CN1735562A - A process for the production of porous inorganic materials or a matrix material containing nanoparticles - Google Patents

Abstract

The present invention relates to a process for the production of porous inorganic materials or a matrix material containing nanoparticles with high uniformity of thickness and/or high effective surface area and to the materials obtainable by this process. By the abovementioned process materials with a defined thickness in the region of +-10%, preferably +-5%, of the average thickness are available.

Description

Method for producing porous inorganic or matrix materials containing nanoparticles

The present invention relates to a method for preparing a porous inorganic material or matrix material containing nanoparticles with a very uniform thickness and/or a high effective surface area, and to the material obtained by this method. By the above method, a material is obtained which defines a thickness in the range of ± 10%, preferably ± 5%, of the average thickness.

Spherical monodisperse SiO is known, for example, from US-A-3,634,588₂And (3) granules. It is obtained by hydrolytic polycondensation of an alkoxide compound.

US-B-3,681,017 discloses a process for preparing a film having a length to thickness ratio of at least 5: 1 and a surface area of 400-500m²A method of making microporous platy silica particles, the method comprising:

(a) an ammonium-stable silicic acid solution is formed,

(b) the solution is frozen and the frozen solution is frozen,

(c) the effluent solution containing the tabular silica particles is thawed and then the tabular silica particles are recovered.

EP-A-325484 relates to pearlescent pigments based on metal oxide-coated micｃA particles or other sheet silicate particles which contain dyes or other color pigments. The pearlescent pigment is obtained by the following method: a) preparing a product of the primary stage from sheet silicate particles and a metal oxide coating, b) leaching the thus obtained metal oxide-coated particles with a mineral acid (optionally together with an oxidizing agent), and c) dyeing the thus prepared metal oxide-coated porous particles which are practically free or free of cations with at least one dye or one colored pigment.

EP-A-275668 discloses highly monodisperse, nonporous, spherical SiO with small particle size₂And (3) granules. These particles are prepared by hydrolytic polycondensation of a sol or suspension of tetraalkoxysilane primary particles in a basic medium, with further addition of tetraalkoxysilane being controlled to give the desired final particle size.

JP-A-06-011872 describes spherical SiO₂Subsequent coating of the particles.

WO 01/57287 discloses a process for preparing optical interference pigments in which a metal oxide layer, in particular a titanium dioxide layer, a core layer, in particular a silicon oxide layer, and a metal oxide layer, in particular a titanium dioxide layer, are evaporated in succession onto a support and subsequently separated from the support.

DE-a-4341162 discloses a method for producing a pigmented layer, which comprises simultaneously vapour-depositing a non-absorbent material and an organic dye on a substrate (e.g. glass, metal, ceramic, plastic, etc.) from different vaporizers.

EP-A-803550 describes coating of individual sites with TiO having ｃA particle size of less than 60nm₂、Fe₂O₃Or ZrO₂Spherical SiO with particle size of 5-500nm₂And (3) granules. By passing through SiO₂Adding TiCl to an aqueous dispersion of particles₄Solution preparation of coated SiO₂. The products obtained are used for dyeing paints, printing inks, plastics and coatings or as sunscreens.

US-A-6,103,209 describes A method of preparing porous spherical silicA particles, the method comprising in sequence: emulsifying an acidic silica sol in a dispersion medium in the presence of an emulsifier liquid and a sol-gelling base, gelling droplets of the sol in the emulsified state, and subsequently heat-treating the resulting gel.

US-B-6,335,396 describes silica in the form of a powder and substantially spherical beads or particles, characterized by a CTAB specific surface of 140 and 240m²And porous distribution, the pore volume formed by pores with diameters of 175-275 ANGSTROM is 50% smaller than the pore volume formed by pores with diameters of 400 ANGSTROM or less. The silica can be used as reinforcing filler for elastomers.

It is an object of the present invention to provide a process for preparing a porous inorganic material or matrix material, in particular a porous silica, comprising nanoparticles with a very uniform thickness and/or a high effective surface area, by means of which it is possible to prepare materials with a high degree of plane parallelism and a defined thickness in the range of the average thickness ± 10%, preferably ± 5%, and/or a defined porosity.

The object has been achieved by a method for preparing a porous material, comprising the steps of:

a) vapor depositing a separating agent on the carrier to prepare a separating agent layer,

b) simultaneously vapor-depositing a material and a separating agent on the separating agent layer (a),

c) separating the material from the separating agent.

The term "0.70. ltoreq. y. ltoreq.1.8 SiO_y"refers to the average of oxygen and silicon on a silicon oxide layerThe molar ratio is 0.70-1.80. The composition of the silicon oxide layer can be determined by ESCA (electron spectroscopy for chemical analysis).

The term "0.70. ltoreq. z.ltoreq.2.0 SiO_z"means that the average molar ratio of oxygen to silicon on the silicon oxide layer is 0.70 to 2.0. The composition of the silicon oxide layer can be determined by ESCA (electron spectroscopy for chemical analysis).

According to the present invention, the term "aluminum" includes aluminum and aluminum alloys. Aluminum alloys such as those exemplified by G.Wassermann described in Ullmanns Enzyklopadie der Industriellen Chemie, 4. aflage, Verlag Chemie, Weinheim, Band 7, page 281-. Particularly suitable are the corrosion-resistant aluminum alloys described in WO 00/12634 on pages 10 to 12, which, in addition to aluminum, contain less than 20% by weight, preferably less than 10% by weight, of silicon, magnesium, manganese, copper, zinc, nickel, vanadium, lead, antimony, tin, cadmium, bismuth, titanium, chromium and/or iron.

The term "silicon/silicon oxide layer or sheet" comprises the heating of SiO in an oxygen-free atmosphere at temperatures above 400 deg.C_yOptionally oxidative heat treatment.

The invention relates to porous, sheet-like (plane-parallel) structures (flakes), in particular SiO with a particle length of 1 μm to 5mm, a width of 1 μm to 2mm, a thickness of 20nm to 1.5 μm and a ratio of length to thickness of at least 2: 1_zA flake, the particle having two substantially parallel faces, the distance between the two parallel faces being the shortest axis of the particle. The porous SiO_zThe flakes are mesoporous materials, i.e., the pores have a width of about 2 to about 50 nm. The pores are randomly connected to each other in a three-dimensional manner. Therefore, when used as a catalyst or a carrier, SiO having a two-dimensional pore arrangement can be prevented₂Channel blockage often occurs in the lamellae. Preferably the porous SiO_zThe specific surface of the sheet is more than 500m²A/g, in particular greater than 600m²(ii) in terms of/g. The BET specific surface area is determined according to DIN 66131 or DIN 66132(R.Haul and G.D. mu. mbgen, chem. -Ing. -Techn.32(1960)349 and 35(1063)586) using the Brunauer-Emmet-Teller method (J.Am.chem. Soc.60(1938) 309).

The shape of the flakes of the present invention is not uniform. However, for simplicity, the sheet is considered to have a "diameter". The silicon/silicon oxide flakes have plane parallelism and are defined to have a thickness of + -10%, in particular + -5%, of the average thickness. The thickness of the silicon/silicon oxide thin slice is 20-2000nm, especially 100-500 nm. It is presently preferred that the flakes have a preferred diameter in the range of about 1 to 60 μm, more preferably about 5 to 40 μm, and most preferably about 2 to 20 μm. Thus, it is preferred that the aspect ratio of the flakes of the present invention be from about 2.5 to 625, more preferably from about 50 to 250.

According to the present invention, the separating agent used for the separating agent layer may be different from the separating agent used for the layer (mixed layer) containing the material and the separating agent. Preferably, the separating agent layer is the same as the separating agent used in the mixed layer. The separating agent is preferably removed by dissolving the separating agent in a solvent and subsequently separating the material from the solvent. Alternatively, an organic separating agent can be used, in particular in the mixed layer, which can be distilled off at temperatures up to 250 ℃ under high vacuum. In addition to suitable organic separating agents as described below, organic pigments (e.g. phthalocyanines, diketopyrrolopyrroles, quinacridones) are suitable as organic separating agents.

The sheet-like material can be produced in various and reproducible variants by merely changing two process parameters, namely the thickness of the mixed layer of material and separating agent and the amount of material contained in the mixed layer.

The invention also relates to a porous sheet material, in particular SiO, obtained by the above method_zFlakes, wherein 0.70. ltoreq. z.ltoreq.2.0, in particular 1.4. ltoreq. z.ltoreq.2.0, very particularly z 2.0, and porous SiO_zFlakes wherein 0.70. ltoreq. z.ltoreq.2.0, in particular 0.95. ltoreq. z.ltoreq.2.0, very particularly z 2.0.

FIG. 1 shows the porous SiO obtained in example 1₂Micrographs of the flakes. Pores or cavities larger than nanometers may be identified. It is apparent from FIG. 2 that these pores or cavities are not limited to porous SiO₂The surface of the sheet.

FIG. 2 is a diagram of porous SiO supported with palladium₂Ultra-thin cross-section of the lamellae. The metal (black dots) is located inside the flakes. The size of the metal dots is 1-3 nm.

FIG. 3 shows porous SiO of example 1₂Atomic Force Microscope (AFM) images of the flakes. The maximum pore diameter can reach 30 nm.

According to the invention, the porous sheet-like material is produced by depositing a material/separating agent mixed layer on a separating agent layer. The porosity of the material can be controlled in a simple manner by controlling the amount of separating agent in the mixed layer.

The mixed layer and the separating agent layer are vapor-deposited under vacuum, wherein the separating agent is mixed with the material by simultaneous vapor deposition under vacuum. Typically the mixed layer comprises from 1 to 60% separating agent by total weight of the material and separating agent.

The (porous) material is preferably a metal, a metal oxide, a non-metal oxide or a mixture thereof. Most preferred non-metal oxides are SiO 0.70. ltoreq. z.ltoreq.2.0, especially 1.4. ltoreq. z.ltoreq.2.0_z. The most preferred metal oxide is TiO₂。

Typically, the pore size of the porous material of the present invention is less than 30nm according to high resolution electron microscopy.

The porous material is prepared by a vapor deposition process. The substance to be deposited is heated and vaporized under high vacuum. The vapor condenses on the cold substrate surface to give the desired thin layer. The gasification can take place in a metal vessel (ship-shaped vessel of tungsten, molybdenum or tantalum metal sheet) which is heated directly by a current path or bombarded by an electron beam.

In the case of the use of a sputtering process or of cathodic atomization, a gas discharge (plasma) is triggered between the substrate and the coating material in sheet form (target). Energetic ions from the plasma (e.g., argon ions) bombard the coating and are thus abraded or atomized. The atoms and molecules of the atomized coating deposit on the substrate and form the desired thin layer.

The metal or alloy is particularly suitable for the sputtering process. They can be atomised at a relatively high rate, particularly in a process known as a DC magnetron. High frequency sputtering can also be used to atomize compounds such as oxides, suboxides, or mixtures of oxides. The chemical composition of these layers is determined by the composition of the coating (target). However, the added species in the plasma-forming gas also affect the chemical composition of the layer. In particular, the oxide or nitride layer is prepared by adding oxygen or nitrogen to the gas phase (see, for example, US-A-5,440,446 and EP-A-733919).

The production is very simple if the mixture layer is formed by two evaporators, the vapor beams of which overlap in order to form the mixture layer in the region of the overlap. Alternatively, vapor deposition can be accomplished using a single evaporator that evaporates both components simultaneously or alternately.

Preference is given to using heat-resistant evaporators, evaporators heated with electron beams, evaporators heated inductively or evaporators operated with electric arcs.

To simplify the separation, the support material should have a smooth or structured surface. The movable carrier may consist of one or more discs, cylinders or other rotationally symmetrical bodies rotating about an axis (see WO 01/25500) and preferably consists of one or more continuous metal strips with or without a polymer coating, one or more polyimide or polyethylene terephthalate strips, so that continuous material manufacture is possible (DE 19844357). Polyimide films or metal films or films of combinations of these materials are particularly suitable as support materials.

The release agent vapor-deposited on the support in step a) can be a lacquer (topcoat), a polymer (for example those (thermoplastic) polymers described in U.S. Pat. No. 4, 6,398,999, in particular acrylic or styrene polymers or mixtures thereof), an organic substance which is soluble in organic solvents or water and vaporizable under vacuum (for example anthracene, anthraquinone, acetaminophenol, acetylsalicylic acid, camphoric anhydride, benzimidazole, 1, 2, 4-benzenetricarboxylic acid, 2-biphenyldicarboxylic acid, bis (4-hydroxyphenyl) sulfone, dihydroxyanthraquinone, hydantoin, 3-hydroxybenzoic acid, 8-hydroxyquinoline-5-sulfonic acid monohydrate, 4-hydroxycoumarin, 7-hydroxycoumarin, 3-hydroxy-2-naphthoic acid, isophthalic acid, 4, 4-methylene-bis-3-hydroxy-2-naphthoic acid, 1, 8-naphthalic anhydride, phthalimide and its potassium salt, phenolphthalein, phenothiazine, saccharin and its salts, tetraphenylmethane, benzo [9, 10] phenanthrene, triphenylmethanol, or a mixture of at least two of these). Preferred separating agents are inorganic salts which are soluble in water and evaporable under vacuum (see, for example, DE-A-19844357), such as sodium chloride, potassium chloride, lithium chloride, sodium fluoride, potassium fluoride, lithium fluoride, calcium fluoride, sodium aluminium fluoride and disodium tetraborate.

Preferred embodiments of the present invention are described in detail below:

preferably, the vapor deposition in steps a) and b) is carried out in a vacuum of less than 0.5 Pa. Preferably, the layer of separating agent in step c) is dissolved under a pressure of 1 to 5X 10⁴At Pa, in particular from 600 to 10⁴Pa, more particularly 10³-5×10³Pa.

In a preferred embodiment of the invention, the vacuum is preferably 10 degrees^-1-10^-3Pa, more preferably 1 to 10^-3The following layers were vapour deposited in sequence by thermal evaporation using a PVD process under Pa:

a separating agent layer, and

-a layer of a desired amount of a material mixed with a separating agent on a layer of separating agent, said separating agent being incorporated into said material by simultaneous vapour deposition using two vaporisers or alternatively by vapour deposition using one vaporiser.

In principle, various inorganic materials which can be processed under the conditions of the process according to the invention can be used in the process according to the invention. Preferably, metals, metal oxides and/or non-metal oxides are used.

If the material is a metal oxide, it is preferably chosen from titanium suboxides, zirconium monoxide, niobium oxide, cerium-metal (treated in air to give CeO)₂) Such as a commercially available cerium mixed metal.

If the material is a metal, it is preferably, for example, aluminum, nickel, iron, cobalt, silver, chromium, zirconium, niobium, molybdenum, vanadium, titanium, or an alloy (e.g., chromium-nickel, iron-chromium, nickel-chromium, etc.). The evaporation of the alloy is in fact carried out using different evaporators and by maintaining the desired molar ratio.

A particularly preferred embodiment of the present invention relates to porous SiO_zPreparation of the flakes: the salts (e.g. sodium chloride), the silicon Suboxides (SiO) being successively vapour-deposited on a support_y) A layer and a layer of a separating agent, in particular sodium chloride or an organic separating agent, which carrier may be a continuous metal belt passing through a gasifier under vacuum of less than 0.5 Pa.

Vapor deposition of silicon Suboxides (SiO) using two different vaporizers_y) And a mixed layer of separating agent, each of the vaporizers being charged with one of the two materials and the vapor beams thereof overlapping, wherein the separating agent is contained in the mixed layer in an amount of 1 to 60% by weight based on the total weight of the mixed layer.

The thickness of the vapour-deposited salt is in the range of about 20nm to 100nm, in particular 30 to 60nm, and the thickness of the mixed layer is in the range of 20 to 2000nm, in particular 50 to 500nm, depending on the intended use of the product.

Next, the endless belt-shaped carrier is passed through a dynamic vacuum lock chamber of known construction (see U.S. Pat. No. 6,270,840) into a pressure of 1 to 5X 10⁴Pa, preferably from 600 to 10⁴Pa, especially 10³To 5X 10³A region of Pa in which the strip-like carrier is immersed in the dissolving bath. The temperature of the solvent should be chosen such that its vapor pressure is within a specified pressure range. With the aid of machinery, SiO if the separating agent of the mixed layer is identical to the separating agent of the separating agent layer_zThe separating agent in the layer dissolves rapidly and the product layer breaks into flakes which are subsequently suspended in a solvent. If two different separating agents are used, a step of dissolving the separating agent of the separating agent layer is performed subsequently to the step of dissolving the separating agent of the mixed layer. In a preferred embodiment, the separating agent of the separating agent layer is sodium chloride and the separating agent of the mixed layer is sodium chlorideOrganic separating agents (e.g., phenolphthalein), wherein sodium chloride is dissolved in water or an aqueous solution (e.g., hydrochloric acid), dissolved in an organic solvent (e.g., isopropanol), or sublimed. Next, the tape was dried without any contaminants adhering thereto. The strip is passed through a second set of dynamic vacuum lock chambers into a vaporization chamber where the release agent and SiO are repeatedly applied_yProcess for separating agent product layer.

The suspension obtained in the two steps, containing the product structure and the solvent in which the separating agent is dissolved, is then further separated using known techniques. For this purpose, the product structure is first concentrated in a liquid and washed several times with fresh solvent in order to wash away the dissolved separating agent. The product, still in the form of a wet solid, is then isolated by filtration, precipitation, centrifugation, decantation or evaporation.

SiO is preferred_1.00-1.8The layer is formed by SiO vapor produced by reacting a mixture of Si and silica in a gasifier at a temperature above 1300 ℃.

SiO is preferred_0.70-0.99The layer is formed by evaporating silicon monoxide with a silicon content of up to 20% by weight at above 1300 ℃.

Can be evaporatedDuring which a porous SiO with z greater than 1 is produced by supplying additional oxygen_zA sheet. For this purpose, the vacuum chamber may be provided with a gas inlet through which the oxygen partial pressure in the vacuum chamber can be controlled to a constant value.

Alternatively, the product may be subjected to oxidative heat treatment after drying. Known methods can be used for this purpose. Passing air or some other oxygen-containing gas through SiO in the form of a loose material or in a fluidized bed at temperatures above 200 ℃, preferably above 400 ℃, in particular 500-_y(wherein y is 0.70, particularly 1 to about 1.8, depending on the conditions of vapor deposition). After several hours, all structures will oxidize to SiO₂. The product is then ground or air sieved to the desired particle size and delivered for further use.

The porous SiO_zThe minimum thickness of the lamellae should be 50nm for processing. The maximum thickness depends on the intended use. For applications where optical interference plays an important role, the thickness range is 150-500 nm.

In order to orient the porous plane-parallel structures of silica approximately parallel to the surface of the surface coating or coatings, the surface tension of the structures can be modified by adding known chemicals to the surface coating, for example by commercially available silane oligomers. These oligomers (commercial products) can also be introduced from the liquid phase or by condensation before the plane-parallel structures are added to the surface coatingIs named as DYNASILAN^TM、HYDROSIL^TM、PROTECTOSIL^TM) Directly on the surface of the plane parallel structure. Since the heat resistance of such organic oligomers is limited, it has proven advantageous to oxidize to SiO at temperatures of from 0 ℃ to 250 ℃₂This treatment is carried out afterwards.

In order to improve the abrasion resistance (scuff resistance) and impact resistance of the surface of such surface coatings or dispersions, porous plane-parallel structures of silica may be incorporated into the surface coating or dispersion layer.

In addition, the surface of the porous plane-parallel structure of silicon dioxide can be represented by the formula ClSiX¹X²X³(wherein X¹、X²And X³Represents an organic group and is compatible withSame or different) of conventional silane coupling agents to impart hydrophobicity. Alternatively, the silica surface may be alkylated by the following steps: the silica surface was first chlorinated with thionyl chloride followed by alkyl lithium displacement to introduce alkyl and eliminate lithium chloride (J.D. Sunseri et al, Langmuir 19(2003) 8608-8610).

In another embodiment, the invention relates to porous, sheet-like SiO comprising (1-y/y + a) silicon_y+aParticles in which 0.70. ltoreq. y.ltoreq.1.8, in particular 1.0. ltoreq. y.ltoreq.1.8, 0.05. ltoreq. a.ltoreq.1.30, the sum of y and a being less than or equal to 2.

Porous SiO_y+aFlakes, in particular SiO comprising (1-y/y + a) silicon nanoparticles₂The flakes may be produced by exposure to a temperature of greater than 400 deg.C (especially 400-1100 deg.C), an oxygen-free atmosphere (i.e., an argon or helium atmosphere), or less than 13Pa (10 Pa)^-1Torr) porous SiO was heated under vacuum_yAnd (4) obtaining the particles.

It is assumed that SiO is formed by heating SiO in an oxygen-free atmosphere_yParticles of SiO_yDisproportionation into SiO₂And Si:

in this disproportionation reaction, porous SiO containing (1- (y/y + a)) Si is produced_y+aFlakes, wherein 0.70. ltoreq. y.ltoreq.1.8, in particular 0.70. ltoreq. y.ltoreq.0.99 or 1. ltoreq. y.ltoreq.1.8, 0.05. ltoreq. a.ltoreq.1.30 and the sum of y and a is equal to or less than 2, SiO_y+aIs a low oxide of silicon that is oxygen-rich. SiO is preferred_yComplete conversion to Si and SiO₂：

Amorphous silicon is formed at temperatures in the range of 400-900 deg.C. Microcrystalline silicon is formed at temperatures in the range of 900-. The average size of the crystallites is in the range from 1 to 20nm, in particular from 2 to 10 nm. In one aspect, the size is temperature dependent. That is, the crystallites formed at 1100 ℃ are larger than those formed at 900 ℃. On the other hand, SiO was found_yThe higher the oxygen content, the moreThere is a clear tendency to form smaller crystallites. According to the preparation method, Si-containing plane-parallel SiO_y+aParticles, in particular SiO₂The particles may exhibit photoluminescence.

The minimum thickness of the porous silicon/silicon oxide flakes should be 50nm for processing. The maximum thickness depends on the intended use. For applications where optical interference plays an important role, the thickness range is 150-500 nm.

Known materials for containing mica and/or SiO can be used₂The general procedure for the central effect pigment deposition of the further layers necessary for optical interference, which will be described below by means of porous SiO_zThe sheet is described in detail.

It is also possible to start the porous SiO from its surface_yIs converted into silicon carbide (SiC) (in the context of the present application, this step is referred to as "carburization"). For this purpose, planar parallel porous SiO, preferably in the form of bulk material, can be introduced into a gas-tight reactor heatable up to about 1500 ℃ at 1500-_yThe structure and a carbon-containing gas, optionally mixed with an oxygen-containing compound such as an aldehyde, ketone, water, carbon monoxide, carbon dioxide, and the like or mixtures thereof, react and preferably expel oxygen, the carbon-containing gas being selected from the group consisting of alkynes (e.g., acetylene), alkanes (e.g., methane), alkenes, aromatics, and the like, and mixtures thereof. To make the reaction milder, an inert gas (e.g., argon or helium) may be mixed with the carbon-containing gas. In this carburizing process, all SiO_yCan be reacted to form SiC, preferably 5 to 90% by weight of SiO_yReact to form SiC.

The invention therefore also relates to plane-parallel structures (pigments) based on porous plane-parallel silicon oxide substrates whose surfaces comprise a silicon carbide-containing layer (SiC). SiO 2_yThe reaction to SiC occurs initially at the surface of the plane parallel structure and is thus a step-wise conversion rather than a sharp change. This means that in this embodiment the SiC-containing layer consists of (silicon/silicon oxide)_aAnd (SiC)_bComposition wherein 0 < a < 1,0 < b < 1, b is 1 at the surface of the pigment, a is 0, and the amount of SiC is close to 0 at the boundary adjacent the silicon/silicon oxide substrate.

May be at least about 200 ℃ and up to about 400 ℃Further oxidizing the SiO remaining in the plane-parallel structure with an oxygen-containing gas (e.g., air)_y。

If possible, after the carbide formation has ended, optionally at least 200 ℃ with an oxygen-containing gas (e.g. air) without destroying the SiC formed, the plane-parallel structure remainsSiO of (2)_yOxidation to SiO₂. In this case, the temperature should not exceed about 400 ℃ in the presence of oxygen, due to the large specific surface area of the plane-parallel structure.

Porous (carburised) silicon oxide flakes, preferably 50-2000nm thick, are novel and are a further subject of the present invention. In order to obtain the property of selective reflection in the infrared, the flakes can be used, for example, as a corrosion-inhibiting additive in coatings having a mohs hardness of 8 to 9 or as a corrosion-inhibiting additive in coating compositions. Furthermore, the porous (carburised) silicon oxide flakes can be used as substrates for optical interference pigments. The pigments are stable to high shear and have a high degree of color saturation and good fastness in plastics, surface coatings or printing inks and, in the case of light interference pigments, a high degree of color flop (see, for example, PCT/EP 03/01323).

Due to their high chemical and thermal stability, large surface area and good compatibility with other materials, the porous silica flakes can be used in many applications, for example in the field of selective separations (M.Asasda, S.Yamasaki, Separation of inorganic/organic gases mixtures using porous silica membranes), Sep.Purif.Technol.25(2001)151-159), catalysts (H.Suquet, S.Chemier, C.Marcilly, D.Barthomef, Preparation of porous materials by chemical activation of the Lanovernite, Miny.26 (1991) 49-60; Y.Deg, C.Lettamann, W.F.Leaching, left in Leaching.Leaching.Leaching.and Ti.31-free porous catalysts (Ti.P.S.A. Alternatives, Ti, P.31-31, P.A. Alternate, Ti, P.S.A. porous catalysts, Ti. porous membranes, P.S.A. Alternate. Alternatives, C.B.M.S.M. Marville, C.M.S. Marville, C.S.S. Marville.M.S. A. 1, A. Leaching. A. A, (iii) Maschmeyer, Synthesis of synthetic Porous silica with a controlled pore size distribution of silica lenses over various lengths), Catal. today 69(2001)331-335), dielectric materials (A. Jain, S. Rogojevic, S. Ponoth, N. Agarwal, I.Matthew, W.N.Gill, P.Persans, M.Tomowa, J.L.Plawsky, E.Monoyi, Porus silicon materials as low-k dielectric for electrical and optical connections, Thin. medium as a Porous silica material for electrical and optical connections, Thin. Sol. 398 (Ki. K.for repair of medical gases as well as coating for medical use of silica with electrical and optical connections), Thin. major, Synthesis of Porous silica with a controlled pore size distribution of silica lenses, N.Agarwal, I.Matthew.G. 69(2001), Gem.K.20. Thin. TM. silica as a coating for medical use of electrical and optical connections, Thin. Thermojun. Mel. 21. Mel. As a coating for medical use of silica for electrical and optical connections, Thin. Melamine (K. Thin. 21. Melamine) as a coating for medical use of silica, Thin. 21. Thin. 21, K, T.Takei, S.Hayashi, A.Yas. mu. moi, K.J.D.MacKenzie, Preparation of microporosius silicon from metaolite by selective leaching method microporous leaching method (microporous silica prepared from diaspore), microporosius mesoparticle Mater.21(1998) 289), heavy metal ion adsorbents (B.Lee, Y.Kim, H.Lee, J.Yi, Synthesis of functionalized microporosius silicon via templating method as heavy metal adsorbents: the introduction of the interfacial hydrophilicity on to the surface of adsorbents by the template method, Microporous Mesoporous Mater.50(2001)77-90), molecular sieves (US-B-5,958,368), as drug delivery vehicles exhibiting sustained release effects (J.F.Chen, H.M.Ding, J.X.Wang, L.Shao, Biomaterials 25(2004) 723-: preparation and application for enzymatic ring-opening polymerization of cyclic phosphates (immobilization of lipases on porous silicｃA beads: preparation and use of cyclic phosphates), Reactive functional Poly.47(2001)153-89), in particular as support for catalyst systems (for example for olefin polymerization or Suzuki coupling), or as reinforcing filler for elastomers (in particular tires or silicone rubbers) (see, for example, U.S. Pat. No. 5, 6,335,396 and EP-A-407262).

Apparently SiO_zThe flakes are ideal supports for catalyst metals such as copper or nickel-based reforming catalysts or palladium-based catalysts for Suzuki reactions. These particles have a very high surface area (about 700 m)²/g) and porosity in nanometer size (2-50 nm).

In a particularly preferred embodiment of the invention, the porous SiO_zThe sheet serves as an ink-receptive layer for the imageable medium. Thus, the invention also relates to an imageable medium, said imageable mediumThe imaging medium comprises a support and a porous SiO-containing layer_zA sheet wherein 0.70. ltoreq. z.ltoreq.2.0, particularly 1.40. ltoreq. z.ltoreq.2.0, and an ink-receptive layer of a hydrophilic binder.

In the present invention, it is preferable that the total amount of the porous silica sheet used for the ink-receiving layer is 2 to 30g/m². The above range is preferable in view of ink absorbability and strength of the ink-receptive layer.

As the support used in the present invention, a plastic resin film (e.g., polyethylene, polypropylene, polyvinyl chloride, diacetate resin, triacetate resin, cellophane, acrylic resin, polyethylene terephthalate, polyethylene naphthalate, etc.), a water-resistant support (e.g., resin-coated paper in which a polyolefin resin is laminated on both sides of the paper), or a water-absorbent support (e.g., high-quality paper, coated paper, chrome-coated paper, etc.) can be used. Preferably, a water resistant carrier is used. These supports are preferably used in a thickness of about 50 to 250 μm.

Hydrophilic binders are added to the ink-receptive layer of the present invention to maintain film-forming characteristics. As the hydrophilic adhesive to be used, those conventionally known in general of various types can be used, and it is preferable to use a hydrophilic adhesive having high transparency and imparting high ink permeability. In the case of using a hydrophilic binder, it is important that the hydrophilic binder does not block the voids due to swelling at the initial stage of ink penetration. From this viewpoint, it is preferable to use a hydrophilic adhesive having less swelling property at about room temperature. One particularly preferred hydrophilic binder is fully or partially saponified polyvinyl alcohol or cationically modified polyvinyl alcohol.

Among these polyvinyl alcohols, partially or completely saponified polyvinyl alcohols having a saponification rate of 80% or more are particularly preferred. Polyvinyl alcohol having an average polymerization degree of 500-5000 is preferable.

Also, as the cation-modified polyvinyl alcohol, for example, there can be mentioned polyvinyl alcohol having a primary to tertiary amine group or a quaternary ammonium group in the main chain or side chain of polyvinyl alcohol disclosed in japanese provisional patent publication No. 10483/1986.

Likewise, other hydrophilic binders may be used in combination, but are preferably used in an amount of 20% or less than 20% by weight of the polyvinyl alcohol.

In the ink-receptive layer of the present invention, porous SiO is preferred₂The weight ratio of particles to hydrophilic binder is from 60: 40 to 92: 8, more preferably from 70: 30 to 90: 10.

The ink-receptive layer of the present invention may contain other inorganic fine particles in addition to the porous silica sheet in an amount of about 30% or less than 30% by weight of the porous silica sheet.

In the present invention, it is preferable that the ink-receiving layer B contains fine particles having an average particle diameter of 3 to 10 μm. As the fine particles, inorganic or organic fine particles, preferably organic resin fine particles, can be used. By adding the above fine particles to the ink-receiving layer B, uneven gloss can be overcome when printing is performed using pigment ink.

Embodiments of the present invention are possible in which the ink-receptive layer comprises other particulate and/or fine particulate materials. Examples of materials that may be suitable for certain uses include calcium carbonate, fumed silica, precipitated silica, alumina, alkyl quaternized bentonite, alkyl quaternized montmorillonite, clay, kaolin, talc, titanium dioxide, chalk, bentonite, aluminum silicate, calcium silicate, magnesium carbonate, calcium sulfate, barium sulfate, silica, barium carbonate, boehmite, pseudoboehmite, alumina, aluminum hydroxide, diatomaceous earth, calcined clay, and the like. Other particles may perform various functions (including ink retention). The various functions of the particles are, for example, colour filling, lubrication, uv absorption, whitening, heat stabilisation etc.

As the above-mentioned organic resin fine particles, there may be mentioned, for example, olefin homopolymers or copolymers (such as polyethylene, polypropylene, polyisobutylene, polyoxyethylene, polytetrafluoroethylene, polystyrene, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylate copolymer, ethylene-vinyl acetate copolymer and the like or derivatives thereof), polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, vinyl chloride- (meth) acrylate copolymer, polyvinylidene chloride, styrene-butadiene rubber, NBR rubber and the like, and one kind of organic resin particles or a mixture of plural kinds of resin particles may be used alone. Incidentally, (meth) acrylic acid or (meth) acrylate herein means acrylic acid and/or methacrylic acid, or acrylate and/or methacrylate.

Preferably, each layer of the ink-receptive layer of the present invention may contain a cationic compound for enhancing water resistance. As the cationic compound, there can be mentioned a cationic polymer and a water-soluble metal compound. As the cationic polymer, there may be mentioned preferably polyethyleneimine, polydiallylamine, polyallylamine, polyalkylamine, and polymers containing primary to tertiary amine groups or quaternary ammonium salt groups. Preferably, these cationic polymers have a molecular weight (weight average molecular weight Mw) of from about 5,000 to about 100,000.

As the water-soluble metal compound used in the present invention, for example, a water-soluble polyvalent metal salt can be mentioned. Metals in the water-soluble salts which may be mentioned are selected from calcium, barium, manganese, copper, cobalt, nickel, aluminium, iron, zinc, zirconium, titanium, chromium, magnesium, tungsten and molybdenum. More specifically, mention may be made of salts such as calcium acetate, calcium chloride, calcium formate, calcium sulfate, barium acetate, barium sulfate, barium phosphate, manganese chloride, manganese acetate, manganese formate dihydrate, manganese ammonium sulfate hexahydrate, copper chloride, copper (II) chloride ammonium dihydrate, copper sulfate, cobalt chloride, cobalt thiocyanate, cobalt sulfate, nickel sulfate hexahydrate, nickel chloride hexahydrate, nickel acetate tetrahydrate, nickel ammonium sulfate hexahydrate, nickel ammonium sulfate tetrahydrate, aluminum sulfate, aluminum sulfite, aluminum thiosulfate, poly (aluminum chloride), aluminum nitrate nonahydrate, aluminum chloride hexahydrate, ferrous bromide, ferrous chloride, ferric sulfate, ferric bromide, zinc chloride, zinc nitrate hexahydrate, zinc sulfate, titanium chloride, titanium sulfate, zirconium acetate, zirconium chloride, zirconium oxychloride octahydrate, zirconium oxychloride basic chloride, zinc sulfate, titanium chloride, titanium sulfate, zirconium acetate, zirconium chloride, zirconium oxychloride octahydrate, and the like, Zirconium nitrate, basic zirconium carbonate, zirconium hydroxide, zirconium lactate, ammonium zirconium carbonate, potassium zirconium carbonate, zirconium sulfate, zirconium fluoride, chromium acetate, chromium sulfate, magnesium chloride hexahydrate, magnesium citrate nonahydrate, sodium phosphotungstate (sodium phosphotungstate), sodium tungsten citrate, dodecatungstophosphate n-hydrate, dodecatungstopilicate hexachlorohydrate, molybdenum chloride, dodecamolybdophosphate n-hydrate, and the like. Among these compounds, a zirconium-based compound having high transparency and water resistance improving effect is preferably used.

The ink receptive layer of the present invention may contain a variety of oil droplets to increase the brittleness of the film. As such oil droplets, hydrophobic high boiling point organic solvents (e.g., liquid paraffin, dioctyl phthalate, tris (tolyl) phosphate, silicone oil, etc.) or polymer particles (e.g., particles in which at least one polymerizable monomer such as styrene, butyl acrylate, divinylbenzene, butyl methacrylate, hydroxyethyl methacrylate, etc. is polymerized) having a solubility in water at room temperature of 0.01% by weight or less than 0.01% by weight may be contained. Such oil droplets may be used in an amount of 10-50% by weight of the hydrophilic adhesive.

In the present invention, a crosslinking agent (curing agent) of a hydrophilic binder may be used in the ink-receiving layer. Specific examples of the curing agent may include aldehyde compounds (e.g., formaldehyde and glutaraldehyde), ketone compounds (e.g., butanedione and chloropentanedione, bis (2-chloroethylureido) -2-hydroxy-4, 6-dichloro-1, 3, 5-triazine), compounds having an active halogen as disclosed in U.S. Pat. No. B-3,288,775, divinylsulfone, compounds having an active olefin as disclosed in U.S. Pat. No. 3,635,718, N-methylol compounds as disclosed in U.S. Pat. No. B-2,732,316, isocyanate compounds as disclosed in U.S. Pat. No. B-3,103,437, cycloethylenimine compounds as disclosed in U.S. Pat. Nos. B-3,017,280 and 2,983,611, carbodiimide compounds as disclosed in U.S. Pat. No. B-3,100,704, epoxy compounds as disclosed in U.S. B-3,091,537, halocarboxaldehyde compounds (e.g., mucochloric acid), Dioxane derivatives (dihydroxydioxane) and inorganic curing agents (such as chromium vanadium, zirconium sulfate, boric acid and borate), may be used singly or in combination of two or more kinds thereof.

Among the above curing agents, boric acid and borate are particularly preferable. As boric acid which can be used in the present invention, orthoboric acid, metaboric acid, hypoboric acid and the like can be mentioned, and as boric acid salts, sodium salts, potassium salts and ammonium salts thereof can be mentioned. Preferably, the boric acid or borate is present in the ink receptive layer in an amount of from 0.5 to 80% by weight of the polyvinyl alcohol.

In the present invention, various generally known additives such as a coloring dye, a coloring pigment, a fixing agent for ink dye, an ultraviolet absorber, an antioxidant, a dispersing agent for pigment, a defoaming agent, a leveling agent, a preservative, a fluorescent whitening agent, a viscosity stabilizer, a pH buffer, and the like may be added to each layer of the ink absorbing layer in addition to the curing agent.

The imageable media of the present invention can be used to make identification cards, driver's licenses, passports, and the like. In a preferred embodiment, the image receptive material is adapted to accept an image comprised of an aqueous ink. In a particularly preferred embodiment, the image-receptive material is suitable for receiving an image comprised of an aqueous pigmented ink suitable for use in an ink jet printer. The printed image of the present invention preferably comprises one or more security markings. Examples of security marks that may be suitable for some uses include a picture of a person's face, a person's fingerprint, a bar code, and/or a signature of a cardholder.

Porous SiO loaded with organic or inorganic pigments_zThe flakes form transparent easily dispersible granules. The inorganic pigment includes: in particular those selected from the group consisting of metal oxides, antimony yellow, lead chromate sulfate, lead molybdate, ultramarine blue, cobalt blue, manganese blue, chromium oxide green, chromium oxide hydrate green, cobalt green and metal sulfurCompounds such as cerium sulfide or cadmium sulfide, cadmium sulfoselenide, zinc ferrite, bismuth vanadate, and mixed metal oxides. Examples of useful organic pigments (and substituted derivatives thereof) are described, for example, in w.herbst, k.hunger, industrille Organische pigment, 2 nd full revision, VCH 1995: 1-aminoanthraquinone pigment: 503 page 511; anthraquinone pigment:pages 504 and 506, pages 513 and 521 and 530; anthrapyrimidine: 513 and 415 pages; azo pigments: pages 219- & 324 & 380- & 398; azomethine pigment: 402-411 pages; quinacridone pigment: 462-481 page; quinacridonequinone pigment: 467-468; quinophthalone pigment: 567 page 570; diketopyrrolopyrrole pigments: page 570-574; dioxazine pigments: 531-538 pages; flavanthrone pigments: 517 + 519 pages, 521 pages; indanthrone pigment: 515 + 517 pages; isoindoline pigment: page 413-429; isoindolinone pigments: page 413-429; iso-and blue-ketone pigments: 528-530 pages; souleline (perinone) pigment: 482-492 pages; perylene pigments: 482-; phthalocyanine pigment: 431- "460 pages"; pyranthrone pigment: 522 page 526; thioindigo pigment (indigo pigment): 497-500. mixtures of these pigments, including solid solutions, may also be used. The term "pigment" also includes luminescent substances. Such SiO_zThe sheet can be obtained, for example, by the following method: by dissolving SiO in a medium in which the pigment is soluble, e.g. concentrated sulfuric acid_zMixing the flakes with an organic pigment, precipitating the pigment by adding a medium which does not dissolve the pigment (e.g. water), filtering off the colored SiO_zAnd (4) slicing and drying. Pigment-loaded porous SiO_zThe flakes can be used to color a substrate (e.g., a high molecular weight organic material).

Porous SiO, preferably loaded with pigments_zThe flakes may be prepared by filling with a so-called latent pigment and converting the latent pigment into a pigment form. Processes for coloring porous materials with latent pigments and also preferred latent pigments are described, for example, in EP-A-648770, EP-A-648817, EP-A-764628, EP-A-761772, EP-A-1086984, WO 98/32802, WO00/63297 and PCT/EP 03/10968.

The latent pigments are generally of the formula A (B)_x(I) Wherein:

x is an integer of 1 to 8,

a is the following chromophore: quinacridone, anthraquinone, perylene, indigo, quinophthalone, indanthrone, isoindolinone, isoindoline, dioxazine, azo, phthalocyanine or diketopyrrolopyridine series, which are linked to group x, group B, by one or more heteroatoms selected from nitrogen, oxygen and sulfur and forming part of group a.

B is a group of the formula:

when x is a number from 2 to 8, each group B may be the same or different, and

l is any desired group suitable for imparting water solubility.

L is preferably a group of the formula:

or

Wherein Y is¹、Y²And Y³Each independently is C₁-C₆An alkyl group, a carboxyl group,

Y⁴and Y⁸Each independently is C₁-C₆Alkyl by oxygen, sulfur or N (Y)¹²)₂Spaced C₁-C₆Alkyl, or unsubstituted or substituted by C₁-C₆Alkyl-, C₁-C₆Alkoxy-, halogen-, cyano-or nitro-substituted phenyl or biphenyl radicals,

Y⁵、Y⁶and Y⁷Each independently is hydrogen or C₁-C₆An alkyl group, a carboxyl group,

Y⁹is hydrogen, C₁-C₆Alkyl or a group of the formula:

or

Y¹⁰And Y¹¹Each independently is hydrogen, C₁-C₆Alkyl radical, C₁-C₆Alkoxy, halo, cyano, nitro, N (Y)¹²)₂Or unsubstituted or substituted by halogen-, cyano-, nitro-, C₁-C₆Alkyl-or C₁-C₆An alkoxy-substituted phenyl group, wherein the phenyl group is substituted with an alkoxy group,

Y¹²and Y¹³Is C₁-C₆Alkyl radical, Y¹⁴Is hydrogen or C₁-C₆Alkyl, and Y¹⁵Is hydrogen, C₁-C₆Alkyl or unsubstituted or substituted by C₁-C₆An alkyl-substituted phenyl group, which is substituted,

q is unsubstituted or substituted by C₁-C₆Alkoxy radical, C₁-C₆Alkylthio radicals or radicals bound to C₂-C₁₂-dialkylamino mono-or polysubstituted p, q-C₂-C₆Alkylene, wherein p and q are different numbers of digits,

x is a heteroatom selected from nitrogen, oxygen and sulfur, and when X is oxygen or sulfur, m is 0, when X is nitrogen, m is 1, and

L¹and L²Each independently of the other being unsubstituted or substituted by-C₁-C₁₂Alkoxy-, -C₁-C₁₂Alkylthio-, -C₂-C₂₄Dialkylamino-, -C₆-C₁₂Aryloxy-, -C₆-C₁₂Arylthio-, -C₇-C₂₄alkylarylamino-or-C₁₂-C₂₄Diarylamino mono-or polysubstituted C₁-C₆Alkyl or [ - (p ', q' -C)₂-C₆Alkylene) -Z-]_n-C₁-C₆Alkyl, n is a number from 1 to 1000, p 'and q' are different numbers of digits, Z is each independently a heteroatom of oxygen, sulfur or C₁-C₁₂Alkyl-substituted nitrogen, and at [ -C₂-C₆alkylene-Z-]C in the repeating unit₂-C₆The alkylene groups may be the same or different,

and L is¹And L²Can be full ofAnd or 1-10 times unsaturated, optionally interrupted or in any position substituted by 1-10 substituents selected from- (C ═ O) -and-C₆H₄-which may be free of further substituents or contain 1 to 10 further substituents selected from halogen, cyano and nitro. Preferred are compounds of formula (I) wherein: l is C₁-C₆Alkyl radical, C₂-C₆Alkenyl or

Wherein Q is C₂-C₄Alkylene group, and

L¹and L²Is [ -C₂-C₁₂alkylene-Z-]_n-C₁-C₁₂Alkyl or by C₁-C₁₂Alkoxy radical, C₁-C₁₂Alkylthio or C₂-C₂₄Dialkylamino mono-or polysubstituted C₁-C₁₂Alkyl, m and n are as defined above.

Particular preference is given to compounds of the formula (I) in which: l is C₄-C₅Alkyl radical, C₃-C₆Alkenyl or

Wherein Q is C₂-C₄Alkylene, X is oxygen, m is 0, and L¹Is [ -C₂-C₁₂alkylene-O-]_n-C₁-C₁₂Alkyl or is substituted by C₁-C₁₂Alkoxy mono-or poly-substituted C₁-C₁₂Alkyl, especially those in which-Q-X-is of the formula-C (CH)₃)₂-CH₂-O-group compounds.

Suitable examples of compounds of formulｃA (I) are disclosed in EP-A-0648770, EP-A-0648817, EP-A-0742255, EP-A-0761772, WO 98/32802, WO 98/45757, WO 98/58027, WO 99/01511, WO 00/17275, WO 00/39221, WO00/63297 and EP-A-1086984.

The pigment precursors may be used alone or may also be used in admixture with other pigment precursors or with colorants such as conventional dyes for the intended uses described above.

A is a basic structure A (H)_xWherein A is preferably inHaving at least one directly attached or conjugated carbonyl group on each heteroatom attached to group x, group B, for example compounds of the formula:

or

Wherein, for example, Z is:

or

And x "is a number from 1 to 16, in particular from 1 to 4;

particularly noteworthy are those water-soluble chromophores of the formula A (H)_xThe pigment of (a) is pigment yellow 13, pigment yellow 73, pigment yellow 74, pigment yellow 83, pigment yellow 93, pigment yellow 94, pigment yellow 95, pigment yellow 109, pigment yellow 110, pigment yellow 120, pigment yellow 128, pigment yellow 139, pigment yellow 151, pigment yellow 154, pigment yellow 175, pigment yellow 180, pigment yellow 181, pigment yellow 185, pigment yellow 194, pigment orange 31, pigment orange 71, pigment orange 73, pigment red 122, pigment red 144, pigment red 166, pigment red 184, pigment red 185, pigment red 202, pigment red 214, pigment red 220, pigment red 221, pigment red 222, pigment red 242, pigment red 248, pigment red 254, pigment red 255, pigment red 262, pigment red 264, pigment brown 23, pigment brown 41, pigment brown 42, pigment blue 25, pigment blue 26, pigment blue 60, pigment blue 64, pigment yellow in the color indexViolet 19, pigment violet 29, pigment violet 32, pigment violet 37, 3, 6-bis (4' -cyano-phenyl) -2, 5-dihydro-pyrrolo [3, 4-c ]]Pyrrole-1, 4-dione, 3, 6-bis (3, 4-dichloro)-phenyl) -2, 5-dihydro-pyrrolo [3, 4-c]Pyrrole-1, 4-dione or 3-phenyl-6- (4' -tert-butyl-phenyl) -2, 5-dihydro-pyrrolo [3, 4-c]Pyrrole-1, 4-dione. Other examples are described by Willy Herbst and Klaus Hunger in "Industrial organic Pigments" (ISBN 3-527-.

The alkyl or alkylene group may be a straight chain alkyl or alkylene group, a branched chain alkyl or alkylene group, a monocyclic or polycyclic alkyl group or an alkylene group.

Thus, C₁-C₁₂Alkyl is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, cyclobutyl, n-pentyl, 2-pentyl, 3-pentyl, 2-dimethylpropyl, cyclopentyl, cyclohexyl, n-hexyl, n-octyl, 1, 3, 3-tetramethylbutyl, 2-ethylhexyl, nonyl, trimethylcyclohexyl, decyl, menthyl, ramie, bornyl, 1-adamantyl, 2-adamantyl or lauryl.

When C is present₂-C₁₂When the alkyl group is mono-or polyunsaturated, it is C₂-C₁₂Alkenyl radical, C₂-C₁₂Alkynyl, C₂-C₁₂Polyalkenyl (alkapolyenyl) or C₂-C₁₂Polyalkynyl (alkapolyynyl), where appropriate with two or more double bonds which may be isolated or conjugated, is, for example, vinyl, allyl, 2-propen-2-yl, 2-buten-1-yl, 3-buten-1-yl, 1, 3-butadien-2-yl, 2-cyclobuten-1-yl, 2-penten-1-yl, 3-penten-2-yl, 2-methyl-1-buten-3-yl, 2-methyl-3-buten-2-yl, 3-methyl-2-buten-1-yl, 1, 4-pentadien-3-yl, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl, 3-cyclohexen-1-yl, 2, 4-cyclohexadien-1-yl, 1-p-menthen-8-yl, 4(10) -limonene-10-yl, 2-norbornen-1-yl, 2, 5-norbornadien-1-yl, 7-dimethyl-2, 4-norbomadiene (norcaradien) -3-yl, and the various isomers of hexenyl, octenyl, nonenyl, decenyl, and dodecenyl.

C₂-C₄Ethylene is, for example, 1, 2-ethylene, 1, 2-propylene, 1, 3-propylene, 1, 2-butylene, 1, 3-butylene, 2, 3-butylene1, 4-butylene and 2-methyl-1, 2-propylene. C₅-C₁₂Alkylene is for example the isomers of pentylene, hexylene, octylene, decylene or dodecylene.

C₁-C₁₂Alkoxy being O-C₁-C₁₂Alkyl, preferably O-C₁-C₄An alkyl group.

C₆-C₁₂Aryloxy being O-C₆-C₁₂Aryl, such as phenoxy or naphthoxy, preferably phenoxy.

C₁-C₁₂Alkylthio being S-C₁-C₁₂Alkyl, preferably S-C₁-C₄An alkyl group.

C₆-C₁₂The arylthio group being S-C₆-C₁₂Aryl, for example phenylthio or naphthylthio, preferably phenylthio.

C₂-C₂₄Dialkylamino is N (alkyl 1) (alkyl 2) and the total number of carbon atoms in the two groups alkyl 1 and alkyl 2 is 2-24, preferably N (C)₁-C₄Alkyl) -C₁-C₄An alkyl group.

C₇-C₂₄The alkylarylamino group is N (alkyl 1) (aryl 2), the two radicals alkyl 1 and aryl 2 having a total number of carbon atoms of from 7 to 24, for example methylphenylamino, ethylnaphthylamino or butylphenanthrylamino, preferably methylphenylamino or ethylphenylamino.

C₁₂-C₂₄The diarylamino group is N (aryl 1) (aryl 2), and the total number of carbon atoms in the two groups aryl 1 and aryl 2 is 12 to 24, and is, for example, diphenylamino or phenylnaphthylamino, preferably diphenylamino.

Halogen is chlorine, bromine, fluorine or iodine, preferably fluorine or chlorine, in particular chlorine.

Preferably, the following method is used, which comprises:

a) adding porous SiO to a solution of a latent pigment_zThe particles are selected from the group consisting of,

b) precipitating the latent pigment on the carrier particles, and

c) the latent pigment is subsequently converted into a pigment (PCT/EP 03/10968).

In a preferred embodiment, for example first at a temperature of from 20 ℃ up to the boiling point of the solvent, will for example

Is completely soluble in an organic solvent (e.g., a mixture of THF and ethanol). The solvent is subsequently added to the porous SiO prepared beforehand_zA suspension of the particles and stirring at a temperature of 20 ℃ up to the boiling point of the solvent for 5-60 minutes. Followed by vigorous stirring at 10-A solvent in which the latent pigment is poorly soluble, typically water, is slowly added dropwise to the mixture over 120 minutes, thereby depositing the latent pigment on the carrier particles. Stirring is continued for 10-120 minutes. The latent pigment pigmented carrier particles are subsequently filtered, washed and dried.

The pigment precursor is converted into its pigmentary form by fragmentation under well-known conditions (e.g. heating), optionally in the presence of other catalysts (e.g. as described in WO 00/36210).

Light interference can be observed if the pores of the flakes are filled with an organic pigment, and thus the color of the pigment can be changed if the thickness of the flakes is in the range of 200-500 nm. If the pore size is less than 50nm, the organic pigment-loaded flakes are transparent.

The pores of the flakes may also be filled with an inorganic pigment (e.g., iron oxide) and thus may be black, yellow, or red in color. These flakes can be readily dispersed in an organic binder. Iron oxide-loaded SiO according to the phase of iron oxide_zThe flakes may be magnetic. SiO loaded with magnetic iron oxide additionally coated with Ag_zThe foil can be used for electromagnetic shielding, for example.

Further, the porous SiO_zThe flakes, and in particular the pores of these flakes, can be coated with carbon (e.g., diamond-like carbon and amorphous carbon) from the gas phase by plasma assisted deposition using Plasma Enhanced Chemical Vapor Deposition (PECVD) or by magnetron sputtering (see, e.g., US-B-6,524,381). The plasma deposition may be carried out, for example, at room temperature and a pressure of 1-50X 10³Pa using argon as buffer or inert gas, methane, ethylene or acetylene as process gas and optionally in the presence of a doping gas.

The invention therefore also relates to a porous SiO-based coating with carbon, in particular diamond-like carbon_zPlane parallel structure of the substrate (pigment). If carbon is not only present in the pores but also forms a layer, the thickness of the carbon layer is 10-150 nm.

Further, the porous SiO_zThe flakes, and in particular the pores of the flakes, may be filled with oxides of the elements titanium, iron or zirconium.

In this case, the SiO_zThe pores of the flakes have a pore size of less than 30nm, thus giving a highly translucent product with high absorption and reflection in the ultraviolet region. For example, by passing through SiO_zAdding titanium tetrachloride solution to the aqueous dispersion of the flakes, and separating the coated SiO_zFlakes, dried and optionally calcined to give the particles. Or hydrolyzing titanium tetrachloride with hydrochloric acid at 0-60 deg.C to obtain rutile type nanometer powder with particle diameter of 1-50nmTiO₂(R.J.Nussba. mu. mer, W.Caseri, T.Tervor and P.Smith, Journal of Nanoparticle Research 2002, 4, 319-. Optionally hydrolyzing Ti (OiPr) with water at 0-50 deg.C₄(tetraisopropyl titanate), followed by removal of the isopropanol formed at 50-100 deg.C under low vacuum (about 200 torr) to produce nano TiO in anatase form having a particle size of 10-40nm₂(crystallite size less than 10nm) (K.I. Gnanasekar et al, Journal of Materials Research 2002, 17(6), 1507-. The titanic acid solution may be added to SiO_zIn a dilute solution of flakes, the titanic acid solution is prepared by hydrolyzing titanium tetrachloride with ammonium hydroxide, followed by H₂O₂And (4) oxidizing to obtain the catalyst. The nano TiO of anatase type with the particle size of about 10nm is spontaneously obtained from the solution by heating at the temperature of 100-250 DEG C₂Particles (H.Ichinose, M.Terasaki and H.Katsuki, Journal of the Ceramic society of Japan, int.edition 1996, 104(8), 715-. While such solutions and dispersions are also commercially available (Kon Corporation, 91-115 Miyano Yamauchi, Kishimagun Sa)ga-prefecture, Japan 849-. SiO loaded with oxides of titanium, zirconium and iron_zThe flakes may be coated with organic or inorganic compounds using known methods. Coated with TiO₂SiO of (2)_zThe flakes can be used as a medium where high translucency is important, for example as a sunscreen in varnishes, paints, plastics or glass and/or cosmetic formulations. Furthermore, with coated SiO_zThe flakes can be used for the coloration of paints, printing inks, plastics and coatings (see for example EP-A-803550). Coated with TiO₂(particularly TiO in the anatase form)₂) SiO of (2)_zThe flakes can have photocatalytic activity. Thus, such sheets exhibit self-cleaning and disinfecting properties upon exposure to ultraviolet radiation. These properties make these sheets useful for sterilization, hygiene and medical applications.

Coated rutile modified TiO₂SiO of (2)_zThe flakes are useful as highly efficient, translucent, little or no photoactive ultraviolet light absorbers, for example, for cosmetics (e.g., sun block), automotive or wood varnishes, and the like. In addition to the UV protection, this SiO_zThe sheet may also improve scratch resistance as well as improve other physical properties (e.g., modulus of elasticity).

According to the invention, the term "coated with TiO₂(or any other material) of SiO_zFlakes "or" coated with TiO₂SiO of (2)_zFlakes "comprising the entire surface coated with TiO₂SiO of (2)_zThe lamellae, pores, or parts of the pores being filled with TiO₂SiO of (2)_zThe flakes and/or individual parts being coated with TiO₂SiO of (2)_zA sheet.

If color is desired, the color effect of pigments is usually adjusted by:

adjusting the TiO₂The thickness of the layer(s) is,

adjusting the thickness of the intermediate layer, and

-adjusting the composition of the intermediate layer.

As described in PCT/EP03/50690, TiO-coated films of 0.70. ltoreq. y.ltoreq.1.8, in particular 1.1. ltoreq. y.ltoreq.1.5, can be initially coated at a temperature of more than 600 ℃ in an oxygen-free atmosphere₂SiO of (2)_yFlake calcinationThen, where appropriate, treating the TiO-coated substrate with air or another oxygen-containing gas at a temperature of above 200 ℃, preferably above 400 ℃ and in particular at 500-₂SiO of (2)_yAnd (3) slicing.

Suppose that TiO is calcined in a non-oxidizing atmosphere₂/SiO_yAn intermediate layer is produced which causes a change in the refractive index. However, it is also contemplated that the intermediate layer may not be a continuous layer, and may simply be TiO₂With SiO_yIndividual regions of the interface undergo transformations which cause a change in the refractive index. It is also hypothesized that the refractive index change is due to TiO₂Is coated with SiO_yAnd (4) reducing. The principle of the invention is therefore based on the use of SiO_yReduction of TiO₂An intermediate layer is prepared that causes a change in the refractive index.

Porous SiO if intermediate layers are not intended to be formed_yThe flakes must be coated with TiO₂Is previously oxidized to SiO₂. It cannot be excluded at present that the temperature of the reaction mixture is controlled by heating at a temperature above 400 ℃ and in particular at 400-1100 ℃ in an oxygen-free atmosphere, i.e.in an argon or helium atmosphere, or at a pressure of less than 13Pa (10 Pa)^-1Torr) vacuum heating of TiO₂/SiO_yParticles other than TiO₂Is coated with SiO_yOutside of reduction, SiO_yAlso disproportionated to SiO₂And Si (PCT/EP 03/50229).

In this disproportionation reaction, SiO containing (1- (y/y + a)) Si is produced_y+aFlakes, wherein 0.70. ltoreq. y.ltoreq.0.99 or 1.0. ltoreq. y.ltoreq.1.8, 0.05. ltoreq. a.ltoreq.1.30, in particular 0.05. ltoreq. a.ltoreq.1.0, and the sum of y and a is equal to or less than 2, SiO_y+aIs a low oxide of silicon that is oxygen-rich.

If the SiO is_zThe flakes carrying the doped material (e.g. tin doped indium oxide as described in example 5 of WO 02/31060) give SiO with high infrared absorption_zA sheet.

If the SiO is_zFlake supported SnO₂、Sb₂O₃/SnO₂、In₂O₃Or In₂O₃/SnO₂Then SiO with high infrared reflection capability can be obtained_zFlakes (see US-B-4,548,836).

For the preparation of the optical interference pigments, the process of the invention can be modified in the following manner: depositing a further layer of metal or metal oxide between the two mixed layers of material and separating agent and/or, in the case of an asymmetric layer structure of the pigment, before the mixed layer of material and separating agent.

The invention therefore also relates to platelet-shaped pigments comprising a layer of a porous material, in particular SiO 0.70. ltoreq. z.ltoreq.2.0_z。

Particularly preferred are pigments comprising:

(a) a metal, in particular an aluminium centre,

(b) SiO optionally on the aluminum center_zA layer, and

(c) on the aluminum center or the SiO_zPorous SiO on a layer_zLayer, wherein 0.70. ltoreq. z.ltoreq.2.0, e.g. porous SiO_zAl/porous SiO_zPorous SiO_z/SiO_z/Al/SiO_zPorous SiO_zWherein the less preferred asymmetric structure is, for example, porous SiO_z/Al/SiO_zOr SiO_z/Al/SiO_zPorous SiO_z。

Preferably, the metal is selected from Ag, Al, Au, Cu, Cr, Ge, Mo, Ni, Si, Ti or alloys thereof. Most preferably Al.

Preferably porous SiO_zLayer (c) comprises an inorganic or organic colorant, such as a dye or an inorganic or organic pigment, especially an organic pigment.

In this embodiment, particular preference is given to pigments comprising, in this order:

(c1) porous SiO_zA layer (thickness of 40-60nm, in particular about 50nm),

(b1)SiO_zlayer (thickness)From 20 to 500nm),

(a) an aluminum center (thickness of 40-60nm, especially about 50nm),

(b2)SiO_za layer (thickness of 20-500nm), and

(c2) porous SiO_zLayers (thickness 40-60nm, in particular about 50nm), where 1.40. ltoreq. z.ltoreq.2.0, in particular 2, where layers (c1) and (c2) comprise dyes or inorganic or organic pigments, in particular organic pigments. The pigments may optionally be coated with a protective layer of a low refractive index material, in particular SiO₂. The pigments are characterized by high chroma due to incorporation into the porous layerAbsorption of the pigment and interference colors of the pigment.

Also particularly preferred are pigments comprising in order:

(a) porous SiO_zA layer;

(b)SiO_za layer, and

(c) optional porous SiO_zLayer, wherein 0.70. ltoreq. z.ltoreq.2.0, preferably by wet-chemical coating of a metal oxide with a high refractive index, in particular TiO₂. That is, the center of the pigment is composed of porous SiO_z/SiO_zOr porous SiO_z/SiO_zPorous SiO_zThe sheet is formed.

The porous SiO_z/SiO_zThe foil is prepared by a PVD process comprising the steps of:

a) vapor-depositing a separating agent on a (mobile) carrier to prepare a separating agent layer,

b) vapor deposition of SiO on a separating agent layer_yAnd a mixed layer of a separating agent,

c) vapor deposition of SiO on the mixed layer_yA layer, wherein y is more than or equal to 0.70 and less than or equal to 1.80,

d) optionally in SiO_yVapor deposition of SiO on a layer_yAnd a mixed layer of a separating agent,

e) a layer of a separating agent dissolved in a solvent, and

f) porous SiO separated from solvent_z/SiO_zA sheet.

Pores of the porous layerThe interstices may be filled with an inorganic pigment as described above, so that it may combine the interference colour with the absorption of the pigment. According to SiO_zThe layer thickness of the layer allows a very high saturation.

The porous SiO_zFlakes, in particular having an effective refractive index of less than SiO₂And between 1.25 and 1.40 of SiO with a refractive index (n ═ 1.46)₂The thin slice can replace SiO₂Flakes or layered silicate flakes (e.g., mica, montmorillonite, talc, etc.) are used as substrates for optical interference pigments.

The present invention therefore also relates to pigments comprising (a) a metal oxide of high refractive index, typically particles having a length of from 1 μm to 5mm, a width of from 1 μm to 2mm, a thickness of from 50nm to 1.5 μm and a ratio of length to thickness of at least 2: 1, wherein the particles comprise porous SiO having two substantially parallel planes_zPorous SiO_z/SiO_z、SiO_zPorous SiO_z/SiO_zOr porous SiO_z/SiO_zPorous SiO_zA center (0.70. ltoreq. z.ltoreq.2.0, in particular 1.1. ltoreq. z.ltoreq.2.0, very particularly 1.4. ltoreq. z.ltoreq.2.0), the distance between two substantially parallel planes being the shortest axis of the center; or pigments comprising (a) a thin translucent metal layer, the particles of which are generally 1 μm in length5mm, 1 μm-2mm in width, 50nm-1.5 μm in thickness and a length to thickness ratio of at least 2: 1, wherein the particles have two substantially parallel planar porous SiO_zPorous SiO_z/SiO_z、SiO_zPorous SiO_z/SiO_zOr porous SiO_z/SiO_zPorous SiO_zThe center (0.70. ltoreq. z.ltoreq.2.0, in particular 1.1. ltoreq. z.ltoreq.2.0, very particularly 1.4. ltoreq. z.ltoreq.2.0), the distance between two essentially parallel planes being the shortest axis of the center.

Suitable metals for the semi-transparent metal layer are, for example, Cr, Ti, Mo, W, Al, Cu, Ag, Au or Ni. The thickness of the semitransparent metal layer is usually 5 to 25nm, in particular 5 to 15 nm. May be in SiO alone_yThe substrate has a metal layer on one parallel side, but preferably the metal layer is present on both parallel sides of the substrate.

Alternatively, the metal layer may be obtained by wet chemical coating or chemical vapor deposition (e.g., by vapor deposition of a metal carbonyl compound). The metal layer is deposited on the substrate by adding a reducing agent in the presence of a metal compound by suspending the substrate in an aqueous and/or organic solvent containing medium. The metal compound is, for example, silver nitrate or nickel acetylacetonate (WO 03/37993).

According to U.S. Pat. No. 4,3,536,520, nickel chloride is used as the metal compound and hypophosphite is used as the reducing agent. According to EP-A-353544, the following compounds can be used as reducing agents for wet-chemical coating processes: aldehydes (formaldehyde, acetaldehyde, benzaldehyde), ketones (acetone), carboxylic acids and their salts (tartaric acid, ascorbic acid), reductones (erythorbic acid, triose reductone, reducing acids) and reducing sugars (glucose).

If a semi-transparent metal layer is desired, the thickness of the metal layer is typically 5-25nm, especially 5-15 nm.

If pigments of metallic appearance (opaque metallic layers) are desired, the thickness of the metallic layer is from > 25nm to 100nm, preferably from 30 to 50 nm. If colored metallic effect pigments are desired, colored or colorless metal oxides, metal nitrides, metal sulfides, and/or other layers of metals may be deposited. These layers are transparent or translucent. It is preferred that the high refractive index layers alternate with the low refractive index layers, or that there is a layer in which the refractive index changes gradually. The weathering resistance can be increased by additional coatings, which at the same time can be made most suitable for adhesive systems (EP-A-268918 and EP-A-632109). Porous coated with e.g. Ag or NiSiO_zThin sheets are conductive, such as may be used for metallization of hybrid microcircuits, solar cells, superconducting circuits, and large area electronic structures such as by inkjet printing.

In a preferred embodiment of the present invention, the optical interference pigment comprises a material having a "high" refractive index (high refractive index as defined herein means a refractive index greater than about 1.65) and optionally a material having a "low" refractive index (low refractive index as defined herein means a refractive index of about 1.65 or less than 1.65). The various materials (dielectrics) that can be used include inorganic materials (e.g., metal oxides, suboxides of metals, metal fluorides, metal oxyhalides, metal sulfides, metal chalcogenides, metal nitrides, metal oxynitrides, metal carbides, combinations thereof, and the like) as well as organic dielectric materials. These materials are readily available and are readily applied by physical or chemical vapor deposition processes or by wet chemical coating processes.

In a particularly preferred embodiment, the substrate is based on porous silica (including porous SiO)_zPorous SiO_z/SiO_z、SiO_zPorous SiO_z/SiO_zAnd porous SiO_z/SiO_zPorous SiO_z) The optical interference pigments of (a) further comprise a layer of a dielectric material of "high" refractive index (i.e., a refractive index greater than about 1.65, preferably greater than about 2.0, and most preferably greater than about 2.2) applied to the entire surface of the silicon/silica substrate. Examples of such dielectric materials are zinc sulfide (ZnS), zinc oxide (ZnO), zirconium oxide (ZrO)₂) Titanium dioxide (TiO)₂) Carbon, indium oxide (In)₂O₃) Indium Tin Oxide (ITO) and tantalum pentoxide (Ta)₂O₅) Chromium oxide (Cr)₂O₃) Cerium oxide (CeO)₂) Yttrium oxide (Y)₂O₃) Europium oxide (Eu)₂O₃) Iron oxides such as iron (II)/(III) oxide (Fe)₃O₄) And Iron (III) oxide (Fe)₂O₃) Hafnium nitride (HfN), hafnium carbide (HfC), hafnium oxide (HfO)₂) Lanthanum oxide (La)₂O₃) Magnesium oxide (MgO), neodymium oxide (Nd)₂O₃) Praseodymium oxide (Pr)₆O₁₁) Samarium oxide (Sm)₂O₃) Antimony trioxide (Sb)₂O₃) Silicon monoxide (SiO), selenium trioxide (Se)₂O₃) Tin oxide (SnO)₂) Tungsten trioxide (WO)₃) Or a combination thereof. Preferably, the dielectric material is a metal oxide. The metal oxide may be a single oxide or a mixture of oxides with or without absorbing properties, e.g. TiO₂、ZrO₂、Fe₂O₃、Fe₃O₄、Cr₂O₃Or ZnO, particularly preferably TiO₂。

Or by reaction with TiO₂Coating a layer of a low refractive index metal oxide (e.g. SiO)₂、Al₂O₃、AlOOH、B₂O₃Or mixtures thereof, preferably SiO₂) And in the metal oxideCoating another TiO on the layer₂Layers (EP-A-892832, EP-A-753545, WO 93/08237, WO 98/53011, WO 98/12266, WO 98/38254, WO 99/20695, WO00/42111 and EP-A-1213330) result in pigments which are more intensely coloured and more transparent. Non-limiting examples of useful low refractive index dielectric materials are: silicon dioxide (SiO)₂) Alumina (Al)₂O₃) Metal fluorides (e.g., magnesium fluoride (MgF)₂) Aluminum fluoride (AlF)₃) Cerium fluoride (CeF)₃) Lanthanum fluoride (LaF)₃) Sodium aluminum fluoride (e.g., Na)₃AlF₆Or Na₅Al₃F₁₄) Neodymium fluoride (NdF)₃) Samarium fluoride (SmF)₃) Barium fluoride (BaF)₂) Calcium fluoride (CaF)₂) Lithium fluoride (LiF), and mixtures thereof) or any other low refractive index material having a refractive index of about 1.65 or less than 1.65. Organic monomers and polymers useful as low refractive index materials are, for example, dienes or alkenes (e.g., acrylates such as methacrylates), polymers of perfluoroalkenes, polytetrafluoroethylene (TEFLON), polymers of Fluorinated Ethylene Propylene (FEP), parylene, p-xylene, combinations thereof, and the like. The above materials also include evaporated, condensed and cross-linked clear acrylate layers that can be deposited by the methods described in US-B-5,877,895, the disclosure of which is incorporated herein by reference.

Thus, preferred optical interference pigments comprise, in addition to (a) a metal oxide of high refractive index, (b) a metal oxide or non-metal oxide of low refractive index, wherein the difference in refractive index is at least 0.1.

Porous silicon oxide (SiO) -based coating that has been applied by wet chemical coating_z) The pigments of the substrate are particularly preferably in the following order: t isiO₂(substrate: silicon oxide; layer: TiO)₂Preferably rutile modification), (SnO₂)TiO₂、Fe₂O₃、Fe₃O₄、TiFe₂O₅、Cr₂O₃、ZrO₂、Sn(Sb)O₂、BiOCl、Al₂O₃、Ce₂S₃、MoS₂、Fe₂O₃、TiO₂(substrate: silicon oxide; Fe₂O₃And TiO₂Mixed layer of) TiO₂/Fe₂O₃(substrate: silicon oxide; first layer: TiO)₂(ii) a A second layer: fe₂O₃)、TiO₂/Berlin blau、TiO₂/Cr₂O₃Or TiO₂/FeTiO₃. The layer thickness is generally from 1 to 1000nm, preferably from 1 to 300 nm.

In another particularly preferred embodiment, the present invention relates to optical interference pigments comprising at least three alternating layers of high and low refractive index, for example TiO₂/SiO₂/TiO₂、(SnO₂)TiO₂/SiO₂/TiO₂、TiO₂/SiO₂/TiO₂/SiO₂/TiO₂Or TiO₂/SiO₂/Fe₂O₃. The preferred layer structure is as follows:

(A) a coating having a refractive index greater than 1.65,

(B) a coating having a refractive index of 1.65 or less,

(C) a coating having a refractive index greater than 1.65, and

(D) an optional outer protective layer.

The respective layer thicknesses of the high and low refractive index layers on the base substrate are important for the optical properties of the pigment. The thickness of the individual layers, in particular of the metal oxide layers, depends on the field of use and is generally from 10 to 1000nm, more preferably from 15 to 800nm, in particular from 20 to 600 nm.

The thickness of the layer (A) is from 10 to 550nm, preferably from 15 to 400nm, in particular from 20 to 350 nm. The thickness of the layer (B) is from 10 to 1000nm, preferably from 20 to 800nm, in particular from 30 to 600 nm. The thickness of the layer (C) is from 10 to 550nm, preferably from 15 to 400nm, in particular from 20 to 350 nm.

Particularly suitable materials for layer (A) are metal oxides, metal sulfides or metal oxide mixtures, such as TiO₂、Fe₂O₃、TiFe₂O₅、Fe₃O₄、BiOCl、CoO、Co₃O₄、Cr₂O₃、VO₂、V₂O₃、Sn(Sb)O₂、SnO₂、ZrO₂Iron titanates, iron oxide hydrates, titanium suboxides (reduced titanium species having an oxidation state of from 2 to < 4), bismuth vanadates, cobalt aluminates and mixtures thereof, or mixed phases of these compounds with one another or with other metal oxides. Preferably the metal sulphide coating is selected from the group consisting of tin, silver, lanthanum, rare earth metal sulphides, preferably cerium, chromium, molybdenum, tungsten, iron, cobalt and/or nickel sulphides.

Particularly suitable materials for layer (B) are metal oxides or corresponding oxide hydrates, such as SiO₂、MgF₂、Al₂O₃、AlOOH、B₂O₃Or mixtures thereof, preferably SiO₂。

Particularly suitable materials for layer (C) are colourless or non-ferrous metal oxides, such as TiO₂、Fe₂O₃、TiFe₂O₅、Fe₃O₄、BiOCl、CoO、Co₃O₄、Cr₂O₃、VO₂、V₂O₃、Sn(Sb)O₂、SnO₂、ZrO₂Iron titanates, iron oxide hydrates, titanium suboxides (reduced titanium species having an oxidation state of from 2 to < 4), bismuth vanadates, cobalt aluminates and mixtures thereof, and also mixed phases of these compounds with one another or with other metal oxides. The TiO is₂The layer may also comprise a material that may be coated with an absorbing material (e.g., carbon), selectively absorb a colorant, selectively absorb a metal cation, may be coated with an absorbing material, or may be partially reduced.

There may be an intermediate layer of absorbent or non-absorbent material between layers (a), (B), (C) and (D). The thickness of the intermediate layer is 1 to 50nm, preferably 1 to 40nm, in particular 1 to 30 nm.

In this embodiment, preferred optical interference pigments have the following layer structure:

porous SiOz	TiO2	SiO2	TiO2
				Porous SiOz	TiO2	SiO2	Fe2O3
Porous SiOz	TiO2	SiO2	TiO2/Fe2O3
				Porous SiOz	TiO2	SiO2	(Sn，Sb)O2
Porous SiOz	(Sn，Sb)O2	SiO2	TiO2
				Porous SiOz	Fe2O3	SiO2	(Sn，Sb)O2
Porous SiOz	TiO2/Fe2O3	SiO2	TiO2/Fe2O3
				Porous SiOz	TiO2	SiO2	MoS2
Porous SiOz	TiO2	SiO2	Cr2O3
				Porous SiOz	Cr2O3	SiO2	TiO2
Porous SiOz	Fe2O3	SiO2	TiO2
				Porous SiOz	TiO2	Al2O3	TiO2
Porous SiOz	Fe2TiO5	SiO2	TiO2
				Porous SiOz	TiO2	SiO2	Fe2TiO5/TiO2
Porous SiOz	TiO suboxide	SiO2	TiO suboxide
				Porous SiOz	TiO2	SiO2	TiO2+SiO2+TiO2+ Prussian blue
Porous SiOz	TiO2	SiO2	TiO2+SiO2+TiO2
				Porous SiOz	TiO2+SiO2+TiO2	SiO2	TiO2+SiO2+TiO2

The pigments of the invention are characterized by porous SiO_zA precisely defined thickness of the lamella and a smooth surface. The porous opaque or translucent silicon/silicon oxide flakes can replace transparent porous SiO_zThe flakes are used as substrates for optical interference pigments.

The metal oxide layer may be applied by CVD (chemical vapor deposition) or wet chemical coating. The metal oxide layer can be obtained by decomposing the metal carbonyl compound in the presence of water vapor (for the use of lower molecular weight metal oxides such as magnetite) or oxygen and, where appropriate, water vapor (for the use of, for example, nickel oxide and cobalt oxide). The metal oxide layer can be applied in particular by the following method: oxidative gas-phase decomposition of metal carbonyls (e.g.iron pentacarbonyl, chromium hexacarbonyl; EP-A-45851), or hydrolytic gas-phase decomposition of metal alcoholates (e.g.tetrｃA-n-propanol/titanium/zirconium tetraisopropoxide; DE-A-4140900) or metal halides (e.g.titanium tetrachloride; EP-A-338428), or oxidative decomposition of organotin compounds (in particular alkyltin compounds, such as tetrabutyltin and tetramethyltin; DE-A-4403678), or gas-phase hydrolysis of organosilicon compounds (in particular di-tert-butoxyacetoxysilanes) as described in EP-A-668329. The coating operation can be carried out in ｃA fluidized-bed reactor (EP-A-045851 and EP-A-106235).

According to the passivation method described in DE-A-4236332 and EP-A-678561, the metal oxide-halide (e.g. CrO) is decomposed by hydrolysis or oxidation in the gas phase₂Cl₂、VOCl₃) In particular oxyhalides of phosphorus (e.g. POCl)₃) Phosphoric acid and phosphites (e.g. dimethyl/ethyl phosphite and trimethyl/ethyl phosphite) and amino-containing organosilicon compounds (e.g. 3-aminopropyl-triethoxy/trimethoxysilane) to produce chromate-and/or titanate-containing and silica-containing metal oxide layers.

The oxides of the metals zirconium, titanium, iron and zinc are preferably applied by wet-chemical methods; hydrated oxides of these metals; titanates of iron; layers of titanium suboxides or mixtures thereof, where appropriate, can reduce the metal oxide. In the case of wet chemical coating methods, wet chemical coating methods developed for the preparation of pearlescent pigment products can be used, and these methods are described in: DE-A-1467468, DE-A-1959988, DE-A-2009566, DE-A-2214545, DE-A-2215191, DE-A-2244298, DE-A-2313331, DE-A-2522572, DE-A-3137808, DE-A-3137809, DE-A-3151343, DE-A-3151354, DE-A-3151355, DE-A-3211602, DE-A-3235017, DE-A-1959988, WO 93/08237, WO 98/53001 and WO 03/6558.

Preferably, the high refractive index metal oxide is TiO₂And/or iron oxide, preferably the low refractive index metal oxide is SiO₂。TiO₂The layer may be a rutile modification or an anatase modification, with the rutile modification being preferred. There may be used, for example, EP-A-735, 114, DE-A-3433657, DE-A-4125134, EP-A-332071, EP-A-707, 050 or WO 93/19131Known processes are described (e.g. ammonia, hydrogen, hydrocarbon vapour or mixtures thereof or metal powders) for the reduction of TiO₂And (3) a layer.

For coating, the substrate particles are suspended in water and one or more hydrolysable metal salts are added at a pH suitable for hydrolysis, the pH being chosen such that the metal oxide or hydrated metal oxide precipitates directly on the particles without secondary precipitation (subfirectionalization). The pH is generally kept constant by simultaneous metered addition of base. The pigment is then isolated, washed, dried, and calcined, as appropriate, the calcination temperature being optimized for the particular coating. If desired, the pigments can be isolated, dried and, where appropriate, calcined and resuspended after the respective coating has been applied in order to precipitate further layers.

The metal oxide layer can also be prepared by a sol-gel process by controlled hydrolysis of one or more metal acid esters in the presence of a suitable organic solvent and a basic catalyst, using a process similar to that described in, for example, DE-A-19501307. Suitable basic catalysts are, for example, amines (e.g. triethylamine, ethylenediamine, tributylamine, dimethylethanolamine and methoxypropylamine). The organic solvent being a water-miscible organic solvent, e.g. C_1-4Alcohols, in particular isopropanol.

Suitable metal acid esters are selected from alkyl and aryl alcoholates of vanadium, titanium, zirconium, silicon, aluminium and boron, carboxylates of vanadium, titanium, zirconium, silicon, aluminium and boron, carboxy-, alkyl-or aryl-substituted alkyl alcoholates or carboxylates of vanadium, titanium, zirconium, silicon, aluminium and boron, preferably triisopropyl aluminate, tetraisopropyl titanate, tetraisopropyl zirconate, tetraethyl orthosilicate and triethyl borate.

According to one embodiment of the present invention, it is preferred to use titanium dioxide as the high refractive index metal oxide, and the method of coating the titanium dioxide layer is described in US-B-3553001.

The aqueous solution of the titanium salt is slowly added to the suspension of the material to be coated which has been preheated to about 50 to 100 c, in particular 70 to 80 c, the pH being kept substantially constant at about 0.5 to 5, in particular about 1.2 to 2.5, by simultaneous metered addition of a base, for example an aqueous ammonia solution or an aqueous alkali metal hydroxide solution. Once the desired thickness of TiO is achieved₂And precipitating the layer, and stopping adding the titanium salt solution and the alkali.

This method (also called "titration" method) differs in that an excess of titanium salt is avoided. This is achieved by adding only hydrated TiO to the hydrolysate per unit time₂Required for uniform coatingThe amount of titanium salt and the amount per unit time that can be adsorbed by the active surface of the particles to be coated. TiO formed in principle in the anatase form on the surface of the starting pigment₂. But by adding small amounts of SnO₂The rutile structure may be forced. For example, as described in WO 93/08237, tin dioxide may be deposited prior to the precipitation of titanium dioxide and the titanium dioxide-coated product calcined at 800-900 ℃.

Optionally reducing the TiO by conventional methods as described in the following documents₂：US-B-4,948,631(NH₃，750-850℃)、WO 93/19131(H₂At > 900 ℃ or DE-A-19843014 (solid reducing agents, for example silicon, > 600 ℃).

The following method may be suitably used on TiO₂Coating SiO on the layer₂(protective) layer: a metered quantity of soda water glass solution is added to the suspension of the material to be coated which has been heated to about 50 to 100 ℃, in particular 70 to 80 ℃, the pH being maintained at 4 to 10, preferably 6.5 to 8.5, by simultaneous addition of 10% hydrochloric acid, and stirring is carried out for a further 30 minutes after the addition of the water glass solution has been completed.

Can be prepared by reacting with TiO₂The layer is coated with a metal oxide (e.g., SiO) having a low refractive index (i.e., a refractive index of less than about 1.65)₂、Al₂O₃、AlOOH、B₂O₃Or mixtures thereof, preferably SiO₂) Then coating a layer of Fe on the metal oxide layer₂O₃And/or TiO₂Layer, resulting in a more intensely colored and more transparent pigment. Such multicoat optical interference pigments comprising a porous silica substrate or a porous silica/silica substrate and alternating layers of metal oxides of high and low refractive index can be prepared in a manner similar to that described in WO 98/53011 and WO 99/20695.

Furthermore, the color of the pigment powder can be improved by applying further layers, for example colored metal oxides, berlin blue, compounds of transition metals (e.g. Fe, Cu, Ni, Co, Cr) or organic compounds (e.g. dyes or lakes).

In addition, the pigments of the invention may also be coated with sparingly soluble, firmly adhering inorganic or organic colorants. Preference is given to using lakes, in particular aluminum lakes. In order to precipitate the aluminium hydroxide lake layer, in a second step, precipitation is carried out using lakes (DE-A-2429762 and DE-A-2928287).

Furthermore, the pigments according to the invention may also have an additional coating which is coated with complex salt pigments, in particular with cyanoferrate complexes (EP-A-141173 and DE-A-2313332).

According to DE-A-4009567, the pigments according to the invention can also be coated with organic dyes, in particular phthalocyanines or metallophthalocyanines and/or indanthrene dyes. A suspension of the pigment is prepared in a solution of the dye and a solvent is added that does not dissolve the dye. Furthermore, metal chalcogenides and/or metal chalcogenide hydrates and carbon black may be used for the additional coating.

The multilayer silicon oxide sheet may be surface-treated for the purpose of improving weather resistance and light resistance, depending on the application. Useful surface treatment methods are described, for example, in the following documents: DE-C-2215191, DE-A-3151354, DE-A-3235017, DE-A-3334598, DE-A-4030727, EP-A-649886, WO 97/29059, WO 99/57204 and US-A-5,759,255. The surface treatment may also facilitate handling of the pigment, especially for incorporation into various application media.

In the case of multilayer pigments, the interference color is determined by the intensification of certain wavelengths, and if two or more of the layers in a multilayer pigment have the same optical thickness, the color of the reflected light is fuller and more intense as the number of layers increases. Furthermore, a particularly strong change in the hue as a function of the viewing angle can be achieved by a suitable choice of the layer thicknesses. A pronounced flop is present, which is required for the pigments according to the invention. The thickness of the individual metal layers, which is independent of their refractive index, is therefore from 20 to 500nm, in particular from 50 to 300 nm.

The number of layers and layer thicknesses depends on the desired effect. If TiO is used₂/SiO_z/TiO₂Three-layer systems, with optically synchronized layer thicknesses of the individual layers, can achieve the desired effect. By using optically thinner TiO₂And SiO₂Layers (layer thickness < 100nm) can be prepared, for example, as pure TiO₂Substantially low TiO of mica pigment₂Content and more intensely coloured and transparent pigments. By depositing thick SiO₂Layers (layer thickness > 100nm) which give pigments which change particularly strongly in hue as a function of the viewing angle.

By depositing other TiO₂And SiO₂Layers, five or more layer systems are available, but the number of layers is limited by cost. By using porous SiO of uniform thickness_zThe wafer or porous silicon/silicon oxide wafer is used as a substrate to achieve a precisely defined interference effect.

In this case, the optical interference system is obtained by applying, for example, 3 layers of the above-described structure (7 thin layers of precisely defined thickness) to the substrate. The reflection and/or transmission spectra of such pigments exhibit a more precise and precisely adjustable structure compared with the spectra of corresponding pigments based on substrates having a wide distribution of thickness, such as mica.

These contain very thin (layer thickness < 50nm) TiO₂The pigments of the layer have been shown to be intenseAnd (4) interference colors. The flop of the interference color is also very pronounced.

The (effect) pigments according to the invention are characterized by high gloss and very uniform thickness, so that high color purity and high color strength are achieved.

The (effect) pigments of the invention can be used for all customary purposes, for example for pigmenting polymers, paints (including effect finishes, effect finishes for automobiles) and printing inks (including offset, gravure, bronzing and flexographic printing), and can be used, for example, in cosmetics, ink-jet printing, textile dyeing, glazing of ceramics and glass, and laser marking of paper and plastics. Such uses are described in references such as "industrille Organische Pigmente" (W.Herbst and K.Hunger, VCH Verlagsgesellschaft mbH Weinheim/New York, 2 nd full revision, 1995).

Another subject of the invention is a process for preparing a matrix material loaded with nanoparticles. The method comprises the following steps:

a) vapor depositing a separating agent on the carrier to prepare a separating agent layer,

b) followed by vapor deposition of a base material and a nanoparticle-forming material simultaneously on the separating agent layer (a),

c) separating the material from the separating agent, in particular by dissolving the separating agent in a solvent,

d) optionally separating the nanoparticle-laden matrix material from the solvent.

This method basically adopts the method as described above except that the material forming the matrix and the material forming the nanoparticles are evaporated, instead of evaporating the materials and the separating agent.

In principle, any material that can be evaporated under high vacuum can be used as the matrix material or the material forming the nanoparticles. Metal oxides and non-metal oxides and also monomers, oligomers or polymers which are substantially transparent in the visible region are preferably used as matrix material. In order to reduce light scattering by the nanoparticle-laden material, it is desirable that the refractive index of the nanoparticle-laden material be the same as the refractive index of the material (e.g., coating, paint, etc.) into which the nanoparticle-laden material is to be incorporated. The refractive index of the nanoparticle-loaded material may be slightly different (in particular not more than 0.3 units) from the refractive index of the material into which the nanoparticle-loaded material is to be incorporated.

In a preferred embodiment of the invention, said radicalsThe bulk material being non-metallic oxygenCompounds, in particular transparent SiO of 1.4. ltoreq. z.ltoreq.2.0_z. Since the product is not visible even in surface coatings having water transparency (because the refractive indices are almost identical), this matrix material is particularly suitable as an additive in abrasion-resistant (scratch-resistant) coatings. SiO 2_zThe function of the flakes is determined by the incorporated nanoparticles.

The flakes prepared by the process of the invention can also be further surface-treated by known methods in order to obtain hydrophobicity, hydrophilicity or antistatic properties or to couple them with organic compounds. The plane parallel structure is oriented parallel to the surface of the article being coated and forms a solid layer on the surface of the surface coating after the following treatment.

In another preferred embodiment, the matrix material is a component of a high molecular weight organic material (particularly a paint, ink or coating) that is vaporizable under vacuum and that can be processed into flakes using the method of the present invention. A suitable matrix should be evaporable without decomposition and should not react with the nanoparticles incorporated in the matrix. Preferably, the matrix material should be able to be used in a continuous PVD process, in particular in an industrial context with evaporation in amounts of more than 1 kg/hour and with virtually no thermal decomposition. The amount of non-condensable cracked gases formed should be substantially less than the capacity of high vacuum pumps conventionally used in such processes. In this embodiment, the matrix material is preferably a solid monomer, macromer, oligomer or polymer that is vaporizable in vacuo and is a common constituent of high molecular weight organic materials, in particular coatings, paints or printing inks. Various monomers (e.g. acrylate monomers) and/or oligomers can optionally be polymerized by heating or irradiation with electrons and/or light (see e.g. US-B-5,440,446 and WO 98/38255).

Examples of evaporable polymers are polyacrylic acid, polymethacrylic acid, copolymers of acrylic acid and methacrylic acid, copolymers of benzyl acrylate and acrylic acid, copolymers of benzyl acrylate and methacrylic acid, copolymers of benzyl methacrylate and acrylic acid, copolymers of benzyl methacrylate and methacrylic acid, copolymers of styrene and acrylic acid, copolymers of styrene and methacrylic acid, copolymers of phenylethyl acrylate and acrylic acid, copolymers of phenylethyl acrylate and phenylethyl methacrylate, copolymers of phenylethyl methacrylate and acrylic acid and copolymers of phenylethyl methacrylate and methacrylic acid or mixtures thereof. Preference is given to homopolymers or copolymers comprising repeating units derived from acrylic acid or methacrylic acid, such as polyacrylic acid, polymethacrylic acid, copolymers of acrylic acid and methacrylic acid, copolymers of benzyl acrylate and acrylic acid, copolymers of benzyl methacrylate and methacrylic acid, copolymers of styrene and acrylic acid, copolymers of styrene and methacrylic acid, copolymers of phenylethyl acrylate and acrylic acid, copolymers of phenylethyl acrylate and methacrylic acid, copolymers of phenylethyl methacrylate and acrylic acid and copolymers of phenylethyl methacrylate and methacrylic acid (see, for example, DE-A-2706392).

In both embodiments described above, the material from which the nanoparticles are preferably formed is an organic pigment or additive (e.g. uv absorber) or a metal, in particular aluminium, silicon or a noble metal such as silver, gold, palladium or platinum, for plastics, paints, coatings, printing inks or cosmetics.

Pigment nanoparticles incorporated into oligomers or polymers can be used as transparent pigments in high molecular weight organic materials, especially paints, without the need for costly dispersion steps (e.g., using ball milling), and are therefore referred to as "stinin" or "readily dispersible" pigments.

The transparent pigments can be used in particular for the preparation of effect varnishes, varnishes for wood and for the colouring of transparent plastics.

In a further preferred embodiment of the invention, SiO is used as matrix material_yAnd TiO as the material forming the nanoparticles is vaporized by an inductively heated evaporator and an electron beam heated evaporator, respectively. After general procedures, the doped SiO is obtained_yTiO nanoparticles in a matrix, which particles can be oxidized at temperatures above 200 ℃ in an oxygen-containing atmosphere to give SiO_zTiO nano in matrixAnd (3) granules. As mentioned above, such particles can be used as UV absorbers which are highly efficient, transparent, have low or almost no photosensitivity.

Luminescent materials, such as those described in WO 02/31060, may be used as the material for forming the nanoparticles. In particular, it is possible to use the volatilizable complexes of the formulｃA described in EP-A-801652:

wherein:

m is Eu, Tb, Dy or Sm;

R₂is hydrogen or C₁-C₆An alkyl group; and is

R₁And R₃Each independently of the other being phenyl, hydrogen or C₁-C₆Alkyl radical, and

l is-N, N-dimethyl-p-aminopyridine, N-methylimidazole or p-methoxypyridine-N-oxide.

In another embodiment, the invention relates to SiO flakes comprising (1-y/y + a) silicon (nanoparticles)_y+aParticles (matrix material) in which 0.70. ltoreq. y.ltoreq.1.8, in particular 1.0. ltoreq. y.ltoreq.1.8, 0.05. ltoreq. a.ltoreq.1.30, the sum of y and a being less than or equal to 2.

In this case, the matrix material and the nanoparticle-forming material are SiO with 0.70. ltoreq. y.ltoreq.1.8_y. SiO containing (1-y/y + a) Si nanoparticles_y+aFlakes, in particular SiO₂The flakes may be obtained by heating in an atmosphere above 400 deg.C (especially 400-1100 deg.C), in an oxygen-free atmosphere (such as an argon or helium atmosphere) or under vacuum at less than 13Pa (10 Pa)^-1Torr) heating SiO_yAnd (4) obtaining the particles.

It is assumed that SiO is formed by heating SiO in an oxygen-free atmosphere_yParticles of SiO_yDisproportionation into SiO₂And Si:

in this disproportionation reaction, SiO containing (1- (y/y + a)) Si is produced_y+aFlakes, wherein 0.70. ltoreq. y.ltoreq.1.80, in particular 0.70. ltoreq. y.ltoreq.0.99 or 1. ltoreq. y.ltoreq.1.8, 0.05. ltoreq. a1.30% or less and the sum of y and a is 2 or less, SiO_y+aIs a low oxide of silicon that is oxygen-rich. SiO is preferred_yComplete conversion to Si and SiO₂：

Amorphous silicon is formed at 400-900 ℃. Microcrystalline silicon is formed at 900-1100 ℃. The average size of the crystallites is in the range from 1 to 20nm, in particular from 2 to 10 nm. In one aspect, the size is temperature dependent. That is, the crystallites formed at 1100 ℃ are larger than those formed at 900 ℃. On the other hand, SiO_yThe higher the oxygen content of (a), the more small crystallites tend to form. According to the preparation method, Si-containing plane-parallel SiO_y+aParticles, in particular SiO₂The particles may exhibit photoluminescence.

SiO containing silicon nanoparticles_yFlakes are obtained by the above-described process, wherein in step b) only one material (i.e. SiO)_y) Is evaporated.

SiO containing silicon nanoparticles_yThe flakes can be used, for example, as substrates for effect pigments. Therefore, the temperature of the molten metal is controlled,another subject of the invention is SiO comprising silicon-containing nanoparticles_y+aLamellar pigments of layers, wherein the SiO is preferred_y+aThe layer forms the center of the pigment.

Known materials for containing mica and/or SiO can be used₂General procedure for the central effect pigment deposition of the further layers required for optical interference by means of porous SiO_zThe sheet is described in detail above.

Metallic or non-metallic, inorganic platelet-shaped particles or pigments are effect pigments (in particular metallic effect pigments or optical interference pigments), that is to say pigments which, in addition to imparting a color to the coating medium, impart other properties, for example a change in color with angle (goniochromatic), sparkling (rather than surface gloss) or texturing. For metallic effect pigments, substantially direct reflection occurs on the directionally oriented pigment particles. For light interference pigments, the color effect results from the phenomenon of light interference in thin, highly refractive layers.

The (effect) pigments of the invention can be used for all customary purposes, for example for coloring polymeric substances, coatings (including effect finishes, effect finishes for automobiles) and printing inks (including offset, gravure, bronzing or flexographic printing; see, for example, PCT/EP03/50690) and can be used, for example, in cosmetics (see, for example, PCT/EP03/09269), ink-jet printing (see, for example, PCT/EP03/50690), textile dyeing (see, for example, PCT/EP03/11188), ceramic and glass glazing and also laser-marking papers and plastics. Such uses are described in references such as "industrille Organische Pigmente" (W.Herbst and K.Hunger, VCH Verlagsgesellschaft mbH Weinheim/New York, 2 nd full revision, 1995).

When the optical interference pigment is a goniochromatic pigment and produces bright, highly saturated (lustrous) colours, it is suitable for use in combination with conventional transparent pigments, for example organic pigments such as diketopyrrolopyrroles, quinacridones, dioxazines, perylenes, isoindolinones and the like. The transparent pigment may have a similar color as the effect pigment. However, similarly to, for example, EP-A-388932 or EP-A-402943, particularly interesting combined effects are obtained when the color of the transparent pigment is complementary to the color of the effect pigment.

The pigments according to the invention can be used to color high molecular weight organic materials with excellent results.

The high molecular weight organic materials which can be pigmented with the pigments or pigment compositions of the invention may beHigh molecular weight organic materials of natural or synthetic origin. Generally, the molecular weight of the high molecular weight organic material is about 10³-10⁸g/mol or more. The high molecular weight organic material may be, for example, a natural resin, drying oil, rubber, casein or a derivative of a natural substance, such as chlorinated rubber, oil-modified alkyd resin, viscose, cellulose ether or ester, such as ethyl cellulose, cellulose acetate, cellulose propionate, cellulose acetobutyrate or cellulose nitrate, but in particular a fully synthetic organic polymer (thermoset and thermoplastic) obtained by polymerization, polycondensation or polyaddition. From the type of polymeric resinMention may in particular be made of polyolefins such as polyethylene, polypropylene or polyisobutylene, substituted polyolefins such as the polymerization products of vinyl chloride, vinyl acetate, styrene, acrylonitrile, acrylates, methacrylates or butadiene, and also the copolymerization products of the monomers mentioned, in particular ABS or EVA.

Among the various polyaddition resins and polycondensation resins, mention may be made, for example, of the condensation products of formaldehyde with phenol (known as "phenoplasts") and of formaldehyde with urea, thiourea or melamine (known as "aminoplasts") and also of the saturated polyesters (such as alkyd resins) or unsaturated polyesters (such as maleate resins) used as coating resins, and also of the linear polyesters, polyamides, polyurethanes or polysiloxanes.

The macromolecular compounds may be present individually or as mixtures in the form of plastic masses or melts. It is also possible to use in the form of dissolved monomers or in the polymerized state as film formers or binders for coatings or printing inks, for example linseed oil, nitrocellulose, alkyd resins, melamine resins, urea-formaldehyde resins or acrylic resins.

Depending on the intended use, it has proven advantageous to use the effect pigments of the invention as toners or in the form of preparations. Depending on the conditioning method or the intended use, it may be advantageous to add to the effect pigments, before or after the conditioning process, a certain amount of a texture-improving agent, provided that this does not adversely affect the use of the effect pigments in the coloration of high molecular weight organic materials, in particular polyethylene. Suitable agents for improving the relief are, in particular, fatty acids containing at least 18 carbon atoms (e.g. stearic acid or behenic acid) or amides or metal salts thereof (in particular magnesium salts) and also plasticizers, waxes, resin acids (e.g. abietic acid), rosin soaps, alkylphenols or fatty alcohols (e.g. stearyl alcohol) or aliphatic 1, 2-dihydroxy compounds containing 8 to 22 carbon atoms (e.g. 1, 2-dodecanediol) and also modified rosin maleate resins or fumaric acid rosin resins. The amount of the texture-improving agent added is preferably from 0.1 to 30%, in particular from 2 to 15%, by weight based on the final product.

The (effect) pigments according to the invention can be added to the high molecular weight organic material to be dyed in any dyeing-effective amount. Advantageously, the pigmented composition of matter comprises a high molecular weight organic material and from 0.01 to 80%, preferably from 0.1 to 30%, by weight, based on the high molecular weight organic material, of a pigment according to the invention. Concentrations of from 1 to 20% by weight, in particular about 10% by weight, are generally used in practice.

The pigmented compositions in high concentrations (for example greater than 30% by weight) are generally in the form of concentrates ("masterbatches") which can be used as colorants for preparing pigmented materials of relatively low pigment content, the pigments of the invention having a very low viscosity in conventional formulations which therefore still have good processability.

The effect pigments of the invention can be added separately to color organic materials. However, it is also possible to add, in addition to the effect pigments of the invention, other color-imparting components in any desired amounts (for example white, colored, black or effect pigments) to the polymeric organic substances in order to achieve different hues or color effects. When colored pigments are used in admixture with the effect pigments of the invention, the total amount is preferably from 0.1 to 10% by weight, based on the high molecular weight organic material. Preferred combinations of the effect pigments of the invention with colored pigments of other colors, in particular complementary colors, provide particularly high goniochromability, the color difference (Δ H) of the colorations obtained with the effect pigments and with the colored pigments being colored at a measurement angle of 10 °^*) 20-340, in particular 150-210.

The effect pigments according to the invention are preferably used together with transparent colour pigments which may be present in the same medium as the effect pigments according to the invention or may also be present in an adjacent medium. One example of a distribution pattern in which the effect pigments and the coloured pigments are preferably present in adjacent media is a multi-layer effect paint.

The process for pigmenting high molecular weight organic material substances with the pigments of the invention is as follows: mixing such pigments (which may be in the form of a suitable masterbatch) with the matrix using a roller mill or mixing or grinding device; the pigmented material is then prepared into the final desired form using known methods (e.g., calendering, compression molding, extrusion, coating, pouring or injection molding). Any conventional additives in the plastics industry, such as plasticizers, fillers or stabilizers, can be added to the polymer in conventional amounts, either before or after incorporation of the pigment. In particular, for the preparation of non-rigid shaped articles or for reducing the brittleness of shaped articles, it is necessary to add plasticizers (for example esters of phosphoric acid, phthalic acid or sebacic acid) to the macromolecular compounds prior to shaping.

For the coloring of coatings and printing inks, the high molecular weight organic materials and the effect pigments according to the invention and, where appropriate, conventional additives (for example fillers, further pigments, siccatives or plasticizers) are finely dispersed or dissolved in the same organic solvent or solvent mixture, it being possible for the individual components to be dissolved or dispersed separately or for a plurality of components to be dissolved or dispersed together and then for all the components to be mixed together.

The dispersion of the effect pigments of the invention in the high molecular weight organic material to be dyed, and the processing of the pigment compositions of the invention, is preferably carried out under conditions which keep the shear forces occurring only relatively low, so that the effect pigments are not broken up into smaller pieces.

The pigments according to the invention are used in the plastics in amounts of 0.1 to 50% by weight, in particular 0.5 to 7% by weight. The pigments according to the invention are used in the coating in amounts of 0.1 to 10% by weight. In the dyeing of binder systems, for example paints and printing inks for gravure, offset or screen printing, the pigments are incorporated in the printing inks in amounts of from 0.1 to 50% by weight, preferably from 5 to 30% by weight, in particular from 8 to 15% by weight.

The colorations obtained, for example, in plastics, paints or printing inks, in particular in paints or printing inks, more particularly in paints, are distinguished by very good properties, in particular by very high saturation, outstanding fastness, high color purity and high goniochromicity.

When the polymeric material being dyed is a coating, the coating is preferably a specialty coating, most preferably an automotive finish.

The effect pigments according to the invention are also suitable for making up the lips or the skin, or for coloring hair or nails.

The present invention therefore also relates to cosmetic preparations comprising, based on their total weight, from 0.0001 to 90% of the pigments according to the invention, in particular effect pigments, and from 10 to 99.9999% of a cosmetically suitable carrier material.

Such cosmetic preparations are, for example, lipsticks, blushes, foundations, nail varnishes and hair shampoos.

The pigments of the invention may be used alone or in mixtures, and may also be used in combination with other pigments and/or colorants as described above or well known in cosmetic formulations.

Preferably, the cosmetic preparations according to the invention contain from 0.005 to 50% by weight of the pigment according to the invention, based on the total weight thereof.

Suitable carrier materials for the cosmetic preparations of the present invention include conventional materials used in such compositions.

The cosmetic preparation of the present invention may be in the form of: such as a stick, ointment, cream, emulsion, suspension, dispersion, powder or solution. For example, the cosmetic preparation is a lipstick, a mascara preparation, a blusher, an eye shadow, a foundation, an eyeliner, a powder or a nail varnish.

If the preparation is in the form of a stick (e.g. lipstick, eye shadow, blusher or foundation), the preparation contains a considerable amount of fatty ingredients, which may consist of one or more waxes, for example ozokerite; lanolin; lanolin alcohol; hydrogenating lanolin; acetylated lanolin; lanolin wax; beeswax; candelilla wax; microcrystalline wax; carnauba wax; cetyl alcohol; stearyl alcohol; cocoa butter; lanolin fatty acids; vaseline; petrolatum; mono-, di-or triglycerides or fatty acid esters thereof which cure at 25 ℃; silicone waxes (e.g., methyl octadecanoxy polysiloxane and poly (dimethylsiloxy) stearoxysilane); stearic acid monoethanolamine; rosin and its derivatives (e.g., rosin esters of ethylene glycol and rosin esters of glycerol); hydrogenated oil solidified at 25 ℃; glycerol esters of sucrose, and calcium, magnesium, zirconium and aluminum salts of oleic acid, myristic acid, lanolin acid, stearic acid, dihydroxystearic acid.

The fatty component may also consist of at least one wax and at least one oil, in which case suitable oils are, for example: paraffin oil, purcelline oil, perhydrosqualene, sweet almond oil, avocado oil, crabapple oil, castor oil, sesame oil, jojoba oil, mineral oil having a boiling point of about 310-140 ℃, silicone oil (e.g., dimethylpolysiloxane), linoleol, linolenyl alcohol, oleyl alcohol, grain fusel oil (e.g., wheat germ oil), isopropyl lanolate, isopropyl palmitate, isopropyl myristate, butyl myristate, cetyl stearate, butyl stearate, decyl oleate, acetyl glycerides, caprylic and capric esters of alcohols and polyols (e.g., ethylene glycol and glycerol), ricinoleic esters of alcohols and polyols (e.g., cetyl alcohol, isostearyl alcohol), isocetyl lanolate, isopropyl adipate, hexyl laurate and octyldodecanol.

The content of fatty constituents in such stick preparations is generally up to 99.91% by weight of the total weight of the preparation.

The cosmetic preparations according to the invention may also comprise further components, such as, for example, glycols, polyethylene glycols, polypropylene glycols, monoalkanolamides, colourless fillers (polymeric, inorganic or organic), preservatives, UV filters or other auxiliaries and additives conventionally used in cosmetics (for example, natural or synthetic or partially synthetic di-or triglycerides, mineral oils, silicone oils, waxes, fatty alcohols, Guerbet alcohols or esters thereof), lipophilic functional cosmetic active ingredients (including sun protection filters or mixtures of such substances)).

Lipophilic functional cosmetic active ingredients, active ingredient compositions or active ingredient extracts suitable for use in skin cosmetics are one or a mixture of ingredients which can be applied to the skin or topically. Mention may be made, for example, of the following:

active ingredients having a cleansing action on the skin surface and on the hair, these active ingredients including all substances which can be used for cleansing the skin, such as oils, soaps, synthetic detergents and solid substances;

active ingredients with deodorant and antiperspirant action, these active ingredients including antiperspirant agents based on aluminium or zinc salts, deodorant agents containing bactericidal or bacteriostatic deodorant substances (for example triclosan, hexachlorophene, alcohols or cationic substances (such as quaternary ammonium salts)) and odor absorbers (for example Grillocin (zinc ricinoleate in combination with various additives) or triethyl citrate (optionally in combination with antioxidants such as butylhydroxytoluene) or ion exchange resins);

sunscreen active ingredients (uv filters), suitable active ingredients being filter substances (sunscreens) capable of absorbing the uv radiation from the sun and converting it into heat, the following sunscreens being preferred according to the desired action: a light aging preventive (UV-B absorber) which selectively absorbs the high-energy ultraviolet radiation in the wavelength range of about 280-315nm causing tanning and transmits the ultraviolet radiation in the longer wavelength range (e.g., 315-400nm, i.e., UV-A range) and a light aging preventive (UV-A absorber) which absorbs only the ultraviolet radiation in the longer wavelength range of 315-400 nm; suitable light stabilizers are, for example, the following types of organic UV absorbers: p-aminobenzoic acid derivatives, salicylic acid derivatives, benzophenone derivatives, dibenzoylmethane derivatives, diphenylacrylate derivatives, benzofuran derivatives, polymeric ultraviolet absorbers containing one or more organosilicon groups, cinnamic acid derivatives, camphor derivatives, triphenylamino-s-triazine derivatives, phenylbenzimidazolesulfonic acid and its salts, menthyl anthranilate, benzotriazole derivatives and/or inorganic fine pigments selected from titanium dioxide, zinc oxide or mica coated with aluminum oxide or silicon dioxide;

active ingredients against insects (repellents), which are agents that prevent insects from touching and moving on the skin, which repel insects and evaporate slowly, the most commonly used repellent being diethyltoluamide (deet), other common repellents being found, for example, on page 161 of "Pflegekosmetik" (W.Raab and U.Kindl, Gustav-Fischer-Verlagg Stuttgart/New York, 1991);

active ingredients to protect against chemical and physical influences, including all substances that form a barrier between the skin and external harmful substances, such as paraffin oil, silicone oil, vegetable oil, PCL products and lanolin to protect the skin against aqueous solutions, film-forming agents to protect the skin against organic solvents (such as sodium alginate, triethanolamine alginate, polyacrylates, polyvinyl alcohols or cellulose ethers) or substances based on mineral oils, vegetable oils or silicone oils as "lubricants" to protect the skin against strong mechanical stresses on the skin;

wetting agents, for example the following substances can be used as moisture regulators (wetting agents): sodium lactate, urea, alcohol, sorbitol, glycerol, propylene glycol, collagen, elastin, and hyaluronic acid;

-active ingredients with a keratinocyte proliferation effect: benzoyl peroxide, retinoic acid, colloidal sulfur, and resorcinol;

antibacterial agents, such as triclosan or quaternary ammonium compounds;

oily or oil-soluble vitamins or vitamin derivatives which can be applied to the skin, such as vitamin a (retinol in the form of the free acid or its derivatives), panthenol, pantothenic acid, folic acid and mixtures thereof, vitamin E (tocopherol), vitamin F, essential fatty acids or nicotinamide (nicotinic acid amide);

vitamin-based placenta extract, the active ingredient composition of which comprises especially vitamin A, C, E, B₁、B₂、B₆、B₁₂Folic acid, vitamin H, amino acids and enzymes, and trace elements of magnesium, silicon, phosphorus, calcium, manganese, iron or copper;

-a skin repair complex obtained from a non-viable culture and a decomposed culture of lactobacillus bifidus bacteria;

plants and plant extracts, for example arnica, aloe vera, lichen, ivy, nettle, ginseng, henna, chamomile, marigold, rosemary, sage, equisetum or thyme;

-animal extracts, such as royal jelly, propolis, proteins or thymus extracts;

cosmetic oils which can be applied to the skin, such as, for example, neutral oil of Miglyol 812, almond oil, avocado oil, babassu oil, cottonseed oil, borage oil, thistle oil, peanut oil, gamma-orynol, rose seed oil, hemp oil, hazelnut oil, blackcurrant seed oil, jojoba oil, cherry seed oil, salmon oil, linseed oil, corn oil, macadamia nut oil, almond oil, evening primrose oil, mink oil, olive oil, pecan oil, peach kernel oil, pistachio nut oil, rape oil, rice-seed oil, castor oil, safflower oil, sesame oil, soybean oil, sunflower seed oil, tea tree oil, grapeseed oil or wheat germ oil.

Preferably, the stick formulation is anhydrous, but in some cases may contain water, typically not exceeding 40% of the total weight of the cosmetic formulation.

If the cosmetic preparations according to the invention are products in semisolid form, that is to say in the form of ointments or creams, they may likewise be anhydrous or aqueous. Such formulations are, for example, mascaras, eyeliners, foundations, blushers, eye shadows or compositions for treating bags under the eyes.

On the other hand, if such ointments or creams are aqueous, they are in particular emulsions of the water-in-oil or oil-in-water type which, in addition to the pigment, comprise from 1 to 98.8% by weight of a fatty phase, from 1 to 98.8% by weight of an aqueous phase and from 0.2 to 30% by weight of an emulsifier.

Such ointments and creams may also contain other conventional additives, such as perfumes, antioxidants, preservatives, gelling agents, UV filters, colorants, pigments, pearlizing agents, colorless polymers, and inorganic or organic fillers.

If the formulation is in powder form, it consists essentially of mineral, inorganic or organic fillers (e.g. talc, kaolin, starch, polyethylene powder or polyamide powder) and auxiliaries (e.g. binders, colorants), etc.

Such preparations may also contain various adjuvants conventionally used in cosmetics, such as perfumes, antioxidants, preservatives, and the like.

If the cosmetic preparation according to the invention is a nail varnish, this preparation consists essentially of nitrocellulose and a natural or synthetic polymer in the form of a solution in a solvent system, which may contain further auxiliaries (for example pearlescent agents).

In an embodiment of the invention, the amount of colored polymer is about 0.1 to 5% by weight.

The cosmetic preparations according to the invention can also be used for coloring hair, in which case preparations in the form of shampoos, creams or gels composed of the basic substances conventionally used in the cosmetics industry and the pigments according to the invention can be used.

The cosmetic formulations of the present invention may be prepared using conventional methods, for example by mixing or stirring the components together, optionally with heating to melt the mixture.

The following examples illustrate the invention without limiting its scope. Unless otherwise specified, percentages and parts are by weight.

Examples

Example 1

To a vacuum chamber (< 10)^-1Pa) were charged with SiO and NaCl powder, respectively. The rotary support, which was mechanically attached with aluminum foil, was placed on an evaporator. A NaCl layer (90nm) was first sublimated onto the aluminum foil. The SiO evaporator is then heated and sublimation of the SiO begins while the salt is sublimed. In this way, the salt and SiO are sublimated simultaneously onto the NaCl layer. The simultaneous gasification of the salt and SiO was continued until a thickness of 300nm was reached. The sublimation was terminated, the aluminum foil of the carrier was removed, and immersed in distilled water. The NaCl layer and the salt contained in the SiO matrix were dissolved in water, thereby obtaining a silicon oxide sheet. If passing the normal procedure SiO_yNot completely converted into SiO₂Porous SiO can then be obtained by heating silicon oxide flakes in air at a temperature above 500 ℃ for several hours₂A sheet.

FIG. 3 shows porous SiO of example 1₂Atomic Force Microscope (AFM) image of a thin sheet (BET 712 m)²In terms of/g). The pore diameter can reach 30nm at most.

Example 2

Two crucibles, each with an energy supply, were placed in a vacuum chamber. The first crucible was filled with SiO and the second crucible with NaCl. The vaporization rate of each material can be measured by a quartz resonator (quartz crystal oscillator). Using a flap valve to separate each evaporator from the stainless steel substrate

The crucible containing NaCl was heated until the quartz resonator showed a vaporization rate of 0.3. + -. 0.04 nm/s. The flap valve was opened until the thickness of NaCl-Schicht sublimated onto the stainless steel substrate reached 100 nm. The lid is then closed.

While maintaining the crucible containing NaCl at the same temperature, the crucible containing SiO was heated until the quartz resonator showed a vaporization rate of 2.8 ± 1.2 nm. The flap valve is then opened. Simultaneous sublimation of NaCl and SiO was continued until a thickness of 420nm was reached. The SiO evaporator is then switched off and the NaCl evaporator is continued for about 100 seconds, after which the flap valve is closed.

The substrate was taken out of the vacuum chamber. The salt was dissolved in water and the resulting silica flakes were washed with water and dried. High resolution electron microscopy analysis showed the silica flakes to have a pore size of about 10.5 nm.

If passing the normal procedure SiO_yNot completely converted into SiO₂Porous SiO can then be obtained by heating a silicon oxide wafer in air at a temperature above 500 ℃ for several hours₂A sheet.

Example 3

0.27g (4.49mmol) of porous SiO from example 1 are introduced into a 100ml round-bottomed flask at room temperature under a nitrogen atmosphere₂(BET＝712m²Per g) with 10.0g (52.7mmol) TiCl₄Mix and stir overnight (17 hours) with a magnetic stirrer whereupon TiCl₄React with the absorbed water to form nano TiO₂. Vacuum removal of excess TiCl₄The solid material was subsequently dried in a rotary evaporator at 80 ℃ and 0.01 mbar, giving about 0.3g of a grey powder which showed a light interference color.

Elemental analysis: 0.47% C, 2.23% H, < 0.3% Cl, 12.40% Ti, equivalent to TiO₂Is present in an amount of about 20% by weight.

Example 4

The coating formulations used in this example are shown in the following table:

components	Description of the invention	Sample 1 (invention)	Sample 2 (comparative)
				Porous silica sheet of example 1	Silicon dioxide flakes	100	-
Sipernat(Degussa AG)	Precipitated silica	-	80
				MOX(Degussa AG)	Fumed silica	-	20
Celvol(Celanese)	Polyvinyl alcohol	30	30
				DP6(Ciba SC)	Polyvinylpyrrolidone (PVP)	1.3	1.3

All coatings were applied to uncoated free paper (freeboard) using a manual calendering applicator (K303 Multicoater, RK Print-coatInstructions) (xerographic paper, distributed by corporation Express, paper basis mass 75g/m²21.59 cm. times.27.94 cm, TAPPI brightness 84), gives the target low coating quality (3 g/m)²) And high coating quality (4.5 g/m)²)。

Because of the high viscosity of sample 1, sample 1 must have a lower solids content (12%) than sample 2 (19%) in order to be able to be applied with a manual calendar applicator.

The coated paper containing sample 1 exhibited a metallic pearlescent texture.

Furthermore, the coating containing sample 1 showed a higher wash resistance (wash resistance: determined according to the dip (clip) test (2ml water, 45 degree angle) in the specification for HP) than the coating containing sample 2： $\mathrm{\&Delta;E}=\sqrt{\mathrm{\&Delta;}{L}^{*2}+\mathrm{\&Delta;}{a}^{*2}+\mathrm{\&Delta;}{b}^{*2}}).$

Example 5

a) Preparation of porous silica containing metallic palladium nanoparticles

500mg of porous SiO obtained in a manner analogous to that described in example 1₂(BET 750m²Per g) and 53mg of a precisely defined palladium complex which decomposes slowly on heating [ (C)₆H₄CH₂NMe₂-2)Pd(OAc)(PPh₃)](see WO 03/13723) was mixed in 5ml of xylene. The mixture was stirred vigorously and heated to reflux under a nitrogen atmosphere and held at this temperature for 2 hours. During this time, the color of the reaction mixture turned black. After cooling to room temperature, the porous silica was separated by filtration, followed by washing with xylene 1 time,washed 3 times with ether. The grey silica was dried in vacuo. 506mg of gray coloured porous silica are obtained. Elemental analysis showed that the material contained 1.75% by weight of palladium (see FIG. 2, which is a palladium-loaded porous SiO solid)₂Ultra-thin cross-sections of the lamellae).

b) Suzuki coupling using palladium catalysts immobilized on porous silica from example 5a)

190mg of 3-bromoanisole, 183mg of phenylboronic acid and 275mg of potassium carbonate were mixed in 2ml of xylene. To this mixture was added 27mg of the catalyst from example 5a (corresponding to 0.5 mol% palladium). The reaction mixture was stirred and heated to 130 ℃ under a nitrogen atmosphere and held at this temperature for 2 hours. GC analysis showed that all the starting material was consumed and 3-methoxybiphenyl was selectively formed (100% conversion).

After cooling the reaction mixture to room temperature, the catalyst was isolated by filtration, washed with xylene, ethanol, water, ethanol and diethyl ether and dried in vacuo. The catalyst was used repeatedly under the same conditions once. GC analysis of the reaction mixture showed that the reaction mixture was again converted to 3-methoxybiphenyl with a high conversion (> 80% conversion).

Example 6

In a four-necked flask, 0.600g of porous SiO having a maximum particle diameter of 40 μm obtained in a manner similar to that described in example 1 was placed₂(BET：660m²/g) are suspended in 35ml of water and subsequently heated to 65 ℃ with stirring with an oil bath. The pH of the suspension was controlled to 1.4 with 1N HCl. Subsequently, 24ml of TiOCl stabilized with concentrated hydrochloric acid were added at 65 ℃ under nitrogen over a period of 8 hours₂Aqueous solution (0.5% Ti). The pH was maintained at 1.4 by slow addition of 2N NaOH in water. After the addition of TiOCl₂After that, the suspension was stirred for another 30 minutes. The bluish suspension is subsequently cooled to 25 ℃, filtered through a 20 μm sieve, washed with water and methanol and dried at 50 ℃ in vacuo to give a bluish product (BET: 650 m)²In terms of/g). TiO of the product₂The content was about 8.2% by weight.

Example 7

500mg of C.I. pigment Red 179 are dissolved in 60g of sulfuric acid (96%) at room temperature and stirred 1And (4) hours. 500mg of porous SiO obtained in a manner analogous to that described in example 1 are mixed under stirring₂Sheet (BET: 700 m)²/g) are added in portions to the dark purple solution. The suspension was subsequently stirred for 2 hours. Thereafter 60g of ice water are slowly added to the suspension with stirring, the pigment being in porous SiO₂To obtain a strong red pigment. 1000ml of deionized water were added to the red suspension and the resulting suspension was stirred for 30 minutes, filtered, washed with water and dried in vacuo. A red composite pigment is obtained.

Example 8

200mg of the mixture

Dissolved in a mixture consisting of 10g of 1-methyl-2-pyrrolidone (NMP) and 25g of ethanol (99%). To this solution was added 2g of porous SiO obtained in a manner analogous to that described in example 1₂Sheet (BET: 700 m)²Per g) and heated to 60 ℃.25 g of ethanol (99%) are added, and the suspension is subsequently stirred for a further 2 hours at 60 ℃. 1000ml of water are added to this homogeneous suspension with stirring at 60 ℃ over a period of several seconds, the latent pigment being precipitated. The yellow-orange suspension was cooled to room temperature with stirring, filtered and washed with 1000g of deionized water, dried at room temperature for 16 hours and subsequently dried in a vacuum oven (100hPa) at 100 ℃ for 12 hours. The pale pink powder was heated to 180 ℃ and held for 20 minutes to completely remove the BOC groups. A red composite pigment is obtained.

Example 9

500mg of porous SiO obtained in a manner analogous to that described in example 1₂Sheet (BET: 700 m)²Per g) suspended in a suspension containing 4g FeCl₃·6H₂O in a dilute solution of 150 ml of deionized water, followed by stirring at 50 ℃ for 6 hours. Subsequently, 4% sodium hydroxide solution was slowly added dropwise with stirring until a dark brown precipitate (pH3.5) was obtained. The suspension was stirred for 12 hours, filtered and the filter cake was rinsed with 4% hydrochloric acid and 1000g of deionized water. Precipitating with goldThe lake was first dried at room temperature for 16 hours, followed by drying in a vacuum oven at 100 deg.C (100hPa) for 12 hours. A golden yellow composite pigment is obtained, which can optionally be calcined at temperatures of 700-.

Claims (20)

1. A method of making a porous material, the method comprising the steps of:

a) vapor depositing a separating agent on the carrier to prepare a separating agent layer,

b) simultaneously vapor-depositing a material and a separating agent on the separating agent layer (a),

c) separating the material from the separating agent.

2. The method of claim 1, wherein the material is a metal, metal oxide or metalloid oxide, particularly 0.70 ≦ z ≦ 2.0 SiO₂。

3. The process of claim 2, wherein in step b) the SiO is_yThe separating agent layer is vapor-deposited by two different vaporizers, wherein the first vaporizer contains a material containing Si and SiO₂SiO_yOr mixtures thereof, wherein y is more than or equal to 0.70 and less than or equal to 1.8, and a second gasifier is filled with the material containing the separating agent.

4. The method of claim 3, wherein the method further comprises a step d) wherein the SiO is heated by heating in an oxygen-containing atmosphere_yConverted into SiO with z being more than or equal to 1.40 and less than or equal to 2.0_zOr by heating SiO in an oxygen-free atmosphere_yConversion to SiO containing (1-y/y + a) silicon_y+aWherein 0.70. ltoreq. y.ltoreq.1.8, in particular 1.0. ltoreq. y.ltoreq.1.8, 0.05. ltoreq. a.ltoreq.1.30 and the sum of y and a is less than or equal to 2.

5. The method of any one of claims 1 to 4, wherein the separating agent is an inorganic salt soluble in water and vaporizable under vacuum or an organic substance soluble in an organic solvent or water and vaporizable under vacuum.

6. Porous sheet material, in particular SiO, obtained by the process according to any one of claims 1 to 5_zWherein 0.70. ltoreq. z.ltoreq.2.0, in particular 1.4. ltoreq. z.ltoreq.2.0, or SiO comprising (1-y/y + a) silicon_y+aWherein 0.70. ltoreq. y.ltoreq.1.8, in particular 1.0. ltoreq. y.ltoreq.1.8, 0.05. ltoreq. a.ltoreq.1.30 and the sum of y and a is less than or equal to 2.

7. Porous SiO_zFlakes, wherein 0.70. ltoreq. z.ltoreq.2.0, in particular 0.95. ltoreq. z.ltoreq.2.0, in particular a porous SiO_zFlakes, wherein the porous SiO_zThe pores of which are filled with TiO in rutile or anatase form₂Nano-particlesParticles, or carrying tin-doped indium oxide, SnO₂、Sb₂O₃/SnO₂、In₂O₃Or In₂O₃/SnO₂。

8. A flake pigment, comprising:

z is more than or equal to 0.70 and less than or equal to 2.0 of porous SiO_zLayer of or

Porous SiO containing (1-y/y + a) silicon_y+aLayer, wherein 0.70. ltoreq. y.ltoreq.1.8, in particular 1.0. ltoreq. y.ltoreq.1.8, 0.05. ltoreq. a.ltoreq.1.30.

9. The pigment of claim 8, comprising:

(a) a metal, in particular an aluminium centre,

(b) optionally SiO on the aluminum center_zA layer, and

(c) on the aluminum center or the SiO_zPorous SiO on a layer_zA layer, wherein 0.70. ltoreq. z.ltoreq.2.0, in particular 1.40. ltoreq. z.ltoreq.2.0.

10. The pigment of claim 9 in which the porous SiO_zThe layer carries an inorganic or organic colorant, in particular an inorganic or organic pigment, wherein 0.70. ltoreq. z.ltoreq.2.0, in particular 1.40. ltoreq. z.ltoreq.2.0.

11. The pigment of claim 8, comprising:

(a) porous SiO_zPorous SiO_z/SiO_zPorous SiO_z/SiO_zPorous SiO_zOr SiO_zPorous SiO_z/SiO_zA center, wherein 0.70. ltoreq. z.ltoreq.2.0, in particular 1.40. ltoreq. z.ltoreq.2.0, and

(b) metal oxides of high refractive index, especially TiO₂、ZrO₂、Fe₂O₃、Fe₃O₄、Cr₂O₃Or ZnO, or

A layer containing SiC, or

A carbon, in particular a diamond-like carbon layer, or

A semi-transparent metal layer, or

An opaque metal layer.

12. A method of making a nanoparticle-loaded matrix material, the method comprising:

a) vapor depositing a separating agent on the carrier to prepare a separating agent layer,

b) followed by vapor deposition of a base material and a nanoparticle-forming material simultaneously on the separating agent layer (a),

c) separating the material from the separating agent, in particular by dissolving the separating agent in a solvent, and

d) optionally separating the nanoparticle-laden matrix material from the solvent.

13. The process of claim 12, wherein the matrix material is a transparent metal oxide or metalloid oxide, in particular 0.70. ltoreq. z.ltoreq.2.0 SiO_z。

14. The method of claim 12, wherein the matrix material is a solid monomer, oligomer or polymer vaporizable under vacuum.

15. The method according to claim 13 or 14, wherein the nanoparticle-forming material is an organic pigment, a uv absorber or a metal, in particular aluminium, silicon or a noble metal such as silver, gold, palladium or platinum.

16. The method of claim 12, wherein the matrix material and the nanoparticle-forming material are 0.70 ≦ y ≦ 1.8 SiO_yAnd SiO containing (1-y/y + a) silicon nanoparticles₂The substrate material is prepared by heating SiO in an oxygen-free atmosphere at 400-1100 deg.C, especially at 900-1100 deg.C_yObtained wherein 0.70. ltoreq. y.ltoreq.1.8, in particular 1. ltoreq. y.ltoreq.1.8, 0.05. ltoreq. a.ltoreq.1.30 and the sum of y and a is less than or equal to 2.

17. A matrix material comprising nanoparticles, the matrix material being obtainable by the method of any one of claims 12 to 16.

18. Flaky SiO_y+aParticles (matrix material) comprising (1-y/y + a) silicon (nanoparticles), wherein 0.70. ltoreq. y.ltoreq.1.8, in particular 1. ltoreq. y.ltoreq.1.8, 0.05. ltoreq. a.ltoreq.1.30, and the sum of y and a is less than or equal to 2.

19. An imageable medium comprising a support and an ink-receptive layer comprising the porous SiO of claim 7 or obtained by the method of any of claims 1 to 5_zFlakes and a hydrophilic binder, wherein 0.70. ltoreq. z.ltoreq.2.0, in particular 1.40. ltoreq. z.ltoreq.2.0, very particularly z is 2.0.

20. Use of the pigments according to any of claims 8 to 11 for ink-jet printing, for dyeing textiles and for pigmenting surface coatings, printing inks, plastics, cosmetics, glazes for ceramics and glass.

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