WO2016097416A1 - Effektpigmente mit hoher transparenz, hohem chroma und hoher brillanz, verfahren zu ihrer herstellung und verwendung derselben - Google Patents

Effektpigmente mit hoher transparenz, hohem chroma und hoher brillanz, verfahren zu ihrer herstellung und verwendung derselben Download PDF

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Publication number
WO2016097416A1
WO2016097416A1 PCT/EP2015/080859 EP2015080859W WO2016097416A1 WO 2016097416 A1 WO2016097416 A1 WO 2016097416A1 EP 2015080859 W EP2015080859 W EP 2015080859W WO 2016097416 A1 WO2016097416 A1 WO 2016097416A1
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Prior art keywords
layer
metal
metal oxide
effect pigment
transparent effect
Prior art date
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Ceased
Application number
PCT/EP2015/080859
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German (de)
English (en)
French (fr)
Inventor
Michael GRÜNER
Günter KAUPP
Ralph Schneider
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.)
Eckart GmbH
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Eckart GmbH
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Application filed by Eckart GmbH filed Critical Eckart GmbH
Priority to EP15813863.6A priority Critical patent/EP3234023B1/de
Priority to KR1020177018329A priority patent/KR102535159B1/ko
Priority to JP2017533484A priority patent/JP6957351B2/ja
Priority to US15/536,206 priority patent/US10934436B2/en
Priority to CN201580068744.XA priority patent/CN107109079B/zh
Publication of WO2016097416A1 publication Critical patent/WO2016097416A1/de
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/0015—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • 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
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/0241—Containing particulates characterized by their shape and/or structure
    • A61K8/0254—Platelets; Flakes
    • A61K8/0258—Layered structure
    • A61K8/0262—Characterized by the central layer
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/25—Silicon; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
    • A61Q1/02—Preparations containing skin colorants, e.g. pigments
    • A61Q1/10—Preparations containing skin colorants, e.g. pigments for eyes, e.g. eyeliner, mascara
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
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    • 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
    • C09C1/0009—Pigments for ceramics
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/20—Chemical, physico-chemical or functional or structural properties of the composition as a whole
    • A61K2800/26—Optical properties
    • A61K2800/262—Transparent; Translucent
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/42—Colour properties
    • A61K2800/43—Pigments; Dyes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01P2002/52—Solid solutions containing elements as dopants
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    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
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    • C01P2004/52—Particles with a specific particle size distribution highly monodisperse size distribution
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    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
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    • 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
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    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
    • C01P2006/64—Optical properties, e.g. expressed in CIELAB-values b* (yellow-blue axis)
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    • C01—INORGANIC CHEMISTRY
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    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
    • C01P2006/65—Chroma (C*)
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    • 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
    • C09C2200/10—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
    • C09C2200/1033—Interference pigments characterized by the core material the core consisting of glass or silicate material like mica or clays, e.g. kaolin comprising an intermediate layer between the core and a stack of coating layers having alternating refractive indices
    • C—CHEMISTRY; METALLURGY
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    • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/10—Interference pigments characterized by the core material
    • C09C2200/1087—Interference pigments characterized by the core material the core consisting of bismuth oxychloride, magnesium fluoride, nitrides, carbides, borides, lead carbonate, barium or calcium sulfate, zinc sulphide, molybdenum disulphide or graphite
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    • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/20—Interference pigments comprising a layer with a concentration gradient or a gradient of the refractive index
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    • 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
    • C09C2200/301—Thickness of the core
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    • 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
    • C09C2200/302—Thickness of a layer with high refractive material
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    • 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
    • C09C2200/304—Thickness of intermediate layers adjacent to the core, e.g. metallic layers, protective layers, rutilisation enhancing layers or reflective layers
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    • 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
    • C09C2200/305—Thickness of intermediate layers within the stack
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    • 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
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    • 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
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    • 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 present invention relates to transparent effect pigments comprising a non-metallic platelet-shaped substrate and a coating applied thereto, wherein the coating comprises at least one spacer layer, a method for producing the transparent
  • Multilayer pigments which comprise at least one layer sequence of alternately high, low, and high refractive index layers based on a non-metallic platelet-shaped substrate are described, for example, in EP 1 572 812 A1, EP 1 213 330 A1, EP 1 025 168 B2, EP 1 621 585 A2 , EP 0 948 572 A1, EP 0 950 693 A1, EP 1 306 412 A1, EP 1 587 881 A2, EP 2 632 988 A1 or EP 1 474 486 A2.
  • the multi-layered pigments may exhibit a strong color change depending on the viewing angle, e.g.
  • Multilayered pigments are distinguished from monolayered effect pigments with only a single identical first layer by a higher gloss and, if appropriate, by a higher chroma, the same substrate and the same particle size being used here
  • EP 1 422 268 A2 discloses a pigment having a multilayer structure, said pigment having two or more metal oxide layers, wherein said at least one metal (ion) of said metal oxide layer is selected from the group consisting of cerium, tin, titanium, iron, zinc and zirconium; is selected.
  • the aim of this application are highly chromatic and highly brilliant pigments, which in their
  • a small pore volume should, according to EP 1 422 268 A2, ensure an optically high-quality coating.
  • US 2015/0344677 A1 relates to effect pigments based on coated platelet-shaped substrates.
  • the coating comprises a first and a second high-index layer and a third component which is intended to partially or completely diffuse into one or both of the high-index layers.
  • the third component may be Si0 2 or another Metal oxide act.
  • the aim of this application is to obtain an Si0 2 population without agglomeration in the case of effect pigments having a D 50 value of 15 ⁇ m or less.
  • Object of the present invention is to provide a highly chromatic pigment with high gloss available, which has no or the lowest possible absorption color, high mechanical stability and high chemical stability and at the same time with low material usage in a simple manner can be produced.
  • a layer 2 comprising at least one metal oxide, metal hydroxide and / or
  • a layer 3 comprising at least one metal oxide, metal hydroxide and / or
  • the layers 2 or 3 contains at least two different metal ions and the layers 2 and 3 are interrupted by a spacer layer.
  • Distance position are spaced from each other or kept at a distance.
  • metal oxide, metal hydroxide and / or metal oxide hydrate By the general term “metal oxide, metal hydroxide and / or metal oxide hydrate” according to the invention is meant “metal oxide and / or metal hydroxide and / or metal oxide”. This is true even if the metal or metal ion is specified, for example, as titanium (ion), iron (ion), tin (ion), zirconium (ion), etc.
  • a metal ion is meant according to the invention not a single metal ion but a plurality of metal ions.
  • the optional layer 1 lies directly on the non-metallic platelet-shaped substrate, the layer 2 directly follows the layer 1 and the layer 3 follows the layer 2, wherein the layers 2 and 3 are interrupted by a spacer layer.
  • the layer 2 lies directly on the non-metallic platelet-like substrate and the layer 3 follows the layer 2, wherein the layers 2 and 3 are interrupted by a spacer layer.
  • the object is achieved by providing a method for producing the transparent effect pigment according to the invention, the method comprising the following steps:
  • step (iii) calcining the product obtained in step (ii) at a temperature in the range of 600 ° C to 1000 ° C to obtain the transparent effect pigment comprising at least one spacer layer.
  • the object is achieved by providing a method for producing the
  • dissolved transparent effect pigment according to the invention, the method comprising the following steps:
  • step (ii) calcining the product obtained in step (i) at a temperature in the range of 600 ° C to 1000 ° C to obtain the transparent effect pigment comprising at least one spacer layer.
  • the invention furthermore relates to the use of the transparent effect pigment according to the invention in cosmetic formulations, plastics, films, textiles, ceramic materials, glasses, paints, printing inks, inks, paints, powder coatings and / or in functional applications, for example for laser marking, IR reflection , Photocatalysis.
  • the object underlying the invention is further achieved by providing an article, wherein the article has at least one inventive transparent effect pigment.
  • the non-metallic platelet-shaped substrates to be coated according to the invention are preferably transparent, ie they are at least partially permeable to visible light. Under partially permeable is understood according to the invention that the coverage quotient D q , defined
  • L dß preferably at ⁇ 0.35, more preferably at ⁇ 0.28, more preferably at ⁇ 0.22 and most preferably at ⁇ 0.20.
  • the coverage quotient here is based on lacquer applications on black and white cover cards (Byko-Chart 2853, Byk-Gardner) of a nitrocellulose lacquer mixed with 10% by weight of the respective substrate (Erco bronze mixed enamel 2615e colorless, Maeder Kunststofflack AG). according to llc
  • L * warz 25 SCh or L * 25 we i ß are under a measurement angle of 25 ° on black or white background of black and white coverage card, preferably with the multi-angle colorimeter BYK-mac of Fa. Byk-Gardner, measured brightness values.
  • the non-metallic platelet-shaped substrates may be selected from the group consisting of natural mica flakes, synthetic mica flakes, glass flakes, Si0 2 flakes, Al 2 O 3 flakes, kaolin flakes, talc flakes, and bismuth oxychloride flakes.
  • the transparent effect pigments can also be based on mixtures of the above-mentioned non-metallic platelet-shaped substrates.
  • the abovementioned non-metallic platelet-shaped substrates can also have one or more layers of or with at least one high and / or low refractive index metal oxide, metal hydroxide and / or metal oxide hydrate and be calcined.
  • the substrates to be used according to the invention are uncoated, non-metallic platelet-shaped, substantially transparent, preferably transparent, substrates.
  • the non-metallic platelet-shaped substrates are selected from the group consisting of natural mica platelets, synthetic mica platelets, glass platelets, Si0 2 platelets, Al 2 0 3 platelets and mixtures thereof. Particularly preferred are the
  • non-metallic platelet-shaped substrates from the group consisting of natural
  • Mica flakes, synthetic mica flakes, glass flakes and mixtures thereof are preferred as the non-metallic flake-form substrate.
  • the glass flakes usable as the substrate may be composed of silicate glass such as soda lime glass, lead crystal glass, E glass, A glass, C glass, ECR glass, Durang glass, window glass, laboratory glass, aluminosilicate glass or borosilicate glass.
  • the glass platelets preferably have a composition according to the teaching, in particular corresponding to the main claim, EP 1 980 594 B1, particularly preferably according to the teaching, in particular corresponding to the respective main claim, EP 1 829 833 B1 or EP 2 042 474 B1.
  • the production of the glass flakes which can be used as a substrate is preferably carried out by the process described in EP 289 240 B1.
  • the glass flakes can be selectively colored by the addition of at least one inorganic colorant during their preparation.
  • Colorants are those which do not decompose at the respective melting temperature of the glass composition.
  • the proportion of colorant is in this case preferably in a range from 0.1% by weight to 20% by weight, more preferably in a range from 0.2% by weight to 15% by weight and very particularly preferably in a range from 0.5% to 10% by weight in total, based in each case on the total weight of the glass composition.
  • Suitable colorants are in particular elemental noble metals, such as Au, Pd or Pt, the cations or complex anions of the elements Cu, Cr, Mn, Fe, Ti and / or Co and mixtures of the colorants listed above.
  • the refractive index of the usable as a substrate is in particular elemental noble metals, such as Au, Pd or Pt, the cations or complex anions of the elements Cu, Cr, Mn, Fe, Ti and / or Co and mixtures of the colorants listed above.
  • Glass flakes in a range of 1.45 to 1.80, preferably in a range of 1.50 to 1.70.
  • the platelet-shaped substrates in particular glass platelets, may be enveloped by a layer comprising or consisting of silicon oxide, silicon hydroxide, silicon oxide hydrate.
  • a layer comprising or consisting of silicon oxide, silicon hydroxide, silicon oxide hydrate.
  • the synthetic mica platelets usable as a substrate may have a composition according to the main claim of CN 102718229 A or according to the main claim of
  • the synthetic mica flakes which can be used as the substrate are preferably fluorophlogopite of the formula KMg 3 AISi 3 OioF 2 , KMg 2 1 / (Si 4 Oi 0 ) F 2 or NaMg 2 1 / (Si 4 Oi 0 ) F 2 , in particular Fluorophlogopite of the formula KMg 3 AISi 3 OioF 2 , which according to
  • X-ray fluorescence analysis preferably comprises the components listed in Table 1 as the respective metal oxide in the areas listed there.
  • Table 1 Preferred compositions of synthetic mica platelets according to RFA
  • the average thickness of the non-metallic platelet-shaped substrates to be coated is preferably in a range of 50 nm to 5000 nm, more preferably in a range of 60 nm to 3000 nm, and most preferably in a range of 70 nm to 2000 nm. Below the average thickness According to the invention, the arithmetic mean is understood, unless stated otherwise.
  • the average thickness for glass flakes as the non-metallic platelet substrate to be coated ranges from 750 nm to 1500 nm, preferably from 850 nm to 1400 nm, and more preferably from 900 nm to 1300 nm.
  • Thinner platelet Substrates lead to a lower overall thickness of the transparent effect pigments according to the invention.
  • glass platelets whose average thickness is in a range from 50 nm to 700 nm, more preferably in a range from 101 nm to 600 nm, particularly preferably in one, are likewise preferred Range of 160 nm to 500 nm and most preferably in a range 200 nm to 400 nm.
  • the average thickness of the natural or synthetic mica platelets as the non-metallic platelet-shaped substrate to be coated is preferably in a range of 80 nm to 1300 nm, more preferably in a range of 90 nm to 1000 nm, particularly preferably in a range of 99 nm to 800 nm and most preferably in a range of 200 nm to 600 nm.
  • Coating non-metallic platelet-shaped substrates below an average thickness of 50 nm with, for example, high refractive index metal oxides extremely fragile pigments are obtained, which already incorporated into the respective Application medium can break, which in turn causes a significant reduction in gloss. Above a mean substrate thickness of 5000 nm, the pigments as a whole may become too thick.
  • the relative standard deviation of the thickness distribution of the non-metallic platelet-shaped substrates is 15% to 100%, preferably 17% to 70%, more preferably 19% to 61% and most preferably 21% to 41%.
  • Standard deviation in [%] is the quotient of calculated standard deviation and average thickness.
  • platelet-shaped transparent substrate determined by at least 100 effect pigments and is averaged statistically.
  • average according to the invention is always meant the arithmetic mean unless otherwise stated.
  • the transparent effect pigments according to the invention optionally comprise a layer 1 which comprises or consists of tin oxide, tin hydroxide and / or tin oxide hydrate.
  • the layer 1 may optionally be present at least partially as a mixed layer with a layer directly adjacent to the layer 1, for example the layer 2.
  • the layers 2 and 3 of the transparent effect pigments according to the invention are preferably high-index layers or in each case a high-index layer whose refractive index is preferably n> 1, 8, particularly preferably n> 1, 9 and very particularly preferably > 2.1.
  • metal ions in the layers 2 and / or 3 are carried out such that the metal oxide (s), metal hydroxide (s) and / or metal oxide hydrate (e) formed in the layers 2 or 3 preferably each have an average refractive index of n> 1, 8 or have.
  • the at least one metal oxide, metal hydroxide and / or metal oxide hydrate of layers 2 or 3 comprises at least two different metal ions, preferably selected from the group of metals consisting of Ti, Fe, Sn, Mn, Zr, Ca, Sr, Ba, Ni, Sb , Ag, Zn, Cu, Ce, Cr and Co, more preferably selected from the group of metals consisting of Ti, Fe, Sn, Mn, Zr, Ag, Zn, Cu and Ce, more preferably selected from the group of metals consisting of Ti, Fe, Sn, Ag, Zr and Ce, and most preferably selected from the group of metals consisting of Ti, Fe and Sn.
  • the selection of the at least two takes place here
  • Coverage quotient here is based on lacquer applications on black and white cover cards (Byko-Chart 2853, Byk-Gardner) of a nitrocellulose lacquer mixed with 6% by weight of the respective effect pigment according to the invention (Erco bronze mixed enamel 2615e colorless, Maeder Kunststofflack AG). determined in accordance with the following information in section llc "Coverage comparison".
  • the weight ratio of non-coloring metal ions to be colored metal ions in the transparent effect pigment according to the invention is preferably> 6, more preferably> 8 and most preferably> 10.
  • Coloring metal ions from the group of metals Ti and Sn relate in particular to Ti of the oxidation state +3 or +2 and Sn of the oxidation state +2.
  • the at least two different metal ions are preferably either homogeneously distributed in the layers 2 and / or 3 or form a gradient therein. In exceptional cases, the at least two different metal ions can also be inhomogeneously distributed in the
  • At least two different metal ions is meant according to the invention that at least two metal ions of different elements are present, for example titanium and
  • the various metal ions may be present in a mixture of metal oxides and / or metal hydroxides and / or metal oxide hydrates and / or in mixed oxides and / or mixed hydroxides and / or mixed oxide hydrates in layer 2 and / or layer 3 of the transparent effect pigment according to the invention.
  • the layer 2 and / or layer 3 this mixture of metal oxides and / or metal hydroxides and / or
  • Metal oxide hydrates and / or mixed oxides and / or mixed hydroxides and / or Mischoxidhydraten include or consist of.
  • the iron ion-containing portion of the respective layer is present as iron titanate, preferably as pseudobrookite and / or pseudorutil.
  • one of the two layers 2 or 3 comprises only one type of metal ion, preferably selected from the group of metals consisting of Ti, Sn, Zr and Zn, more preferably consisting of Ti, Sn and Zr.
  • the respective other of the two layers 3 or 2 has at least two different metal ions, preferably selected from the group of metals consisting of Ti, Sn, Zr and Zn, more preferably consisting of Ti, Sn and Zr.
  • both the layer 2 and the layer 3 comprise at least one metal oxide, metal hydroxide and / or metal oxide hydrate, the metal ions of the at least one metal oxide, metal hydroxide and / or metal oxide hydrate comprising at least two different metal ions, preferably selected from the group of metals, consisting of Ti, Sn, Zr and Zn, more preferably consisting of Ti, Sn and Zr, comprise or are.
  • the layers 2 and 3 interrupted by the spacing layer are identical with respect to the respective composition.
  • the transparent effect pigments according to the invention comprise at least one coloring metal ion selected from the group of metals consisting of Fe, Ti, Sn, Mn, Cu, Cr, Co, Ag and Ce, their proportion is determined in each case by means of RFA and in each case calculated as elemental metal, preferably at a total of ⁇ 4% by weight, more preferably in a range from 0.1% by weight to 3.4% by weight, particularly preferably in a range of 0.2% by weight in total to 3.7 wt .-% and most preferably in a range of from 0.3 wt .-% to 2.8 wt .-%, in each case based on the total weight of the transparent effect pigment.
  • the coloring metal ion selected from the group of metals consisting of Fe, Ti, Sn, Mn, Cu, Cr, Co, Ag and Ce
  • At least one of the layers 2 or 3 comprises at least two different metal ions selected from the group of metals consisting of Ti, Fe, Sn, Mn, Zr, Ca, Sr, Ba, Ni, Sb, Ag, Zn. Cu, Ce, Cr and Co, wherein at least one of these two metal ions is selected from the group of metals consisting of Ti, Sn, Zr and Zn and wherein the proportion of coloring metal ions selected from the group of metals consisting of Fe, Ti, Sn, Mn, Cu, Cr, Co, Ag and Ce, in each case determined by means of RFA and in each case calculated as elemental metal, preferably at a total of ⁇ 4 wt .-%, based on the total weight of the transparent effect pigment according to the invention.
  • At least one of the layers comprises 2 or 3 metal oxides, metal hydroxides and / or metal oxide hydrates, wherein the metal ions of the metal oxides, metal hydroxides and / or metal oxide hydrates include or are the metals Ti and Fe, wherein the Weight ratio of Ti to Fe, each determined by RFA and each calculated as elemental metal, preferably at> 6, more preferably> 12, more preferably> 48 and most preferably> 96, and wherein the proportion of Fe, determined by RFA and calculated as elemental metal, preferably at ⁇ 4 wt .-%, based on the total weight of the transparent effect pigment according to the invention is.
  • At least one of the layers 2 or 3 comprises metal oxides, metal hydroxides and / or metal oxide hydrates, wherein the metal ions of the metal oxides, metal hydroxides and / or metal oxide hydrates comprise or are the metals Ti and Sn, wherein the weight ratio of Ti to Sn, in each case determined by means of RFA and in each case calculated as elemental metal, preferably> 2, more preferably> 4, particularly preferably> 5 and very particularly preferably> 6, and the proportion of Sn, determined by means of RFA and calculated as elemental Metal, preferably from a range of 1 wt .-% to 25 wt .-%, more preferably from a range of 2 wt .-% to 19 wt .-%, more preferably from a range of 4 wt .-% to 17 Wt .-%, more preferably from a range of 7 wt .-% to 14 wt .-%, particularly preferably from a range of 10
  • the metal oxide, metal hydroxide and / or metal oxide hydrate contents of the transparent effect pigments according to the invention are determined as the respective metal oxide by means of X-ray fluorescence analysis (RFA) and can be calculated as the respective elemental metal.
  • RFA X-ray fluorescence analysis
  • the transparent effect pigment is incorporated into a lithium tetraborate glass tablet, in
  • the average layer thickness of the layer 1 is preferably less than 10 nm, particularly preferably less than 5 nm and very particularly preferably less than 3 nm, wherein the layer 1 completely envelopes or does not completely envelop the nonmetallic platelet-shaped substrate or an optionally present coating.
  • Each of the effect pigments is preferably in a range from 30 nm to 300 nm, more preferably in a range from 35 nm to 250 nm, particularly preferably in a range from 40 nm to 230 nm and very particularly preferably in a range from 50 nm up to 180 nm.
  • the average layer thickness of the layers 2 and 3 is almost equal.
  • a "virtually equal average layer thicknesses” is understood to mean that the quotient of the average layer thickness of the layer 2 and the mean layer thickness of the layer 3 is preferably in a range from 0.5 to 1.8, more preferably in a range from 0, 7 to 1, 6, particularly preferably in a range from 0.8 to 1.4, and very particularly preferably in a range from 0.9 to 1.2
  • the optical layer thickness of the layers 2 and 3 may or may not follow the known Lambda / 4.
  • the optical layer thickness is defined as the product of refractive index and average layer thickness of the respective layer.
  • the average layer thickness of the entire coating of the transparent effect pigments according to the invention is preferably ⁇ 750 nm.
  • the average layer thickness of the entire coating is preferably in a range from 50 nm to 550 nm, particularly preferably in a range from 78 nm to 430 nm and very particularly preferably in a range of 95 nm to 340 nm.
  • Total coating is understood as meaning the complete coating extending perpendicularly from the substrate surface in one direction.
  • the relative standard deviation of the layer thickness distribution of layers 2 and 3 is 2% to 74%, preferably 3% to 63%, more preferably 4% to 57%, and most preferably 5% to 49%, and relative
  • Standard deviation of the coating thickness distribution of the entire coating 0.3% to 31%, preferably from 1% to 27%, particularly preferably from 1.2% to 24% and very particularly preferably from 1.9% to 22%.
  • the relative standard deviation in [%] is the quotient of calculated
  • the spacing between the layers 2 and 3 is preferably arranged substantially parallel to the surface of the non-metallic platelet-shaped substrate.
  • substantially parallel is meant in the context of this invention that in one
  • scanning electron microscopic cross-section recording a regression line laid through a spacer layer with respect to a level of regression placed on the surface of the non-metallic platelet-shaped substrate has a slope of preferably close to zero.
  • the position of the spacer layer within the entire coating may vary. For example, if the average layer thicknesses of the layers 2 and 3 are almost identical, then the distance position, with respect to the entire coating, is approximately in the middle of the entire
  • Coating preferably of optional layer 1 and the layers 2 and 3, since the optional layer 1 is preferably extremely thin, more preferably only a few atomic layers thick.
  • the spacing layer is preferably arranged, with respect to the entire coating, preferably of optional layer 1 and the layers 2 and 3, between the first sixth and the sixth sixth of the entire coating.
  • the first sixth indicates the proportion of the entire coating facing away from the non-metallic platelet-shaped substrate and the sixth sixth of the non-metallic platelet-shaped substrate, preferably of optional layer 1 and layers 2 and 3 (FIG. 7).
  • the spacer layer formed between the layers 2 and 3 preferably has connections, which may also be referred to as spacers, which connect the layers adjoining on both sides of the spacer layer to one another and at a distance from one another.
  • these compounds or spacers e.g. in the form of webs, which may also be referred to as columns, be arranged at an angle of about 90 °, for example from 80 ° to 100 °, to the surface of the non-metallic platelet-shaped substrate. But you can also take any other angle between 5 ° and 175 °.
  • the spacers in particular webs, preferably the longitudinal axes of the spacers, preferably webs, at an angle from a range of 15 ° to 150 ° and more preferably at an angle from a range of 35 ° to 135 °, respectively to the surface of the non-metallic platelet-shaped substrate arranged.
  • the angle the angle
  • Substrate plane the first leg.
  • One of the outsides of each considered bridge forms the second leg.
  • the compounds or spacers can assume different geometric shapes and are preferably distributed uniformly over the entire spacer layer.
  • the compounds or spacers can be reticulated, grid-like, ladder-like, sponge-like or
  • honeycomb shape present.
  • structural elements which are similar to those in a photonic or inverse photonic crystal, as known, for example, from EP 2 371 908 A2, EP 1 546 063 A1 or EP 1 121 334 A1.
  • the compounds or spacers comprise at least one metal oxide, metal hydroxide and / or metal oxide hydrate.
  • the compounds or spacers comprise an identical material composition as the layers located on both sides of the spacer layer. Also, alternatively, within the connections or
  • Spacer may be a gradient formed between different metal oxides, metal hydroxides and / or metal oxide.
  • the compounds or spacers comprise a metal oxide, metal hydroxide and / or metal oxide hydrate, wherein the metal ions of the metal oxides, metal hydroxides and / or metal oxide hydrates at least two metal ions selected from the group of metals consisting of Ti, Fe, Sn, Mn , Zr, Ca, Sr, Ba, Ni, Ag, Zn, Cu, Ce, Cr and Co, more preferably from the group consisting of Ti, Fe, Sn, Mn, Zr, Ag, Zn, Cu and Ce, especially preferably from the group consisting of Ti, Fe, Sn, Zr, Ag and Ce, and most preferably from the group consisting of Ti, Fe and Sn, comprise or are.
  • the entire coating preferably of optional layer 1 and layers 2 and 3, and the non-metallic
  • platelet-containing substrate is very good in the transparent effect pigments according to the invention. Even extreme shear conditions, such as those that occur in the so-called Waring Blender test, survive the transparent effect pigments of the invention without detectable
  • the spacing of the transparent effect pigments of the invention preferably has a mean height h a from a range of 5 nm to 120 nm, more preferably from a range of 10 nm to 105 nm, further preferably from a range of 16 nm to 90 nm, more preferably from a range of 21 nm to 76 nm, more preferably from a range of 22 nm to 67 nm and most preferably from a range of 26 nm to 60 nm ( Figure 6).
  • the upper and lower substrate surfaces are each used as a baseline on the basis of scanning electron micrographs.
  • the upper and lower substrate surface in the scanning electron micrograph cross section recording in each case the longer side of the
  • the baseline will be in the
  • Image processing software Axio Vision 4.6.3. (Zeiss) examined. In the 90 ° angle to the upper and lower base line, which correspond to the two surfaces of the platelet-shaped substrate, are drawn in 50 nm distance as many parallel lines that on the in the
  • a grid of scanning electron micrographs is shown ( Figure 4).
  • the magnification of the scanning electron micrograph is preferably at least 50,000 times, based on Polaroid 545 (4 " ⁇ 5").
  • the layer thicknesses of the layers 2 and 3 result by subtraction.
  • the layer thickness of the layer 2 results from the difference between the respective measured intersection points at the respective boundary layer 2 to the spacer layer and either the optional layer 1 to layer 2 or the base line to layer 2, provided that the non-metallic platelet-shaped substrate is not pre-occupied with further layers.
  • the layer thickness of the layer 3 results from the difference of the respective measured intersections of the layer 3 to the environment or any further applied layer and the distance to the layer 3.
  • the layer thickness of the entire coating results from the difference of the respective intersections of the layer 3 Environment or any further applied layer to the environment and the respective baseline.
  • the height h a of the distance position results from the difference of the respective measured intersection points
  • the respective arithmetic average values are formed, in order to determine the values given above, the average layer thicknesses, or the average height h a.
  • the measurements described above will be at least 100% perpendicular to the baselines
  • the height h ma denotes the center of the distance position. It is the sum of the
  • the relative height h Rma of the center of the distance position is formed by the ratio of h ma and
  • the standard deviation of the relative height OH Rma is preferably in a range of 0.2% to 18%, more preferably in a range of 0.3% to 15%, more preferably in a range of 0.4% to 1 1%, and most preferably in a range of 0.5% to 8%.
  • the standard deviation of the relative height oh Rma is a measure that the distance position in a defined position parallel to the surface of the
  • non-metallic platelet-shaped substrate is disposed within the entire coating.
  • the distances of the centers of the statistically distributed pores to the substrate surface were also determined by scanning electron microscopic cross-section recordings according to the method described above. For this purpose, in the 90 ° angle to the upper and lower base line, which correspond to the two surfaces of the platelet-shaped substrate, in the 50 nm distance so many parallel lines were drawn in that a grid was placed over the pearlescent pigment shown in the scanning electron micrograph cross section recording without spacing. If one of the parallel lines came to rest over one or more pores, its height (s), its center of pore (e) and the distance of the center of the pore or of the pore centers to the substrate surface were determined. From the statistical distribution of the pore centers can also determine a standard deviation.
  • Pearlescent pigments without spacing at> 20%.
  • the standard deviation of the distances between the centers of the statistically distributed pores to the substrate surface thus differs significantly in value from the standard deviation of the relative height of the center of the spacer layer of the transparent effect pigments according to the invention.
  • the standard deviation of the distances of the pore centers to the substrate surface of pearlescent pigments without spacing position can be contrasted with the standard deviation of the relative height of the center of the spacing layer of transparent effect pigments according to the invention.
  • the method just described for measuring the individual layers and the spacing layers is correspondingly transmitted.
  • the relative standard deviation of the height distribution of the spacer layer is 4% to 75%, preferably 7% to 69%, more preferably 9% to 63% and most preferably 13% to 60%.
  • the relative standard deviation in [%] of the height distribution is the quotient of the calculated standard deviation and the mean height.
  • the transparent according to the invention is 4% to 75%, preferably 7% to 69%, more preferably 9% to 63% and most preferably 13% to 60%.
  • the relative standard deviation in [%] of the height distribution is the quotient of the calculated standard deviation and the mean height.
  • Effect pigments within the at least one spacer layer a number of spacers per micrometer from a range of 0 to 17, more preferably from a range of 0 to 14, more preferably from a range of 1 to 1 1, and most preferably from a range from 1 to 9 on.
  • the transparent according to the invention is transparent.
  • Effect pigments within the at least one spacer layer a number of webs, defined as the number of connections or spacers per number of lines in percent, of ⁇ 85%, preferably from a range of 1% to 75%, particularly preferably from a range of 1% to 63 %, and most preferably from 1% to 49%.
  • the transparent effect pigments according to the invention comprise at least one spacer layer arranged substantially parallel to the surface of the non-metallic platelet-shaped substrate, the at least one spacer layer each having a mean height h a from 19 nm to 83 nm, particularly preferably from one Range of 27 nm to 66 nm and most preferably from a range of 33 nm to 57 nm.
  • the transparent effect pigments according to the invention have at least one distance layer of average height h a from 16 nm to 79 nm, preferably from 21 nm to 66 nm and very particularly preferably from 23 to 57 nm wherein, within the at least one spacer layer, the number of spacers per micrometer ranges from 0 to 8, preferably from a range from 0 to 6, more preferably from 1 to 5, and most preferably from one range from 1 to 4, is selected.
  • the spacer layer comprises in addition to the compounds described above or
  • Spacers cavities are spatially limited by the layers 2 and 3 and the compounds or spacers.
  • the cavities within the spacing of the transparent effect pigments of the invention can have a mean height h H from a range of 2 nm to 119 nm, preferably from a range of 6 nm to 105 nm, particularly preferably from a range of 1 1 nm to 85 nm and completely particularly preferably from a range of 18 nm to 53 nm occupy.
  • the height h H is understood to mean the greatest distance between the lowest and the highest cavity boundary. It is determined according to the procedure described above for the height h a by specifying
  • the average height h a represents a maximum value for the mean height h H. Accordingly, within the spacing position, a plurality of cavities can also be present one above the other.
  • the average height of the spacer layer h a and the average height of the cavities h H is based on a cured paint film in which the transparent effect pigments according to the invention are aligned substantially plane-parallel to the ground, according to the statements in
  • Section llk Determination of the mean thickness of the non-metallic platelet-shaped substrates, the average layer thickness of the layers 2 and 3, the average layer thickness of the entire coating, the average height h a of the spacer layer and the average height h H of
  • FIB focused ion beam
  • ions eg gallium, xenon, neon or helium
  • the ions release a large part of their energy upon impact with the effect pigment surface and destroy the coating at that point, resulting in a line-wise removal of material.
  • the average height h a , the average layer thickness of the layers 2 and 3, and the average layer thickness of the entire coating can also be determined by the scanning electron micrographs then taken using the method described above. Also, the average thickness of the non-metallic platelet-shaped substrate can be determined by
  • the transparent according to the invention comprise
  • Effect pigments within the spacer layer distributed over the entire effect pigment, measured on the basis of scanning electron micrographs cross-section recordings, an area fraction
  • Voids from a range of 51% to 99%, preferably from a range of 63% to 96%, more preferably from a range of 76% to 95%, and most preferably from a range of 84% to 94%.
  • the compounds or spacers preferably have an area fraction of from 1% to 49%, preferably from a range of 4% to 37%, more preferably from a range of 5% to 24% and most preferably from a range of 6% to 16%.
  • the total volume occupied by the compounds or spacers is smaller than that occupied by the cavities
  • the total volume occupied by the compounds or spacers is preferably less than 50% by volume, more preferably less than 30% by volume, particularly preferably less than 20% by volume and very particularly preferably less than 10% by volume. -% of the total volume occupied by the cavities.
  • the cavities lying within the spacing layer are expressly different from the pores of the teaching according to EP 1 422 268 A2 desired.
  • EP 1 422 268 A2 a coating with low porosity and the smallest possible pores is required to obtain pigments with high chroma and high brilliance.
  • the pigments according to EP 1 422 268 A2 have no spacing. According to the invention, they do not arbitrarily disperse within the entire coating but substantially parallel to the surface of the non-metallic platelet-shaped substrate within the
  • the transparent effect pigments according to the invention are distinguished from monolayer-coated pigments by a higher gloss and optionally a higher chroma, the same
  • non-metallic platelet-shaped substrate same particle size and identical first
  • the gloss of the transparent effect pigments according to the invention is determined on the basis of black-and-white registration cards with the aid of a Micro-Tri-Gloss gloss meter, Byk-Gardner, as described in the section "Gloss Measurements” in the following:
  • the chroma of the transparent effect pigments according to the invention also becomes determined by black and white cover cards with the multi-angle colorimeter BYK-mac (Byk-Gardner) according to the following remarks in Section IIb "Angle-dependent color measurements”.
  • Other visual effects, such as glitter and graininess, will be described in the following
  • the transparent effect pigments according to the invention comprise, in addition to the above-described layers 1, 2 and 3, further high- and / or low-refraction layers which are either below the optional layer 1 or layer 2 and / or viewed from the non-metallic platelet-shaped substrate. or above the layer 3 may be arranged.
  • These further layers may comprise metal oxides, metal hydroxides, metal oxide hydrates, wherein the metal ions of the metal oxides, metal hydroxides, metal oxide hydrates at least one metal ion from the group of metals consisting of Ti, Fe, Sn, Mn, Zr, Ca, Sr, Ba, Ni, Ag , Zn, Cu, Ce, Cr and Co, preferably selected from the group of metals consisting of Ti, Fe, Sn, Zr, Ag, Zn, Cu, Ce, Cr, and more preferably selected from the group of metals consisting include or are Ti, Fe and Sn.
  • these other layers may be semitransparent metals selected from the group consisting of Ag, Al, Cr, Ni, Au, Pt, Pd, Cu, Zn and Ti, preferably selected from the group consisting of Ag, Au and Cu, respectively their alloys and / or mixtures thereof.
  • the further layers are selected such that the proportion of coloring metal ions selected from the group of metals consisting of Fe, Ti, Sn, Mn, Cu, Cr, Co, Ag and Ce, in each case determined by means of RFA and in each case calculated as elemental metal, preferably at a total of ⁇ 4% by weight, more preferably in a range from 0.1% by weight to 3.4% by weight, particularly preferably in a range of 0.2% by weight in total to 3.7 wt .-% and most preferably in a range of from 0.3 wt .-% to 2.8 wt .-%, in each case based on the total weight of the transparent effect pigment is. Furthermore, the proportion of at least one
  • semitransparent metal determined by means of RFA, preferably at a total of ⁇ 2 wt .-%, more preferably in a range of from 0.03 wt .-% to 1, 3 wt .-%, and most preferably in a range of 0.1 Wt .-% to 0.8 wt .-%, each based on the
  • transparent effect pigments regardless of whether in the non-metallic platelet-shaped substrate or in the coating, at least one coloring metal ion and at least one semitransparent metal, their proportion is preferably at a total ⁇ 4 wt .-%, based on the total weight of the transparent effect pigment.
  • each of the layers of the transparent effect pigments of the invention may be doped, the doping being metal oxides,
  • the proportion of doping is preferably at a total ⁇ 1 wt .-%, more preferably at a total of ⁇ 0.5 wt .-% and most preferably at a total of ⁇ 0.2 wt .-%, each based on the total weight of the transparent effect pigments.
  • the entire coating of the transparent effect pigments according to the invention may comprise, in addition to the spacing between the layers 2 and 3, at least one further spacing layer, which is also arranged substantially parallel to the surface of the non-metallic platelet-shaped substrate.
  • the transparent effect pigments according to the invention preferably have no more than four spacer layers within the entire coating, since their optical quality then decreases.
  • the transparent effect pigment according to the invention comprises more than one spacing, there is no spacing in relation to the entire coating neither in the first sixth nor in the sixth sixth of the entire coating.
  • the transparent effect pigments according to the invention can thus have different interference colors depending on their coating.
  • the D 50 values of the transparent effect pigments according to the invention are preferably in a range from 3 ⁇ m to 350 ⁇ m.
  • the D 50 values of the transparent effect pigments according to the invention are preferably in a range from 4 [im to 21 1 [im, more preferably in a range from 6 [im to 147 [im, particularly preferably in a range from 7 [im to 99]. in and most preferably in a range from 8 [im to 56 [im.
  • the transparent effect pigments according to the invention have a D 50 value in the range from 3 ⁇ m to 15 ⁇ m (in or from 10 ⁇ m to 35 ⁇ m or from 25 ⁇ m to 45 ⁇ m in or out of one range from 30 [im to 65 [in or out of a range of 40 [im to 140 [in or out of a range of 135 [im to 250 [im on.
  • the Dio values of the transparent effect pigments according to the invention preferably comprise a range from 1 [im to 120 [im. Particularly preferred are the Di 0 values of
  • the D 90 values of the transparent effect pigments according to the invention preferably comprise a range from 6 to 500 ⁇ m. Particularly preferred are the D 90 - values of
  • transparent effect pigments of the invention in a range from 8 [im to 250 [im or in a range of 10 ⁇ to 150 ⁇ or in a range of 40 [im to 70 [in or in a range of 68 ⁇ to 1 10 [in or in a range of 120 [im to 180 [in or in a range of 400 [im to 490 [im.
  • Size distribution function indicates that 10%, 50% and 90%, respectively, of the measured effect pigments have a volume-matched diameter that is equal to or less than the specified value.
  • Absorption behavior of the particles includes.
  • the advantages of narrow size classification in terms of color purity and / or gloss of the resulting effect pigments are described, for example, in EP 2 217 664 A1, EP 2 346 950 A1, EP 2 356 181 A1, EP 2 346 949 A1, EP 2 367 889 A1.
  • a non-calcined layer comprising tin oxide, tin hydroxide and / or
  • Tin oxide hydrate comprises or consists of, by adding a water-soluble tin salt with simultaneous addition of a mineral liquor,
  • Metal oxides, metal hydroxides and / or metal oxide hydrates by sequential addition of three water-soluble metal salts, each with the simultaneous addition of mineral lye, wherein the second water-soluble metal salt - to produce the layer B - with respect to the metal ion different from the other two water-soluble metal salts to produce the layer A or layer C,
  • the transparent according to the invention is transparent.
  • the deposition, preferably deposition, of the respective metal oxides, metal hydroxides and / or metal oxide hydrates is preferably carried out at a constant pH in a range from pH 1.4 to 10.0, depending on the metal salt.
  • the metal ions present in layer B probably diffuse into layer A and / or layer C to form mixed metal oxides and / or mixed metal hydroxides and / or metal oxide hydrates and / or mixtures of metal oxides and / or metal hydroxides and / or metal oxide hydrates layer A and / or layer C.
  • layers 2 and 3 according to the invention and the spacer layer between them are formed during calcination, at least one of the two layers 2 and 3 comprises at least two different metal ions. From the originally three successively deposited layers A, B and C, the layers 2 and 3 and the intermediate spacer layer thus result during calcination, at least one of the two layers 2 and 3 comprising at least two different metal ions.
  • the differential mobility of the metal oxides, metal hydroxides and / or metal oxide hydrates to one another during calcination is responsible for the formation of the spacer layer.
  • the mobility of the metal ions contained in the layer B competes with the mobility of the metal ions contained in the layers A and / or C, provided that the metal ions diffuse from the layer B into at least one of the adjacent layers A and / or C and the metal ions from at least one of the layers A and / or C diffuses into the layer B.
  • the inventors assume that if the mobility of the metal ions contained in the layer B during the calcination is higher than the mobility of the metal ions contained in the layers A and / or C, one of the possible explanations for the formation of the spacer layer. Furthermore, it is believed that a concentration gradient with respect to the metal ions promotes the formation of a spacer layer, ie, when more mobile metal ions from layer B into one of the adjacent layers
  • Metal oxide hydrates at least one metal ion selected from the group of metals consisting of Ti, Sn and Zr.
  • the first and the third metal oxide, metal hydroxide and / or metal oxide hydrate produce the layer A or layer C after application.
  • Metal oxide hydrates produces layer B and comprises at least one metal ion selected from the group of metals consisting of Fe, Sn, Zr and Ce other than the metal ions of the metal oxides, metal hydroxides and / or metal oxide hydrates deposited to form layer A and layer C. is.
  • the deposited, preferably deposited, metal oxides, metal hydroxides and / or metal oxide hydrates may be the same or different from each other with respect to the metal ion (s).
  • the transparent effect pigments according to the invention can be prepared as follows:
  • Metal oxides, metal hydroxides and / or metal oxide hydrates by sequential addition of two water-soluble metal salts, each with simultaneous addition of mineral lye, wherein the first water-soluble metal salt - to produce the layer B - with respect to the metal ion different from the other water-soluble metal salt to produce the layer C. and the layer which directly adjoins the layer B in the direction of the substrate, Separating the coated substrates from the coating solution (s), optionally washing and / or optionally drying the coated substrates,
  • the deposition, preferably deposition, of the respective metal oxides, metal hydroxides and / or metal oxide hydrates is also carried out here preferably at a constant pH in the range from pH 1.4 to 10.0, depending on the metal salt.
  • Metal hydroxides and / or metal oxide hydrates and / or mixtures of metal oxides and / or metal hydroxides and / or metal oxide hydrates in the layer C diffuse. Due to the diffusion of the metal ions from the layer B at least into the layer C, the layer 3 according to the invention and the spacer layer are formed during calcination. From the originally two successively deposited layers B and C, the layer 3 and the spacer layer thus result during calcination, wherein at least the layer 3 comprises at least two different metal ions. The layer 2 is already present here. As layer 2 is the outermost
  • that layer to which the layer B is applied comprises, in accordance with the invention, a high refractive index metal oxide, metal hydroxide and / or metal oxide hydrate.
  • the layer to which layer A is applied may comprise, in accordance with the invention, a high refractive or a low refractive index metal oxide, metal hydroxide and / or metal oxide hydrate.
  • a layer 2 comprising a metal oxide, metal hydroxide and / or metal oxide hydrate, the metal ions of the metal oxide, metal hydroxide and / or metal oxide hydrate comprising titanium ions and / or iron ions or are, one
  • Spacer layer and a layer 3 comprising a metal oxide, metal hydroxide and / or
  • Metal oxide hydrate wherein the metal ions of the metal oxide, metal hydroxide and / or
  • Metal oxide hydrate include or are titanium ions and / or iron ions. At least one of the layers comprising a metal oxide, metal hydroxide and / or metal oxide hydrate, wherein the metal ions of the metal oxide, metal hydroxide and / or metal oxide hydrate comprise or are titanium ions and / or iron ions, contains an iron titanate, preferably pseudobrookite and / or pseudorutil. With regard to the amounts used, the above statements on coloring and non-coloring metal ions also apply here. If, for example, successively a water-soluble titanium (IV) salt, a water-soluble
  • a layer 2 comprising a metal oxide, metal hydroxide and / or metal oxide hydrate, the metal ions of the metal oxide, metal hydroxide and / or metal oxide hydrate comprising titanium ions and / or tin ions or a spacer layer and a layer 3 comprising a metal oxide, metal hydroxide and / or metal oxide hydrate, wherein the metal ions of the metal oxide, metal hydroxide and / or metal oxide hydrate include or are titanium ions and / or tin ions.
  • a water-soluble titanium (IV) salt is added to a suspension of an optionally coated, non-metallic platelet-shaped substrate, calcined after deposition of titanium dioxide, titanium hydroxide and / or titanium oxide hydrate, this product is resuspended after calcining and a water-soluble tin (IV) salt is successively removed and in turn to add a water-soluble titanium (IV) salt, formed on re-final calcination, viewed in SEM cross-section starting from the substrate, on the optionally existing coating and the layer 2 comprising a metal oxide, metal hydroxide and / or Metal oxide hydrate wherein the metal ion of the metal oxide, metal hydroxide and / or metal oxide hydrate comprises or are at least titanium ions, a spacer layer and a layer 3 comprising a metal oxide, metal hydroxide and / or metal oxide hydrate wherein the metal ions of the metal oxide, metal hydroxide and / or metal oxide hydrate are titanium ions and or include t
  • transparent effect pigments of the invention have, in addition to the at least two or three, preferably sequentially deposited, metal oxides,
  • Metal hydroxides and / or metal oxide hydrates further layers comprising metal oxides, metal hydroxides and / or metal oxide hydrates, so may also within the other
  • Layers form further spacer layers, provided that the above, at least two or three sequentially applied, preferably deposited, metal oxides, metal hydroxides and / or metal oxide hydrates described process steps are met.
  • the transparent effect pigments according to the invention may optionally be provided with at least one outer protective layer which further increases the weather stability and / or chemical stability and / or reduces the photoactivity.
  • the UV resistance as well as the
  • the optional protective layer comprises metal oxides, metal hydroxides and / or
  • Metal oxide whose metal ions are selected from the group of metals selected from Si, Ce, Cr, Al, Zr, Zn and mixtures thereof, preferably from the group of metals Si, Ce, Al, Zr and mixtures thereof.
  • the proportion of optional metals selected from the group of metals selected from Si, Ce, Cr, Al, Zr, Zn and mixtures thereof, preferably from the group of metals Si, Ce, Al, Zr and mixtures thereof.
  • Protective layer present preferably in a range of 0.1 wt .-% to 7.0 wt .-%, more preferably in a range of 0.2 wt .-% to 5.2 wt .-% and most preferably in one Range of 0.3 wt .-% to 3.1 wt .-%, each based on the
  • the optionally present protective layer can furthermore be surface-modified, for example by silanes.
  • the silanes can have no functional binding group or one or more functional binding group (s).
  • Silanes having at least one functional bonding group are also referred to below as organofunctional silanes.
  • one or more silanes may be applied to this outer protective layer.
  • the silanes can be alkylsilanes having branched or unbranched alkyl radicals having 1 to 24 C atoms, preferably 6 to 18 C atoms.
  • the silane without a functional linking group is an alkylsilane.
  • the alkylsilane preferably has the formula R (4_Z ) Si (X) z .
  • R is a substituted or unsubstituted, unbranched or branched alkyl chain having 10 to 22 carbon atoms and X is a halogen and / or alkoxy group. Preference is given to alkylsilanes with alkyl chains having at least 12 carbon atoms. R may also be cyclically connected to Si, in which case z is usually 2.
  • organofunctional silane which permits chemical bonding to a plastic, a binder of a lacquer or a paint, etc., for surface modification.
  • the functional groups of the organofunctional silane may also be referred to as coupling groups or functional linking groups and are preferably selected from the group consisting of hydroxy, amino, acryl, methacryl, vinyl, epoxy, isocyanate, cyano and mixtures thereof.
  • organofunctional silanes which preferably have surface-modifying agents and which have suitable functional groups are commercially available and are manufactured, for example, by Evonik and marketed under the trade name "Dynasylan.” Further products can be obtained from the company Momentive (Silquest-Silane) or from from Wacker, for example standard and ⁇ -silanes from the GENIOSIL product group.
  • Examples of these are 3-methacryloxypropyltrimethoxysilane (Dynasylan MEMO, Silquest A-174NT), vinyltri (m) ethoxysilane (Dynasylan VTMO or VTEO, Silquest A-151 or A-171),
  • Methyltri (m) ethoxy silane _i (Dynasylan MTMS or MTES), 3-mercaptopropyl trimethoxysilane (Dynasylan MTMO; Silquest A-189), 3-glycidoxypropyltrimethoxysilane (Dynasylan GLYMO, Silquest A-187), tris [3- (trimethoxysilyl) propyl _i ] isocyanurate (Silquest Y-1 1597), Bis [3-
  • Methacryloxypropyltriacetoxysilane 3-methacryloxypropylmethyldimethoxysilane, vinyltrichlonsilane, Vinyltrimethoxysilane (GENIOSIL XL 10), vinyltris (2-methoxyethoxy) silane (GENIOSIL GF 58), vinyltriacetoxysilane or mixtures thereof.
  • organofunctional silanes are 3-methacryloxypropyltrimethoxysilane
  • Methacryloxymethyltri (m) ethoxysilane (GENIOSIL XL 33, XL 36),
  • organofunctional silanes on the particles of the invention or the pigments of the invention.
  • aqueous aminosiloxane (Dynasylan
  • Hydrosil 1 151 aqueous amino- / alkyl-functional siloxane (Dynasylan Hydrosil 2627 or 2909), aqueous diaminofunctional siloxane (Dynasylan Hydrosil 2776), aqueous epoxy-functional siloxane (Dynasylan Hydrosil 2926), amino- / alkyl-functional oligosiloxane (Dynasylan 1 146), vinyl- / alkyl functional oligosiloxane (Dynasylan 6598), oligomeric vinylsilane (Dynasylan 6490) or oligomeric short chain alkyl functional silane (Dynasylan 9896).
  • the organofunctional silane mixture contains, in addition to at least one silane without a functional bond group, at least one amino-functional silane.
  • the amino function is a functional group that can undergo one or more chemical interactions with most groups present in binders. This can be a covalent bond, such as with isocyanate or carboxylate functions of the binder, or hydrogen ! bridge bonds as with OH or COOR functions or ionic ones
  • Interactions include.
  • An amino function is therefore very well suited for the purpose of chemically attaching the pigment to various binders.
  • the following compounds are preferably used for this purpose: 3-aminopropyltrimethoxysilane (Dynasylan AMMO, Silquest A-1 110), 3-aminopropyltriethoxysilane (Dynasylan AMEO), [3- (2-aminoethyl) aminopropyl] trimethoxysilane (Dynasylan DAMO, Silquest A-1 120 ), [3- (2-aminoethyl) aminopropyl] triethoxysilane, triamine in-functional trimethoxysilane (Silquest A-1130), bis (gamma-trimethoxysilylpropyl) amine (Silquest A-1 170), N-ethyl-gamma-aminoisobutyltrimethoxysilane
  • the optionally present protective layer has the features described in the respective main claims of WO 2006/021386 A1, WO 2012/130897 A1 or WO
  • the transparent effect pigments of the invention can be combined with a
  • the effect pigments in different media easier.
  • the effect pigments preferably have one of the surface modifications disclosed in the main claims of EP 2 698 403 A1 or EP 2 576 702 A1.
  • the transparent effect pigments according to the invention may have an outermost coating in accordance with WO 2006/136435 A2, claim 32, which is preferably obtained by the spray-drying method according to
  • the transparent effect pigments according to the invention can also be used in mixtures with transparent and / or opaque organic white, colored and black pigments and / or metallic effect pigments and / or pearlescent pigments and / or fillers in the respective desired application.
  • the amount of transparent effect pigments according to the invention used depends on the particular application and on the optical effect to be achieved.
  • the transparent effect pigments according to the invention can be used in cosmetic formulations, plastics, films, textiles, ceramic materials, glasses, paints, printing inks, inks, paints and / or powder coatings. Furthermore, the transparent effect pigments of the invention can also be used for functional applications, such as laser marking, greenhouse films or agricultural films.
  • the transparent effect pigments according to the invention can be combined with suitable raw materials, auxiliaries and active ingredients for each application become.
  • Formulation may be between 0.001% by weight for rinse-off products and 40.0% by weight for leave-on products, each based on the total weight of the formulation.
  • the transparent effect pigments according to the invention can be present in a compact particle form.
  • Compact particle form is understood as meaning pellets in the form of preferably cylinders and / or beads.
  • the cylinders in this case preferably have a diameter from a range of 0.2 cm to 4.2 cm, more preferably from a range of 0.5 cm to 2.3 cm and most preferably from a range of 0.7 cm to 1 , 7 cm and preferably has a length from a range of 0.2 cm to 7.1 cm, more preferably from a range of 0.6 cm to 5.3 cm and most preferably from a range of 0.8 cm to 3, 7 cm up.
  • the beads preferably have a radius of ⁇ 1 cm, more preferably from a range of 0.2 cm to 0.7 cm, and most preferably from a range of 0.3 cm to 0.5 cm.
  • the present invention relates to a transparent
  • Effect pigment comprising a non-metallic platelet-shaped substrate, preferably a synthetic mica flake or a glass flake, and an applied thereto
  • a layer 2 comprising at least one metal oxide, metal hydroxide and / or metal oxide hydrate wherein the metal ion comprises or is at least one metal ion selected from the group of metals consisting of Ti, Sn and Fe,
  • a layer 3 comprising at least one metal oxide, metal hydroxide and / or metal oxide hydrate, wherein the metal ion comprises or is at least one metal ion selected from the group of metals consisting of Ti, Sn, Zr and Fe
  • Effect pigment comprising a non-metallic platelet-shaped substrate, preferably a synthetic mica flake or a glass flake, and an applied thereto
  • a layer 2 comprising at least one metal oxide, metal hydroxide and / or metal oxide hydrate, the metal ion comprising or being at least one non-coloring metal ion selected from the group of metals consisting of Ti, Sn and Zr,
  • a layer 3 comprising at least one metal oxide, metal hydroxide and / or metal oxide hydrate, the metal ion comprising or being at least one non-coloring metal ion selected from the group of metals consisting of Ti, Sn and Zr,
  • the layers 2 or 3 comprises at least two different metal ions from the groups listed above, the layers 2 and 3 by a
  • Distance layer are interrupted, and wherein the effect pigments have a span AD from a range of 0.8 to 1, 9.
  • the present invention relates to a transparent
  • Effect pigment comprising a non-metallic platelet-shaped substrate, preferably a synthetic mica flake or a glass flake, and an applied thereto
  • a layer 2 comprising at least one metal oxide, metal hydroxide and / or metal oxide hydrate, wherein the metal ion comprises or is at least one metal ion selected from the group of metals consisting of Ti, Fe, Sn and Zr,
  • a layer 3 comprising at least one metal oxide, metal hydroxide and / or metal oxide hydrate, wherein the metal ion comprises or is at least one metal ion selected from the group of metals consisting of Ti, Fe, Sn and Zr
  • the layers 2 or 3 comprises at least two different metal ions, wherein the proportion of coloring metal ions, each determined by XRF and in each case calculated as elemental metal, in a range from 0.01 wt .-% to 3.9 wt %, preferably in a range of altogether 0.1% by weight to 2.9% by weight, and very particularly preferably in a range of altogether 0.7% by weight to 2.1% by weight.
  • the layers 2 and 3 are interrupted by a distance layer of the mean height h a from a range of 12 nm to 71 nm, preferably from a range of 21 nm to 53 nm.
  • the present invention relates to a transparent effect pigment comprising a non-metallic platelet-shaped substrate, preferably a synthetic mica flake or a glass flake, and a coating applied thereto
  • a layer 2 comprising at least one metal oxide, metal hydroxide and / or metal oxide hydrate, wherein the metal ion comprises or is at least one metal ion selected from the group of metals consisting of Ti, Fe, Sn and Zr,
  • a layer 3 comprising at least one metal oxide, metal hydroxide and / or metal oxide hydrate, wherein the metal ion comprises or is at least one metal ion selected from the group of metals consisting of Ti, Fe, Sn and Zr
  • the layers 2 or 3 comprises at least two different metal ions from the groups listed above, wherein the proportion of coloring metal ions, in each case determined by XRF and in each case calculated as elemental metal, in a range of 0.03 wt .-% to 2.1% by weight, preferably in a range of 0.06% by weight to
  • the layers 2 and 3 are interrupted by a spacer layer and the effect pigment a
  • the present invention relates to a transparent effect pigment comprising a non-metallic platelet-shaped substrate, preferably a synthetic mica flake or a glass flake, and one thereon
  • a layer 2 comprising at least one metal oxide, metal hydroxide and / or metal oxide hydrate, the metal ions comprising or being at least two metal ions selected from the group of metals consisting of Ti and Sn,
  • a layer 3 comprising at least one metal oxide, metal hydroxide and / or metal oxide hydrate, wherein the metal ions comprise or are at least two metal ions selected from the group of metals consisting of Ti and Sn
  • Coating further high and / or low refractive index layers comprises and the effect pigment at least one further, substantially parallel to the surface of the non-metallic
  • the present invention relates to a transparent platelet-shaped substrate extending spacer layer of the average height h a from a range of 1 1 nm to 58 nm, preferably from a range of 17 nm to 47 nm.
  • the present invention relates to a transparent platelet-shaped substrate extending spacer layer of the average height h a from a range of 1 1 nm to 58 nm, preferably from a range of 17 nm to 47 nm.
  • the present invention relates to a transparent
  • Effect pigment comprising a non-metallic platelet-shaped substrate, preferably a synthetic mica flake or a glass flake, and an applied thereto
  • Coating the coating having at least one spacer layer substantially parallel to the surface of the non-metallic platelet-shaped substrate, and the effect pigment being obtainable by i) optionally applying a non-calcined tin oxide, tin hydroxide and / or tin oxide hydrate layer on the non-metallic platelet-shaped substrate, ii ) sequentially applying three non-calcined metal oxides, metal hydroxides and / or metal oxide hydrates, the second of these three non-calcined metal oxides,
  • Metal hydroxides and / or metal oxide hydrates is materially different from the others and is such that it is present in at least one of the other non-calcined metal oxides,
  • step ii) calcining the product obtained in step ii) at a temperature in the range from 720 ° C to 970 ° C.
  • the present invention relates to a transparent effect pigment comprising a non-metallic platelet-shaped substrate, preferably a synthetic mica flake or a glass flake, and a coating applied thereto, the coating comprising at least one spacer layer substantially parallel to the surface of the non-metallic flake-form substrate the average height h a from a range of 14 nm to 51 nm, and the effect pigment is obtainable by i) optionally applying a non-calcined tin oxide, Zinnhydroxid- and / or
  • non-metallic platelet-shaped substrate ii) sequentially applying a first layer A using a water-soluble titanium (IV) salt, a second layer B below
  • the coating of the inventive transparent effect pigments comprises instead of the at least one metal oxide, metal hydroxide and / or
  • the coating of the transparent effect pigments of the invention comprises, in addition to the at least one metal oxide, metal hydroxide and / or Metal oxide hydrate at least one metal suboxide, metal fluoride, metal nitride, metal oxynitride,
  • the pH of the suspension was lowered to pH 1.9 and then a solution of 400 ml TiCl 4 (200 g TiO 2 / l demineralized water) was metered into the suspension. After the end of the addition, the mixture was stirred for 10 minutes and then the pH was adjusted to pH 2.6. Subsequently, 30 ml of an aqueous iron chloride solution having a density of 1.42 g / cm 3 were added. After successful Metered addition was stirred for 10 minutes and 405 ml of a further solution of TiCl 4 (200 g TiO 2 / l deionized water) added to the suspension. 15 minutes after completion of the addition, the suspension was filtered off and the filter cake was washed. The filter cake was dried and calcined at 850 ° C for 60 minutes. Extremely chromatic, high gloss, transparent effect pigments with blue interference color were obtained.
  • the metered addition was stirred for 10 minutes and added 400 ml of another solution of TiCl 4 (200 g Ti0 2 / l deionized water) in the suspension. 15 minutes after completion of the addition, the suspension was filtered off and the filter cake was washed. The filter cake was dried and calcined at 850 ° C for 60 minutes. Extremely chromatic, high gloss, transparent effect pigments with blue interference color were obtained.
  • the suspension was filtered off and the filter cake was washed.
  • the filter cake was dried and calcined at 800 ° C for 60 minutes. Extremely chromatic, high gloss, transparent effect pigments with blue interference color were obtained.
  • Example 4 100 g of the effect pigment obtained in Example 4 were suspended in 850 ml of deionized water and heated to 85 ° C. with turbulent stirring. The pH was lowered to pH 4.2 with dilute hydrochloric acid. Then, a solution of 0.93 g of Ce (NO 3 ) 3 ⁇ 6 H 2 0 dissolved in 40 ml of deionized water was added. At the same time, the pH was kept constant by dropwise addition of a 10% NaOH solution. After the solution was completely added, the mixture was stirred for one hour and then the pH was adjusted to pH 10 with dilute sodium hydroxide solution.
  • Comparative Example 3 Effect pigment with blue interference color based on synthetic mica platelets, coated with titanium dioxide, SYMIC C261, ECKART.
  • Multilayer pigment with blue interference color based on natural mica flakes coated with titanium dioxide, silicon dioxide, titanium dioxide, Lumina Royal Blue, BASF.
  • the size distribution curve of the transparent effect pigments according to the invention and the pigments of the comparative examples was determined with the apparatus Mastersizer 2000, Malvern, according to the manufacturer's instructions. For this purpose, about 0.1 g of the respective pigment was added as an aqueous suspension, without the addition of dispersing aids, with constant stirring by means of a Pasteur pipette in the sample preparation cell of the meter and measured several times. The mean values were calculated from the individual measurement results. The evaluation of the scattered light signals was carried out according to the Fraunhofer method.
  • the mean particle size D 50 is understood as meaning the D 50 value of the cumulative frequency distribution of the volume-related size distribution function as obtained by laser diffraction methods.
  • the D 50 value indicates that 50% of the pigments have a volume-equivalent diameter which is equal to or less than the stated value, for example 20 ⁇ m.
  • the D 10 or D 90 value indicates that 10% or 90% of the pigments have a volume-related diameter which is equal to or less than the respective measured value.
  • the span AD defined as indicates the width of the particle size distribution. in the
  • the effect pigments according to the invention were pigmented at a level of 6% by weight (pigments) or 10% by weight (substrates), in each case based on the total weight of the wet paint, stirred into a conventional nitrocellulose lacquer (Erco bronze mixed enamel 2615e colorless, Maeder Kunststofflack AG).
  • the respective pigments or the respective non-metallic platelet-shaped substrates were initially introduced and then dispersed with a brush into the lacquer.
  • the finished lacquer was applied to a doctor blade puller (RK Print Coat Instr. LTd. Citenco puller model K 101) with a
  • Angle of incidence of 45 ° (according to manufacturer's instructions) at different observation angles relative to the glancing angle determines the color values on the black background of the cover map.
  • the chroma value C * i 5 was used, which was measured at a measurement angle of 15 ° away from the gloss angle on the black background of the black and white card.
  • the transparent effect pigments according to the invention with blue interference color from Examples 2, 3 and 5 are significantly more intense in color than that with only a single titanium dioxide layer occupied pigment with blue interference color of Comparative Example 3. Their optical impression is approximately comparable to that of a multi-layered pigment with blue interference color from Comparative Example 2. llc cover comparison
  • the viewing angle is measured away from the specular reflection in the illumination plane.
  • the effect pigments according to the invention have a high transparency.
  • Their coverage quotient D q is preferably ⁇ 0.55.
  • the coverage ratio D q of the transparent effect pigments according to the invention of Examples 1 to 5 is, as shown in Table 4, in each case well below 0.5. lld gloss measurements
  • the shine is a measure of the directed reflection.
  • the gloss values of the transparent effect pigments according to the invention and of the pigments of the comparative examples are shown in Table 4.
  • the transparent effect pigments according to the invention from Examples 1 to 5 show in part significantly higher gloss values than the single-layer coated pigment from Comparative Example 3.
  • the gloss values of the transparent effect pigments according to the invention are sometimes even significantly higher than those of the multilayer pigments with the structure
  • Glitter intensity S_i, glitter area S_a and granularity G are summarized in Table 4.
  • Multilayer pigments from Comparative Examples 2, 4 and 5 are at least equivalent to the optical effects, but in most cases better.
  • the Waring Blender test now simulates these conditions and serves to evaluate the loop and shear stability. Especially pigments whose coating is not sufficiently anchored to the carrier material show in this test strong deviations of the chroma values in comparison to the untreated applications.
  • the Waring Blender test can thus be understood as a measure of the intermediate adhesion of the pigment coating to shear forces.
  • the transparent effect pigments according to the invention or the pigments of the comparative examples were weighed in according to the following batch and gradually pasted into a 880 ml beaker with a conventional acrylic lacquer. Thereafter, the viscosity was adjusted to 17 "in DIN 4 mm beaker with butyl acetate / xylene 1: 1.
  • a total of 600 g of paint were prepared, of which 400 g were introduced into a double-walled 1 kg vessel with water cooling and dried under the Dispermate (Waring Stirring time was 13,500 rpm for 8 minutes, then 200 g of paint was removed and the remainder was stirred for a further 12 minutes.
  • Table 5 shows the color change AC * 15 ° and the gloss change AGlance 60 ° of the sample subjected to the Waring Blender test to the untreated sample on the basis of Example 4 according to the invention.
  • the test sheet of Example 4 of the invention thus meets the criteria of the test.
  • the color difference is negligible and hardly noticeable to the naked eye. Even under the light microscope hardly any changes such as flaking of the coating or other surface defects could be detected.
  • the transparent effect pigments according to the invention show shear stability despite their distance position extremes.
  • the chemical resistance of the transparent effect pigments according to the invention and of the pigments of the comparative examples was determined on the basis of lacquer applications on plastic panels. 6 g of the respective pigment were stirred into a mixture of 90 g of a conventional colorless acrylic varnish and 10 g of butyl acetate 85. Thereafter, the viscosity was adjusted to 17 "in a DIN 4 mm beaker with a mixture of butyl acetate 85 and xylene in a ratio of 1: 1. Each 100 g of this coating was applied to the panels in a similar manner to IIf using an automatic spray gun the panels were baked for 30 minutes at 80 ° C.
  • Pigments with a ⁇ (15 °) ⁇ 3 can be considered to be chemically stable.
  • the transparent effect pigments according to the invention from Examples 3 and 4 are significantly lower, while the pigments of Comparative Examples 1, 2 and 5 clearly exceed the limit value.
  • the metal oxide, metal hydroxide and / or metal oxide hydrate contents of the transparent effect pigments according to the invention and of the pigments of the comparative examples were determined by means of X-ray fluorescence analysis (XRF).
  • XRF X-ray fluorescence analysis
  • the respective pigments were incorporated into a lithium tetraborate glass tablet, fixed in solid-state measuring cups and measured therefrom.
  • the instrument used was the device Advantix ARL, from Thermo Scientific.
  • the measured values are shown in Table 7.
  • the data for the different contents for titanium were given as Ti0 2 , for iron as Fe 2 0 3 , for zirconium as Zr0 2 and for tin as Sn0 2 .
  • the transparent effect pigments according to the invention or the pigments of the comparative examples were incorporated into a water-based paint system and the test applications were prepared by spray painting on aluminum sheets.
  • the basecoat was overcoated with a commercial 1K clearcoat and then baked.
  • the pigment of Comparative Example 6 had a strong swelling behavior and a poor interlayer adhesion.
  • the transparent effect pigment of Example 6 according to the invention was stable and showed almost no changes before and after the test.
  • the UV resistance of the transparent effect pigments according to the invention and of the pigments of the comparative examples was determined on the basis of the UV rapid test described in EP 0 870 730 A1 for determining the photochemical UV activity of TiO 2 pigments.
  • 1.0 g of the corresponding pigment was dispersed in 9.0 g of a double-bond-rich melamine-containing paint.
  • Squeegee prints were made on white board and these were dried at room temperature. The squeegee prints were divided and stored in each case one of the two sections as an unloaded reference sample in the dark.
  • the pigment of Comparative Example 6 had a significantly greater color change ( ⁇ *) after corresponding exposure than Example 6.
  • the transparent effect pigments according to the invention 10% were incorporated in a 2K clearcoat Autoclear Plus HS Fa. Sikkens GmbH with a sleeve brush, applied by means of a spiral blade (26 ⁇ wet film thickness) on a film and dried. After 24 h
  • Drying time cross sections were made by these doctor blade draws.
  • the cross-sections were measured in the SEM, with at least 100 individual pigments being measured to determine the average thickness of the non-metallic platelet-shaped substrates in order to obtain meaningful statistics.
  • the average thickness of the layers 2 and 3 was here in the scanning electron microscopy
  • the scanning electron micrograph was preferably at least 50,000 times, based on Polaroid 545. Starting from the respective upper and lower base line of the non-metallic platelet-shaped substrate in the direction of layer 3, the distances between the intersections of these lines at the respective interfaces of the optional layer 1 to layer 2 , Layer 2 to the distance position, distance to layer 3 and layer 3 to
  • the respective arithmetic mean values were formed in order to determine the values of the average layer thicknesses, the mean height h H and the mean height h a given above.
  • the measurements described above were performed on at least 100 lines.
  • FIB focused ion beam
  • a fine beam of highly accelerated ions eg gallium, xenon, neon or helium
  • ion optics Focused on one point and guided line by line over the effect pigment surface to be processed.
  • the ions release a large part of their energy upon impact with the effect pigment surface and destroy the coating at that point, resulting in a line-wise removal of material.
  • the average height h a , the average layer thickness of the layers 2 and 3, and the average layer thickness of the entire coating can also be determined by the scanning electron micrographs then taken using the method described above.
  • the average thickness of the non-metallic platelet-shaped substrate can also be determined by means of scanning electron micrographs of the effect pigments which have been cut by the FIB method.
  • h ma center of the distance position (sum of the layer thickness of the optional layer 1, the layer 2 and the half height h a )
  • n s average number of lands per ⁇
  • Table 7 shows the mean height h a of the distance of the measured pigments. All transparent effect pigments according to the invention have, in contrast to the pigments of Comparative Examples 1 to 5, a spacing layer.
  • the pigment of Comparative Example 3 does not have a spacer layer but randomly distributed pores within the coating (Figure 5).
  • Table 10 for Comparative Example 3, with the value in the column oh Rma [%], the standard deviation of the pore centers is
  • Substrate surface area is 30.4%, which proves that the pores are randomly distributed within the entire coating is present.
  • the situation is different with the transparent effect pigment of Example 5 according to the invention.
  • the web number density S D is quite high at 66.5%, but the standard deviation of the relative height of the center of the distance layer h Rma is 6.4%, which shows the spacer layer lies in a defined position within the coating.
  • the standard deviation of the distances of the pore centers to the substrate surface of the pigment from Comparative Example 3 can thus be compared with the standard deviation of the relative height of the center of the spacer layer of the transparent effect pigments according to the invention from Examples 2 to 5.
  • the distance position influences the optical properties of the transparent effect pigments according to the invention.
  • the transparent effect pigments of the invention have a very good mechanical and chemical stability. None of the pigments from the comparative examples has, in the overall view, satisfactorily exhibited the properties mentioned.
  • the scanning electron micrographs were obtained on the basis of cross-sections of the transparent effect pigments according to the invention with the scanning electron microscope Supra 35 (Zeiss) (for example, Figures 1 -4).
  • the energy-dispersive X-ray microanalysis (EDX analysis) was carried out with the EDAX Sapphire device, EDAX.
  • the effect pigment of Example 1 can be used in the range of 0.1 to 2.5% by weight, based on the total weight of the body lotion formulation.
  • the balance to 100 wt .-% of the formulation can be made with water.
  • Keltrol CG-T was dispersed in phase A and heated to 75 ° C. Phase B was heated separately to 75 ° C. Subsequently, Phase B was added slowly to Phase A. While stirring, the emulsion was cooled to room temperature and phase C added individually.
  • Example 5 The effect pigment of Example 5 can be used in a range of 5 to 30.0 wt .-%, based on the total weight of the eyeshadow formulation. The balance to 100 wt .-% of the formulation can be done with Isohexadecane.
  • Phase A was mixed and heated to 85 ° C, then Phase B was added to Phase A with stirring. After filling into a corresponding container, the mixture is cooled to room temperature.
  • the effect pigment of Example 4 can be used in a range from 0.01 to 1.0% by weight, based on the total weight of the shower gel formulation.
  • the balance to 100 wt .-% of the formulation can be made with water.
  • Phase A was stirred, then Phase B was added and stirred until a homogeneous appearance was achieved.
  • Phase C was weighed separately, mixed briefly and added to Phase AB. It was then stirred again and added phase D individually.
  • the effect pigment of Example 3 can be used in a range of 5.0 to 40.0% by weight, based on the total weight of the eyeshadow formulation.
  • the balance to 100 wt .-% of the formulation can be made with talc.
  • Phase A was mixed for 30s at 2500 rpm in a high speed mixer.
  • Phase B was added and the mixture was mixed for 60 seconds at 3000 rpm in the same mixer. Finally, the powder mixture is pressed by means of an eyeshadow press at 100 bar for 30 seconds in the form.
  • Linoleic Acid (and) Linolenic Acid Vitamin F (1 +
  • the effect pigment of Example 1 can be used in a range from 1, 0 to 10.0 wt .-%, based on the total weight of the mascara formulation.
  • the balance to 100 wt .-% of the formulation can be done with the water from phase A.
  • Phase A was stirred under high shear.
  • Phase B was weighed separately. Phase A and Phase B were heated separately to 85 ° C, then Phase B was added to Phase A.
  • phase AB was cooled to 45 ° C and gradually added while cooling phase C with stirring.
  • Application Example 6 Hair gel
  • the effect pigment of Example 1 can be used in a range of 0.01 to 2.0 wt .-%, based on the total weight of the Haargel formulation.
  • the balance to 100 wt .-% of the formulation can be made with water.
  • the effect pigment of Example 1 can be used in a range of 0.2 to 5.0% by weight, based on the total weight of the body powder formulation.
  • the compensation for 100% by weight of the formulation can be carried out with Synafil S 1050.
  • Phase A was mixed and then the powder was filled into a suitable container.
  • the effect pigment of Example 1 can be used in a range of 0.10 to 8.00 wt .-%, based on the total weight of the lip gloss formulation.
  • the compensation to 100 wt .-% of the formulation can be done with Versagel ME 750.
  • Phase A was heated to 85 ° C, then the effect pigment from Example 1 of Phase B was added, stirred until a uniform consistency was obtained and then filled into a lip gloss vessel.
  • the effect pigment of Example 1 can be used in the range of 0.5% to 20.0% by weight, based on the total weight of the lipstick formulation.
  • the compensation for 100 wt .-% of the formulation can be done with Eutanol G.
  • Phase A was heated to 85 ° C, then Phase B was added to Phase A and mixed. Subsequently, this mixture was filled at a temperature of 75 ° C in a lipstick form.
  • Application Example 10 Liquid Eyeliner
  • the effect pigment of Example 3 can be used in a range of 0.5 to 8.0 wt .-%, based on the total weight of the eyeliner formulation.
  • the balance to 100 wt .-% of the formulation can be made with water.
  • Optigel WX-PC was dispersed in Phase A water and stirred for 10 minutes. Phase A and Phase B were separately heated to 80 ° C. Thereafter, Phase B was added slowly to Phase A with stirring. After cooling to 45 ° C, the ingredients of Phase C were gradually added and filled into a suitable package.
  • the effect pigment of Example 1 can be used in a range of 0.1 to 8.0 wt .-%, based on the total weight of the mousse formulation.
  • the balance to 100% by weight of the formulation can be made with Dow Corning 9041 Elastomer.
  • Phase A was mixed and heated until everything had melted.
  • Phase B was weighed separately and mixed with a high speed mixer for 60s at 2400 rpm. Half of the molten phase A was added to phase B and mixed again in the blender at 2400 rpm for 30 seconds. Subsequently, the remaining portion of Phase B was also added to Phase A and mixed again at 2400 rpm for 30 seconds. Finally, Phase C is added to Phase AB and mixed again at 2400 rpm for 30 seconds in the high speed mixer.
  • the effect pigment of Example 5 can be used in a range of 0.1 to 8.0 wt .-%, based on the total weight of the nail polish formulation.
  • the balance to 100 wt .-% of the formulation can be done with International Lacquers Nailpolish.
  • Phase A and Phase B were mixed and then filled into an appropriate container.
  • Example 2 Nitrocellulose (and) Isopropyl Alcohol Nailpolish Base 15244 Lacquers
  • the effect pigment of Example 2 can be used in the range of 0.1 to 8.0% by weight, based on the total weight of the nail varnish formulation. The balance to 100 wt .-% of the formulation can be done with International Lacquers Nailpolish.
  • Phase A was mixed, added to Phase B, and then the nail polish was placed in an appropriate container.
  • the pigments of Examples 1 to 6 can be used in an aqueous nail polish according to WO 2007/115675 A2 Example 1.
  • the pigmentation level is in this case 0.1 to 10.0 wt .-%, based on the total weight of the formulation.
  • the effect pigment of Example 3 can be used in the range of 0.10 to 20.00% by weight, based on the total weight of the eyeshadow formulation.
  • the balance to 100 wt .-% of the formulation can be made with water.
  • Phase A was stirred, then the Phase B ingredients were added individually to Phase A and stirred until a uniform consistency was obtained. Thereafter, the ingredients of phase C were added individually to phase AB and stirred until a uniform consistency again resulted.
  • Figure 1 Scanning electron micrograph cross-section of an inventive
  • Figure 4 Section of the scanning electron micrograph cross section of Figure
  • FIG. 2 with a baseline at the interface of non-metallic platelet-shaped substrate.
  • FIG. 5 Scanning electron microscopic cross section of comparative example 3 in FIG.
  • Figure 6 Schematic representation of the distance position.
  • Figure 7 Schematic representation of the position of the spacer layer.

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PCT/EP2015/080859 2014-12-19 2015-12-21 Effektpigmente mit hoher transparenz, hohem chroma und hoher brillanz, verfahren zu ihrer herstellung und verwendung derselben Ceased WO2016097416A1 (de)

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EP15813863.6A EP3234023B1 (de) 2014-12-19 2015-12-21 Effektpigmente mit hoher transparenz, hohem chroma und hoher brillanz, verfahren zu ihrer herstellung und verwendung derselben
KR1020177018329A KR102535159B1 (ko) 2014-12-19 2015-12-21 고 투명도, 고 채도 및 고 휘도를 갖는 효과 안료, 그의 제조 방법 및 그의 용도
JP2017533484A JP6957351B2 (ja) 2014-12-19 2015-12-21 高い透明度、高い彩度、および高い輝度を有する効果顔料、それを生産するための方法、ならびにその使用
US15/536,206 US10934436B2 (en) 2014-12-19 2015-12-21 Effect pigments having high transparency, high chroma and high brilliancy, method for the production and use thereof
CN201580068744.XA CN107109079B (zh) 2014-12-19 2015-12-21 具有高透明性、高色饱和度和高亮度的效应颜料、其制备方法和用途

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EP14199293.3 2014-12-19
EP14199293.3A EP3034564B1 (de) 2014-12-19 2014-12-19 Effektpigmente mit hoher Transparenz, hohem Chroma und hoher Brillanz, Verfahren zu ihrer Herstellung und Verwendung derselben

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US11167375B2 (en) 2018-08-10 2021-11-09 The Research Foundation For The State University Of New York Additive manufacturing processes and additively manufactured products
CN113015512A (zh) 2018-12-27 2021-06-22 莱雅公司 用于护理和/或化妆角蛋白材料的无水组合物
CN110231371A (zh) * 2019-07-15 2019-09-13 新疆大学 一种Au/g-C3N4湿敏材料的制备方法
WO2022018208A1 (en) 2020-07-23 2022-01-27 Eckart Gmbh Solvochromic effect pigments, method of production and use thereof
FR3122334B1 (fr) * 2021-04-30 2024-03-01 Oreal Composition solide comprenant de la cire de tournesol, de la cire de candelilla, des huiles esters non volatiles et son utilisation
KR102641528B1 (ko) * 2021-06-28 2024-02-28 씨큐브 주식회사 개선된 스파클링 효과를 갖는 다중 색상 진주 광택 안료 및 이의 제조방법
IL309612A (en) 2021-07-02 2024-02-01 Heliosonic Gmbh A printing method that induces radiation using a mixture of effect pigments
CN114906855B (zh) * 2022-05-13 2023-03-21 西安工程大学 用于展示指进现象的可视化人造岩芯的制备方法
CN119365550A (zh) 2022-12-22 2025-01-24 埃卡特有限公司 耐候性珠光颜料

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CN107109079B (zh) 2019-10-18
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US10934436B2 (en) 2021-03-02
EP3234023A1 (de) 2017-10-25
US20170349756A1 (en) 2017-12-07
KR20170095915A (ko) 2017-08-23
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CN107109079A (zh) 2017-08-29
SI3034564T1 (en) 2018-05-31
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JP2018507924A (ja) 2018-03-22
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