescent pigments, interference pigments, multilayer pigments with transparent, semitransparent and / or opaque layers, holographic pigments.
  • a particularly stabilizing effect is achieved in the case of interference or silver-white effect pigments consisting of a platelet-shaped substrate coated with TiO 2 and / or titanium oxynitride and / or other titanium-containing mixed oxides and optional further layers.
  • effect pigments which have a layer of TiO x N y , with x> 1, 5 and y ⁇ 0.5.
  • the layer of titanium oxynitride may also be a mixture of two or more titanium oxynitrile compounds or other titanium-containing mixed oxides.
  • the titanium oxynitride compounds can be mixed with each other in any ratio.
  • Suitable effect pigments are in particular pearlescent pigments,
  • platelet-shaped TiO 2 synthetic (eg fluorophlogopite) or natural mica, doped or undoped glass platelets, platelet-shaped SiO 2 , platelet-shaped Al 2 O 3 or platelet-shaped iron oxide are suitable.
  • the glass plates may consist of all types of glass known to those skilled in the art, eg A glass, E glass, C glass, ECR glass, waste glass, window glass, borosilicate glass, Duran® glass, Laboratory glass or optical glass.
  • Glass flakes are preferably 1, 45-1, 80, in particular 1, 50-1, 70.
  • the glass substrates of C glass, ECR glass or borosilicate glass.
  • high temperature resistant platelets such as AI2O3, SiC, B 4 C, BN, graphite, TiO 2 and Fe 2 O 3 platelets.
  • Suitable substrate platelets for the pearlescent pigments may be doped or undoped. If they are doped, it is with the
  • Doping preferably by Al, N, B, Ti, Zr, Si, In, Sn, or Zn or mixtures thereof.
  • Other ions can be removed from the group of
  • Transition metals (V, Cr, Mn, Fe, Co, Ni, Cu, Y, Nb, Mo, Hf, Ta, W) and ions from the group of lanthanides serve as dopants.
  • the substrate is preferably undoped or doped with TiO 2 , ZrO 2 or ZnO.
  • the AI 2 O 3 platelets are
  • Suitable Al 2 O 3 platelets are preferably doped or undoped ⁇ -Al 2 O 3 platelets, in particular TiO 2 doped a-Al 2 O 3 platelets. If the substrate is doped, the proportion of doping is preferably 0.01-5% by weight, in particular 0.10-3% by weight, based on the substrate.
  • the size of the carrier substrates is not critical per se and can be tailored to the particular application.
  • the platelet-shaped substrates have a thickness between 0.1 and 5 ⁇ , in particular between 0.2 and 4.5 ⁇ .
  • the extent in the two other areas is usually between 1 and 1000 ⁇ , preferably between 2 and 200 ⁇ , and in particular between 5 and 60 ⁇ .
  • the thickness of the respective layer of metal oxide, metal oxide hydrate, metal suboxide, metal, metal fluoride, metal nitride, metal oxynitride or a mixture thereof is preferably 3 to 300 nm, in particular 20 to 200 nm, on the carrier substrate.
  • the carrier of the carrier of the carrier is preferably 3 to 300 nm, in particular 20 to 200 nm, on the carrier substrate.
  • Effect pigments with one or more transparent, semi-transparent and / or opaque layers containing metal oxides, metal oxide hydrates, metal suboxides, metals, metal fluorides, metal nitrides, metal oxynitrides or mixtures of these materials may be coated.
  • the metal oxide, metal oxide hydrates, metal suboxides, metals, metal fluorides, metal nitrides, metal oxynitrides or mixtures of these materials may be coated.
  • Metal oxide hydrate, metal suboxide, metal, metal fluoride, metal nitride, metal oxynitride layers or mixtures thereof may be low (refractive index ⁇ 1.8) or high refractive index (refractive index> 1.8).
  • Metal oxides and metal oxide are all known in the art metal oxides or metal oxide, such as. Alumina, alumina hydrate, silica, silica hydrate, iron oxide,
  • metal suboxides can be any metal suboxide.
  • the titanium suboxides are used.
  • a metal fluoride for example, magnesium fluoride is suitable.
  • metal nitrides or metal oxynitrides for example, the nitrides or oxynitrides of the metals titanium, zirconium and / or tantalum can be used. Preference is given to metal oxide, metal, metal fluoride and / or metal oxide hydrate layers and very particularly preferably metal oxide and / or
  • Metal oxide hydrate layers applied to the carrier Furthermore, multi-layer constructions of high-refractive and low-refractive index metal oxide, metal oxide hydrate, metal or metal fluoride layers can also be present, alternating preferably high and low refractive index layers. Particularly preferred are layer packages of a high and a low-refractive layer, wherein one or more of these layer packages can be applied to the support. The order of the high- and low-index layers can be adapted to the carrier in order to include the carrier in the multi-layer structure.
  • the metal oxide, metal silicate, metal oxide hydrate, metal suboxide, metal, metal fluoride, metal nitride, metal oxynitride layers may be mixed or doped with colorants.
  • inorganic color pigments such as colored metal oxides, e.g. magnetite,
  • Chromium (III) oxide or colored pigments such as Thenards Blue (a Co-Al Spinel) or elements such as yttrium or antimony, as well as generally pigments from the structural class of perovskites, pyrochlors, rutiles and spinels. Pearlescent pigments containing these layers show a great variety of colors with respect to their body color and in many cases can show an angle-dependent change of color (color flop) due to interference.
  • the outer layer on the support is in a preferred
  • Embodiment of a high refractive index metal oxide may additionally be part of a layer package on the above-mentioned layer packages or, in the case of high-index carriers, for example of TiO 2 , titanium suboxides, Fe 2 O 3 , SnO 2 , ZnO, ZrO 2 , Ce 2 O 3 , CoO, Co 3 O 4 , V 2 O 5, Cr 2 O3 and / or mixtures thereof, such as ilmenite or
  • TiO 2 is particularly preferred, further Fe 2 O 3 . If the carrier platelets are coated with TiO 2 , the TiO 2 is preferably present in the rutile modification, and also in the anatase modification.
  • the processes for producing rutile are known in the art, for example, in US 5,433,779, US
  • a thin tin oxide layer ( ⁇ 10 nm) is applied before the TiO 2 -Avemällung on the substrate platelet, which serves as an additive to convert the TiO 2 in the rutile.
  • effect pigments are known and for the most part commercially available and can be prepared by standard methods known to those skilled in the art.
  • the wet-chemical process is used to prepare the effect pigments, whereby the known wet-chemical coating technologies developed for the preparation of pearlescent pigments can be used, e.g.
  • Particularly preferred effect pigments have the following structure: Subs entplätchen + ⁇ 2
  • high refractive index means a refractive index of> 1.8
  • low refractive index means a refractive index of ⁇ 1.8
  • Suitable aftercoats or after-treatments are, for example, the processes described in DE-PS 22 15 191, DE-OS 31 51 354, DE-OS 32 35 017 or DE-OS 33 34 598.
  • the effect pigments of the invention have increased temperature and heat stability compared to the non-stabilized effect pigments.
  • the stabilized effect pigments can be easily incorporated into engobes and glazes. Depending on the desired effect, the glazes can be matt to glossy or transparent to opaque.
  • the coating of clay, glass and ceramic goods to improve (primer) the surface by fineness or color is usually carried out with ceramic coating compositions.
  • the engobe is generally composed of a glass frit, a binder and possibly a pigment.
  • the engobe generally contains a frit for the firing range of 600 ° to 1200 ° C., the frit being composed of frit components such as Al 2 O 3 , SiO 2 , B 2 O 3 , TiO 2 , ZrO 2 , Sb 2 O 3 , ⁇ 2 ⁇ , Fe 2 O 3 , alkali oxides and alkaline earth oxides composed.
  • frit components such as Al 2 O 3 , SiO 2 , B 2 O 3 , TiO 2 , ZrO 2 , Sb 2 O 3 , ⁇ 2 ⁇ , Fe 2 O 3 , alkali oxides and alkaline earth oxides composed.
  • the frit can also contain inorganic color pigments, for example colored metal oxides and / or metal hydroxides selected from the group consisting of Co, Cr, Cu, Mn, Fe, Zr, V, Al, Ni, Si, Sb, Pr, Ca or CdSSe (Encapsulated) and mixtures thereof, in amounts of 0 to 30 wt.%, Preferably 5 to 20 wt.%, And especially 5 to 15 wt.%, Based on the inorganic
  • the slip slipper may further contain a binder in amounts of from 0 to 70% by weight, preferably from 10 to 60% by weight, in particular from 20 to 50% by weight.
  • a binder in amounts of from 0 to 70% by weight, preferably from 10 to 60% by weight, in particular from 20 to 50% by weight.
  • the choice of binder depends on the technological requirements of the coating to be produced. Suitable binders are in particular all
  • Binder mixtures in particular a screen printing medium.
  • Cellulose nitrate alkylcellulose, hydroxycellulose, hydroxyalkylcellulose ethers, hydroxyalkylcellulose, cellulose acetopropionate, butyrate, polyacrylate, polymethacrylate, polyester, polyphenol, urea, melamine, polyterpene, polyvinyl, polyvinylchloride, polyvinylpyrrolidone resins, Polystyrene and modified polystyrene,
  • Paint binders such as e.g. Polyurethane-acrylate resins, acrylate-melamine resins, alkyd resins, polyester resins, polyurethanes, nitrocellulose, ketone resins, aldehyde resins and polyvinyl butyral, acrylic resins or epoxy resins and mixtures thereof are used as binders.
  • the application may also be carried out without a binder, e.g. dusty, applied.
  • effect pigment and frit powder are dry mixed and applied, e.g. by scattering.
  • the solvent component in the engobe slip has to be adapted to the particular binder, as far as a solvent is needed.
  • Water and all organic solvents preferably those which are emulsifiable or miscible with water, can be used in the preparation.
  • Suitable solvents are those which have hitherto been used in the ceramic coating composition sector, such as pine oil, terpineol, ester alcohol, toluenes, benzines, mineral oils, aliphatic or aromatic hydrocarbons, esters, vegetable oils, aliphatic alcohols, such as those having 2 to 4 carbon atoms, eg Ethanol, butanol, ester alcohols, tridecyl alcohol, isopropanol or ketones, e.g.
  • glycol or glycol ethers e.g. Tripropylene glycol methyl ether, propylene glycol monoethyl ether or diols, e.g. Ethylene glycol and propylene glycol or polyether diols, e.g. Polyethylene glycol and polypropylene glycol or polyols, e.g.
  • triols and tetrols having 2 to 6 carbon atoms such as trimethylolethane, trimethylolpropane, glycerol, 1, 2,4-butanetriol, 1, 2,6-hexanetriol and pentaerythritol, and all other solvents of other classes of compounds or of the mixtures of the abovementioned solvents ,
  • solvents are used in Karsten, Lackrohstofftabellen, 8th edition
  • the engobe usually contains 0 to 90% by weight of water and / or of an organic solvent or solvent mixture, preferably 5 to 80 wt.%, In particular 20 to 70 wt.%, Based on the
  • the slip slip may contain up to 15% by weight, preferably 0.1 to 5% by weight, of one or more viscosity modifiers.
  • Such modifiers are also known in the art and examples thereof include ethylcellulose, nitrocellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, acrylic resins, poly (vinyl) butyral resins, carboxymethylcellulose, and ethylhydroxyethylcellulose.
  • the engobe slip may also contain other modifying ingredients, such as e.g. Dispersants, wetting agents, anti-settling agents, leveling agents, etc.
  • Dispersants e.g. Dispersants, wetting agents, anti-settling agents, leveling agents, etc.
  • the Engobeschlicker containing the frit optionally further
  • Additives, colorants or color pigments is milled to a fineness of 0.1-300 ⁇ , preferably 10-20 ⁇ , preferably wet ground. Finally, the effect pigment is mixed in.
  • the finished engobe slip can be applied to brick, clay, glass or ceramic surfaces using the usual application methods such as spraying, brushing, flooding or dipping. The order can be on burnt or unburnt bricks, burned or unburnt clay and
  • Ceramic goods take place.
  • unfired products are provided with the engobe slip. Subsequently, the applied
  • Engobeschlicker dried preferably 0.5-5 h at 50-200 ° C.
  • the coated product is fired for several hours, preferably at 400-1200 ° C for 2-48 hours.
  • the engobe containing the effect pigment according to the invention gives coatings of pottery, eg unfired roof tiles and ceramics, such as tiles, tiles, significantly improved optical properties in terms of color and gloss and possibilities for new interesting color accents.
  • the effect pigments according to the invention are furthermore suitable for the preparation of flowable pigment preparations and
  • Dry preparations in particular for printing inks and varnishes,
  • Pigments Pigments, binders and optionally one or more additives.
  • the invention furthermore relates to the use of the effect pigments according to the invention in paints, lacquers, printing inks, plastics, ceramic materials, glasses, for the laser marking of plastics and papers, and in cosmetic formulations, in particular in US Pat
  • the pigments according to the invention are also suitable for the preparation of pigment preparations and for the preparation of
  • Dry preparations e.g. Granules, chips, pellets, briquettes, etc.
  • the dry preparations are especially for paints and
  • the invention thus also relates to formulations containing the effect pigment of the invention.
  • the following examples are intended to illustrate the invention without, however, limiting it.
  • Example 1 100 g of Iriodin 103 ® (TiO2 mica pigment Fa. Merck) were stirred in 2 I demineralized water and heated to 70 ° C. This is followed by the metered addition of 60 g of a 32% antimony-chloride solution, wherein the pH of 4.5 is kept constant by simultaneous dropwise addition of a 32% sodium hydroxide solution. After complete addition, stirring is continued for 30 min. The product is filtered off, washed, dried at 110 ° C. for 10 hours and then calcined at 850 ° C. for 30 minutes. Subsequently, a screening takes place.
  • Iriodin 103 ® TiO2 mica pigment Fa. Merck
  • a white-bodied effect pigment with high gloss is obtained, which has the following particle size distribution:
  • the effect pigment of Example 2 is stable at temperatures> 1 100 ° C.
  • a white-body-colored effect pigment with very high gloss and a strongly intense glittering effect is obtained, which has the following particle size distribution:
  • the effect pigment from Example 3 is stable at temperatures> 1000 ° C.
  • a white-bodied effect pigment with high gloss is obtained, which has the following particle size distribution:
  • the effect pigment from Example 4 is stable at temperatures> 1000 ° C.
  • the effect pigment from Example 5 is stable at temperatures> 1000 ° C.
  • Iriodin ® 100 (mica flakes coated with ⁇ 2, effect pigment of Messrs. Merck) were stirred in 2 I demineralized water and heated to 70 ° C. This is followed by metering in 60 g of a 32% strength antimony chloride solution, the pH of 4.5 being kept constant by simultaneous dropwise addition of a 32% sodium hydroxide solution. After complete addition, stirring is continued for 30 min. The product is filtered off, washed, dried at 110 ° C. for 10 hours and then calcined at 1000 ° C. for 30 minutes. Subsequently, a screening takes place.
  • a white-bodied effect pigment with high gloss is obtained, which has the following particle size distribution:
  • the effect pigment from Example 6 is stable at temperatures> 1000 ° C.
  • Example 7 100 g of Iriodin ® 123 (mica flakes coated with ⁇ 2, effect pigment of Messrs. Merck) were stirred in 2 I demineralized water and heated to 70 ° C. This is followed by the metered addition of 60 g of a 32% tin IV-antimony-lll-chloride solution, wherein the pH value of 4.5 by
  • a white-body-colored effect pigment with a moderate gloss and sparkle effect is obtained, which has the following particle size distribution:
  • the effect pigment from Example 7 is stable at temperatures> 1000 ° C.
  • Iriodin ® 6163 synthetic mica platelets coated with ⁇ 2, effect pigment of Messrs. Merck
  • the suspension is heated to 85 ° C.
  • This is followed by the metered addition of 55 g of a 32% antimony-l chloride solution, wherein the pH of 4.5 is kept constant by simultaneous dropwise addition of a 32% sodium hydroxide solution.
  • stirring is continued for 30 min.
  • the product is filtered off, washed, dried at 110 ° C. for 12 hours and then calcined at 850 ° C. for 45 minutes. Subsequently, a screening takes place.
  • a white-body-colored effect pigment having a high gloss and a high sparkle effect is obtained, which has the following particle size distribution:
  • Example 9 The effect pigment from Example 8 is stable at temperatures> 1000 ° C.
  • the effect pigment from Example 9 is stable at temperatures> 1000 ° C.
  • Example 10 The effect pigment from Example 10 is stable at temperatures> 1000 ° C.
  • Pigments are each determined by the application specific test in
  • the non-stabilized pigment for example, Iriodin ® 103 in Example 1
  • the respective stabilized pigment in the same manner and evaluated the two workpieces visually with regard to their color and their pearlescent effect.
  • the stabilized pigments each show a lower discoloration and a better pearlescent effect in comparison to the corresponding commercial or non-stabilized effect pigment.
  • screen-printing oils are used which prevent bleeding of the color pastes after printing and produce contour-sharp prints.
  • additives are used to the known binders, which consist of finely divided natural or artificial waxes and / or finely divided, incorporated into the silicate framework of the flux, when burning, inorganic silicate or oxidic substances.
  • the pearlescent pigment with the appropriate amount of frit and the pressure medium (in the
  • the effect pigment according to Examples 1 to 10 is with the
  • the subsequent steps are independent of the composition of the printing paste.
  • the printing paste obtained can be printed by conventional printing methods,
  • the printing paste is applied to the tiles by means of a squeegee and printing screen.
  • the printed and dried tile is now fired in the kiln by means of a temperature profile.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Paints Or Removers (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Cosmetics (AREA)

Abstract

La présente invention concerne des pigments à effet stables à la glaçure et à l'émaillage, dotés d'une couche de recouvrement en oxyde d'antimoine ou mélange d'oxyde d'antimoine, les pigments à effet présentant une stabilité améliorée, notamment à des températures supérieures à 1000 °C dans des glaçures, des émaux ou des matériaux céramiques ou vitreux.
EP18712176.9A 2017-03-17 2018-03-16 Pigments à effets Withdrawn EP3596170A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102017002554.1A DE102017002554A1 (de) 2017-03-17 2017-03-17 Effektpigmente
PCT/EP2018/056662 WO2018167268A1 (fr) 2017-03-17 2018-03-16 Pigments à effets

Publications (1)

Publication Number Publication Date
EP3596170A1 true EP3596170A1 (fr) 2020-01-22

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Country Status (6)

Country Link
EP (1) EP3596170A1 (fr)
JP (1) JP2020514511A (fr)
CN (1) CN110402273A (fr)
DE (1) DE102017002554A1 (fr)
TW (1) TW201902847A (fr)
WO (1) WO2018167268A1 (fr)

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WO2024017885A1 (fr) 2022-07-19 2024-01-25 Sun Chemical Corporation Pigments à effets avec brillance

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CN113717549A (zh) * 2021-09-30 2021-11-30 福建坤彩材料科技股份有限公司 绿色珠光颜料及其制备方法与应用
CN115304275B (zh) * 2022-05-09 2023-11-17 承德石油高等专科学校 一种适于超临界水中应用的复合绝缘釉及其加工方法
CN116395969B (zh) * 2023-05-24 2025-09-30 佛山欧神诺陶瓷有限公司 一种闪光陶瓷干粒釉、陶瓷砖及其制备方法

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WO2024017885A1 (fr) 2022-07-19 2024-01-25 Sun Chemical Corporation Pigments à effets avec brillance

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CN110402273A (zh) 2019-11-01
DE102017002554A1 (de) 2018-09-20
WO2018167268A1 (fr) 2018-09-20
TW201902847A (zh) 2019-01-16

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