WO2005056621A1 - Matiere colorante a effet contenant des particules composees d'un noyau et d'une enveloppe - Google Patents

Matiere colorante a effet contenant des particules composees d'un noyau et d'une enveloppe Download PDF

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Publication number
WO2005056621A1
WO2005056621A1 PCT/EP2004/013005 EP2004013005W WO2005056621A1 WO 2005056621 A1 WO2005056621 A1 WO 2005056621A1 EP 2004013005 W EP2004013005 W EP 2004013005W WO 2005056621 A1 WO2005056621 A1 WO 2005056621A1
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Prior art keywords
core
shell
effect
particles
effect colorant
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PCT/EP2004/013005
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German (de)
English (en)
Inventor
Holger Winkler
Corinna Weigandt
Goetz Peter Hellmann
Tilmann Eberhard Ruhl
Peter Spahn
Benjamin Viel
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Merck Patent Gmbh
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Publication of WO2005056621A1 publication Critical patent/WO2005056621A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0098—Organic pigments exhibiting interference colours, e.g. nacrous pigments
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D153/00—Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D153/005—Modified block copolymers

Definitions

  • the invention relates to effect colorants containing core-shell particles and to processes for producing the effect colorants and their use.
  • Natural precious opals are made up of domains, consisting of monodisperse, densely packed and therefore regularly arranged
  • Silica gel spheres with diameters of 150-400 nm The play of colors of these opals comes about through Bragg-like scattering of the incident light on the grating planes of the domains arranged in a crystal-like manner.
  • US 4 703 020 describes a method for producing a decorative material which consists of amorphous silica spheres which are arranged three-dimensionally, zirconium oxide or zirconium hydroxide being located in the spaces between the spheres.
  • the beads have a diameter of 150-400 nm.
  • the production takes place in two stages. In a first stage, silica spheres are sedimented from an aqueous suspension. The mass obtained is then dried in air and then calcined at 800 ° C. The calcined material is introduced into the solution of a zirconium alkoxide in a second stage, the alkoxide penetrating into the spaces between the cores and zirconium oxide being precipitated by hydrolysis. This material is then calcined at 1000-1300 ° C.
  • EP-A-0 955 323 describes core / shell particles, their core and
  • Shell materials can form a two-phase system and are characterized in that the shell material is filmable and the cores are essentially dimensionally stable under the conditions of the filming of the shell, cannot swell or only to a very small extent through the shell material and have a monodisperse size distribution, with a difference between the refractive indices of the core material and the shell material of at least 0.001.
  • the production of the core / shell particles and their use for the production of moldings are also described.
  • the process for the production of a shaped body comprises the following steps: application of the core / shell particles to a substrate with low adhesion, if necessary allowing to evaporate or
  • Nuclei do not form in the melt, but only a short-range order of the nuclei in domains. As a result, these particles are only of limited suitability for processing using methods customary for polymers.
  • Shaped bodies are known from patent application WO 03/25035, which essentially consist of core-shell particles, the shell of which forms a matrix and whose core is essentially solid and has an essentially monodisperse size distribution, the shell preferably having an intermediate layer is firmly connected to the core.
  • contrast materials such as pigments
  • the embedded contrast materials cause an increase in the brilliance, contrast and depth of the observed Color effects on these moldings.
  • the processing of such shaped bodies into pigments is also described.
  • the pigments can be produced, for example, by first producing a film from the core-shell particles, which can optionally be hardened. The film can then be suitably cut or cut
  • the pigments obtainable in this way are particularly suitable for use in paints, lacquers, printing inks, plastics, ceramic materials, glasses and cosmetic formulations.
  • the mechanical properties of these moldings or pigments are essentially determined by the shell polymers.
  • Preferred shell polymers are elastomers.
  • the moldings of such preferred embodiments thus necessarily show material properties of elastomers.
  • effect colorants and preparations comprising the effect colorants which are also suitable for providing large-area structures with a color effect which is dependent on the viewing angle and which have mechanical properties which are highly suitable for production, processing and use.
  • a first object of the present invention are therefore effect colorants consisting essentially of core-shell particles, the shell of which forms a matrix and whose core is essentially solid and has an essentially monodisperse size distribution, with a difference between the refractive indices of the core material and the
  • Sheath material exists, which are characterized in that the matrix is brittle.
  • a brittle matrix is understood to mean a matrix which has such a high mechanical hardness that films can be milled with this matrix.
  • a brittle matrix in the sense of the present invention shows no elastomeric properties and does not flow even under mechanical stress.
  • a brittle matrix in the sense of the present invention breaks when subjected to mechanical stress.
  • the brittleness of the matrix is achieved in that the
  • Matrix is essentially formed by cross-linked organic polymers.
  • the glass transition temperature T G of the matrix is above
  • Glass transition temperature can be set by suitable selection of polymers as the shell material of the core-shell particles.
  • the targeted selection does not cause any problems for the person skilled in the art.
  • the jacket material is particularly preferably homo- or copolymeric poly (cyclohexyl methacrylate), polystyrene and substituted
  • Polystyrene derivatives such as. B. poly (iodostyrene) and poly (bromostyrene), polyacrylates and polymethacrylates with a Tg above the temperature of use, high Tg polyvinyl chloride and other vinyl polymers resulting from conversion from polyvinyl acetate, polyacrylonitrile and styrene-acrylonitrile copolymers.
  • Tg temperature of use
  • high Tg polyvinyl chloride and other vinyl polymers resulting from conversion from polyvinyl acetate, polyacrylonitrile and styrene-acrylonitrile copolymers are made up of core-shell particles, as described in WO 03/25035.
  • the core-shell particles have a medium one
  • the core-shell particles have an average particle diameter in the range from about 5 nm to about 2000 nm. It can be particularly preferred if the core-shell particles have an average particle diameter in the range from about 5 to 20 nm, preferably 5 to 10 nm. In this case the nuclei can be called "quantum dots"; they show the corresponding effects known from the literature. To achieve color effects in the visible light range, it is particularly advantageous if the core-shell particles have an average particle diameter in the range of approximately 40-500 nm. Particles in the range from 80 to 500 nm are particularly preferably used, since at
  • Embodiment in which the effect is an opalescence in the visible range Act in the sense of a usual definition of the term the effect colorants according to the invention are photonic crystals (cf. Chemistry News; 49 (9) September 2001; pp. 1018-1025).
  • Jacket particles consist of a material that either does not flow or becomes flowable at a temperature above the flow temperature of the jacket material. This can be achieved by using polymeric materials with a correspondingly high glass transition temperature (T g ), preferably crosslinked polymers, or by using inorganic ones
  • Effect colorants preferably have a difference between the refractive indices of the core material and the cladding material of at least 0.001, preferably at least 0.01 and particularly preferably at least 0.1. If the effect colorants according to the invention are to exhibit technically usable photonic effects, then there are
  • Refractive index differences of at least 1.5 are preferred.
  • nanoparticles are embedded in the matrix phase of the effect colorants in addition to the cores of the core-shell particles.
  • These particles are selected with regard to their particle size so that they fit into the cavities of the spherical packing from the cores and so change the arrangement of the cores only slightly. Through the targeted selection of appropriate materials and / or the particle size, it is possible, on the one hand, to change the optical effects of the effect colorants, for example to increase the intensity.
  • the matrix can be appropriately functionalized by incorporating suitable “quantum dots”.
  • Preferred materials are inorganic nanoparticles, in particular nanoparticles of metals or of II-VI or III-V semiconductors or of materials which influence the magnetic properties of the materials. Examples of preferred nanoparticles are gold, zinc sulfide, hematite or gallium arsenide.
  • the chain ends of the shell polymers generally have the tendency to assume the shape of a coil. If two particles come too close, the balls are compressed according to the model and repulsive forces arise. Since the shell polymer chains of different particles also interact with each other, the polymer chains are stretched according to the model if two particles move away from each other. The effort of the sheath polymer chains to resume a ball shape creates a force that pulls the particles closer together again. After the model presentation, the far-reaching order of the
  • Core-shell particles whose shell is connected to the core via an intermediate layer have proven to be particularly well suited for the production of effect colorants according to the invention.
  • the shell of this core-shell particle consists of organic polymers which are preferably grafted onto the core via an at least partially cross-linked intermediate layer.
  • the core can consist of various materials. It is essential according to the invention, as already stated, that there is a refractive index difference from the cladding and that the core remains solid under the processing conditions.
  • the core consists of an organic polymer, which is preferably crosslinked.
  • chalcogenides are compounds in which an element of the 16th group of the periodic table is the electronegative binding partner; as pnictide those in which an element of the 15th group of the periodic table is the electronegative binding partner.
  • Preferred cores consist of metal chalcogenides, preferably metal oxides, or metal pnictides, preferably nitrides or phosphides.
  • Metal in the sense of these terms are all elements that can appear as electropositive partners in comparison to the counterions, such as the classic metals of the subgroups or the main group metals of the first and second main groups, but also all elements of the third main group and silicon,
  • Germanium, tin, lead, phosphorus, arsenic, antimony and bismuth Germanium, tin, lead, phosphorus, arsenic, antimony and bismuth.
  • the preferred metal chalcogenides and metal pnictides include in particular silicon dioxide, aluminum oxide, gallium nitride, boron and aluminum nitride as well as silicon and phosphorus nitride.
  • the starting material for the production of the core-shell particles according to the invention preferably monodisperse cores made of silicon dioxide are used, which can be obtained, for example, by the process described in US Pat. No. 4,911,903.
  • the cores are produced by hydrolytic polycondensation of tetraalkoxysilanes in an aqueous ammoniacal medium, with a sol of
  • Si0 2 cores which are coated with (semi) metals or non-absorbent metal oxides, such as Ti0 2 , Zr0 2 , Zn0 2 , Sn0 2 or Al 2 0 3 .
  • SiO 2 cores coated with metal oxides is described, for example, in US Pat. No. 5,846,310.
  • Monodisperse cores made of non-absorbent metal oxides such as Ti0 2 , Zr0 2> Zn0 2 , Sn0 2 or Al 2 0 3 or metal oxide mixtures can also be used as the starting material. Their manufacture is, for example, in
  • Cores are separated, washed and dried in the usual way, for example by centrifugation.
  • monodisperse cores made of polymers which contain particles, for example metal oxides are also suitable as the starting material for the production of the core-shell particles according to the invention.
  • Such materials are offered for example by the company micro capseries- undmaschines GmbH in Rostock.
  • Micro-encapsulations based on polyester, polyamides and natural and modified carbohydrates are manufactured according to customer-specific requirements.
  • Monodisperse cores made of metal oxides which are coated with organic materials, for example silanes, can also be used.
  • the monodisperse cores are dispersed in alcohols and modified with common organoalkoxysilanes.
  • the silanization of spherical oxide particles is also described in DE 43 16 814.
  • the cores of the core-shell particles according to the invention can also contain dyes, for example so-called nanocolorants, as described for example in WO 99/40123, can be used.
  • dyes for example so-called nanocolorants, as described for example in WO 99/40123, can be used.
  • the disclosure of WO 99/40123 is hereby expressly included in the disclosure of the present application.
  • Sheath material is filmable, ie that it can be softened, plasticized or liquefied visco-elastically by simple measures to such an extent that the cores of the core / sheath particles can at least form domains of a regular arrangement.
  • the nuclei which are regularly arranged in the matrix formed by filming the cladding of the core / cladding particles form a diffraction grating which causes interference effects and thus leads to very interesting color effects.
  • the materials of the core and shell can, provided they meet the conditions specified above, have an inorganic, organic or even metallic character or they can be hybrid materials.
  • the cores contain one or more polymers and / or copolymers (core polymers) or that they consist of such polymers consist.
  • the cores preferably contain a single polymer or copolymer.
  • the shell of the core / shell particles according to the invention also contains one or more polymers and / or copolymers (shell polymers; matrix polymers) or polymer precursors and, if appropriate, auxiliaries and additives, the
  • Composition of the jacket can be chosen so that it is essentially dimensionally stable and non-tacky in a non-swelling environment at room temperature.
  • Nuclear material gives the skilled worker the freedom of their relevant properties, such as. B. their composition, the particle size, the mechanical data, the refractive index, the glass transition temperature, the melting point and the weight ratio of core: shell and thus also determine the application properties of the core / shell particles, which ultimately also depend on the properties of the resulting effect colorants produced.
  • Polymers and / or copolymers which can be contained in the core material or of which it consists, are high molecular weight compounds which correspond to the specification given above for the core material. Both polymers and copolymers of polymerizable unsaturated monomers are suitable, as are polykonensates and copolycondensates of monomers with at least two reactive groups, such as, for. B. high molecular weight aliphatic, aliphatic / aromatic or fully aromatic
  • epoxy prepolymers are usually used, for example by reaction of bisphenol A or other bisphenols, resorein, hydroquinone, hexanediol or other aromatic or aliphatic diols or polyols or phenol-formaldehyde condensates or mixtures thereof with epichlorohydrin or other di- or
  • Polyepoxides are obtained, mixed with other compounds capable of condensation directly or in solution and allowed to harden.
  • the polymers of the core material are expediently crosslinked (co) polymers, since these usually only show their glass transition at high temperatures.
  • crosslinked polymers can either already in the course of
  • Copolycondensation have been crosslinked or, after the actual (co) polymerization or (co) polycondensation has ended, they can have been crosslinked in a separate process step.
  • the shell material as for the core material, in principle polymers of the classes already mentioned are suitable, provided that they are selected or constructed in such a way that they correspond to the specification given above for the shell polymers.
  • Polymers that meet the specifications for a sheath material can also be found in the groups of polymers and copolymers of polymerizable unsaturated monomers and in the polycondensates and copolycondensates of monomers with at least two reactive groups, such as, for. B. the high molecular weight aliphatic, aliphatic / aromatic or fully aromatic polyesters and polyamides.
  • Shell polymers are in principle for their production selected building blocks from all groups of organic film formers.
  • the choice of the shell polymers can be made almost arbitrarily. It only has to be ensured that these polymers can be provided with crosslinkable groups.
  • Some other examples may illustrate the wide range of polymers suitable for making the sheath.
  • polymers such as polyethylene, polypropylene, polyethylene oxide, polyacrylates, polymethacrylates, polybutadiene, polymethyl methacrylate, polytetrafluoroethylene, polyoxymethylene, polyesters, polyamides, polyepoxides, polyurethane, rubber, polyacrylonitrile and, for example, are suitable
  • sheath is to be comparatively high-index
  • polymers with a preferably aromatic basic structure such as polystyrene, polystyrene copolymers such as. B. SAN, aromatic-aliphatic polyesters and polyamides, aromatic polysulfones and polyketones, polyvinyl chloride, polyvinylidene chloride and, with suitable selection of a high-index core material, also polyacrylonitrile or polyurethane.
  • the core consists of crosslinked polystyrene and the shell consists of a polyacrylate, preferably polyethyl acrylate and / or polymethyl methacrylate, to which crosslinkable monomers have been added.
  • the weight ratio of core to shell is in the range from 2: 1 to 1: 5, preferably in the range from 3: 2 to 1: 3 and particularly preferably is in the range of 1: 1 to 2: 3.
  • the weight ratio of core to shell is in the range from 2: 1 to 1: 5, preferably in the range from 3: 2 to 1: 3 and particularly preferably is in the range of 1: 1 to 2: 3.
  • the core-shell particles to be used according to the invention can be produced by various processes.
  • a preferred possibility of obtaining the particles is a process for the production of core-shell particles, by a) surface treatment of monodisperse cores, and b) application of the shell from organic polymers to the treated cores.
  • the monodisperse cores are obtained in a step a1) by emulsion polymerization.
  • a crosslinked polymeric intermediate layer is preferably applied to the cores in step a)
  • Emulsion polymerization or by ATR polymerization applied which preferably has reactive centers to which the jacket can be covalently attached.
  • ATR-Polymerization stands here for Atomic Transfer Radicalic Polymerization, as for example in K. Matyjaszewski, Practical Atom Transfer Radical Polymerization, Polym.
  • the liquid reaction medium in which the polymerizations or copolymerizations can be carried out consists of the solvents, dispersants or diluents customarily used in polymerizations, in particular in processes of emulsion polymerization. This is done in such a way that the emulsifiers used to homogenize the core particles and shell precursors can develop sufficient effectiveness.
  • Aqueous media, in particular water, are favorable as the liquid reaction medium for carrying out the process according to the invention.
  • polymerization initiators are suitable which either decompose thermally or photochemically, form free radicals and thus initiate the polymerization.
  • thermally activatable polymerization initiators preference is given to those between 20 and 180 ° C., in particular between 20 and 80
  • Particularly preferred polymerization initiators are peroxides such as dibenzoyl peroxide, di-tert-butyl peroxide, peresters, percarbonates, perketals, hydroperoxides, but also inorganic peroxides such as H2O2, salts of peroxosulfuric acid and peroxodisulfuric acid, azo compounds, boralkyl compounds and homolytically disintegrating
  • peroxides such as dibenzoyl peroxide, di-tert-butyl peroxide, peresters, percarbonates, perketals, hydroperoxides, but also inorganic peroxides such as H2O2, salts of peroxosulfuric acid and peroxodisulfuric acid, azo compounds, boralkyl compounds and homolytically disintegrating
  • the initiators and / or photoinitiators which, depending on the requirements of the polymerized material, are used in amounts between 0.01 and 15% by weight, based on the polymerizable components, can be used individually or in combination with one another to take advantage of advantageous synergistic effects be applied.
  • Redox systems are also used, e.g. Salts of peroxodisulfuric acid and peroxosulfuric acid in combination with low-valent sulfur compounds, in particular ammonium peroxodisulfate in combination with sodium dithionite.
  • Polyaddition products are obtained analogously by reaction with compounds which have at least two, preferably three reactive groups, such as, for. B. epoxy, cyanate, isocyanate, or isothiocyanate groups, with compounds that carry complementary reactive groups.
  • isocyanates react with alcohols to form urethanes, with amines to form urea derivatives, while epoxides react with these complementaries to form hydroxyethers or hydroxyamines.
  • polyaddition reactions can advantageously also be carried out in an inert solvent or dispersant.
  • aromatic, aliphatic or mixed aromatic-aliphatic polymers e.g. as polyesters, polyurethanes, polyamides, polyureas, polyepoxides or solution polymers, in a dispersant such as. B. in water, alcohols, tetrahydrofuran,
  • dispersants preferably water-soluble high molecular weight organic compounds with polar groups, such as
  • Vinypyrrolidone partially saponified copolymer list from an acrylic ester and Acrylonitrile, polyvinyl alcohols with different residual acetate content, cellulose ether, gelatin, block copolymers, modified starch, low molecular weight, carbon and / or sulfonic acid group-containing polymers or mixtures of these substances are used.
  • Particularly preferred protective colloids are polyvinyl alcohols with a residual acetate content of less than 35, in particular 5 to 39 mol% and / or vinylpyrrolidone-oleyl propionate copolymers with a vinyl ester content of less than 35, in particular 5 to 30% by weight.
  • Nonionic or ionic emulsifiers can be used.
  • Preferred emulsifiers are, where appropriate, ethoxylated or propoxylated longer-chain alkanols or alkylphenols with different degrees of ethoxylation or propoxylation (e.g. adducts with 0 to 50 mol of alkylene oxide) or their neutralized, sulfated, sulfonated or phosphated derivatives.
  • Neutralized dialkylsulfosuccinates or alkyldiphenyloxide disulfonates are also particularly suitable.
  • Combinations of these emulsifiers with the protective colloids mentioned above are particularly advantageous since they give particularly finely divided dispersions.
  • the particle size can be adjusted by selecting suitable emulsifiers and / or protective colloids or corresponding amounts of these compounds.
  • reaction conditions such as temperature, pressure, reaction time, use of suitable catalyst systems which influence the degree of polymerization in a known manner and the selection of the monomers used for their preparation by type and proportion, the desired combinations of properties of the required polymers can be set in a targeted manner.
  • Monomers which lead to polymers with a high refractive index are generally those which either have aromatic partial structures or those which have heteroatoms with a high atomic number, such as, for example, B. halogen atoms, especially bromine or iodine atoms, sulfur or metal ions, d. H. via atoms or groupings of atoms which increase the polarizability of the polymers.
  • Polymers with a low refractive index are accordingly obtained from monomers or monomer mixtures which do not contain the mentioned partial structures and / or atoms with a high atomic number or only in a small proportion.
  • R represents hydrogen or methyl.
  • the phenyl rings of these monomers can carry further substituents. Such substituents are suitable for modifying the properties of the polymers produced from these monomers within certain limits. They can therefore be used in a targeted manner, in particular to optimize the properties of the effect colorants according to the invention which are relevant in terms of application technology.
  • Suitable substituents are in particular halogen, NO 2 , alkyl having one to twenty carbon atoms, preferably methyl, alkoxy having one to twenty carbon atoms, carboxyalkyl having one to twenty carbon atoms, carbonylalkyl having one to twenty carbon atoms, or - OCOO alkyl with one to twenty
  • alkyl chains of these radicals can in turn be optionally substituted or by double-bonded heteroatoms or structural groups such as. B. -O-, -S-, -NH-, -COO-, -OCO- or -OCOO- in non-adjacent positions.
  • the refractive index of polymers can also be increased by polymerizing in monomers containing carboxylic acid groups and converting the "acidic" polymers thus obtained into the corresponding salts with metals of higher atomic weight, such as, for. B. preferably with K, Ca, Sr, Ba, Zn, Pb, Fe, Ni, Co, Cr, Cu, Mn, Sn or
  • the abovementioned monomers which make a high contribution to the refractive index of the polymers produced therefrom, can be homopolymerized or copolymerized with one another. They can also be copolymerized with a certain proportion of monomers that make a lower contribution to the refractive index.
  • Such copolymerizable monomers with a lower refractive index contribution are, for example, acrylates, methacrylates or vinyl ethers or vinyl esters with purely aliphatic radicals.
  • bifunctional or polyfunctional compounds which can be copolymerized with the abovementioned monomers or which can subsequently react with the polymers with crosslinking can also be used as crosslinking agents for the production of crosslinked polymer cores from free-radically produced polymers or for the subsequent crosslinking of the matrix from matel material ,
  • Group 1 bisacrylates, bismethacrylates and bisvinyl ethers of aromatic or aliphatic di- or polydydroxy compounds, in particular of butanediol (butanediol-di (meth) acrylate, butanediol-bis-vinyl ether), hexanediol (hexanediol-di (meth) acrylate, hexanediol-bis-vinyl ether ), Pentaerythritol, hydroquinone, bis-hydroxyphenylmethane, bis-hydroxyphenyl ether, bis-hydroxymethyl-benzene,
  • Ethylene oxide spacers propylene oxide spacers or propylene oxide spacers.
  • crosslinkers in this group are e.g. B. di- or polyvinyl compounds such as divinybenzene or methylene bisacrylamide, triallyl cyanurate,
  • R is hydrogen or methyl
  • Group 2 reactive crosslinking agents which have a crosslinking effect, but mostly have a postcrosslinking effect, e.g. B. with heating or drying, and which are copolymerized into the core or shell polymers as copolymers.
  • Examples include: N-methylol- (meth) acrylamide, acrylamidoglycolic acid and their ethers and / or esters with C 1 to C 6 alcohols, diacetone acrylamide (DAAM), glycidyl methacrylate (GMA),
  • DAAM diacetone acrylamide
  • GMA glycidyl methacrylate
  • Methacryloyloxypropyl trimethoxysilane MEMO
  • vinyl trimethoxysilane vinyl trimethoxysilane
  • m-isopropenyl benzyl isocyanate TMI
  • Group 3 Carboxylic acid groups which have been incorporated into the polymer by copolymerization of unsaturated carboxylic acids are crosslinked like polyvalent metal ions.
  • unsaturated carboxylic acids are acrylic acid
  • Methacrylic acid, maleic anhydride, itaconic acid and veneric acid are used.
  • Mg, Ca, Sr, Ba, Zn, Pb, Fe, Ni, Co, Cr, Cu, Mn, Sn, Cd are suitable as metal ions.
  • Ca, Mg and Zn, Ti and Zr are particularly preferred.
  • Group 4 Post-crosslinked additives. This is understood to mean additives which are functionalized to a greater or greater extent and which react irreversibly with the polymer (by addition or preferably condensation reactions) to form a network. Examples of this are compounds that are per Molecule have at least two of the following reactive groups: epoxy, aziridine, isocyanate acid chloride, carbodiimide or carbonyl groups, further z. B. 3,4-dihydroxy-imidazolinone and its derivatives (Fixapret brands from BASF).
  • postcrosslinkers with reactive groups such as e.g. B. epoxy and isocyanate groups complementary reactive groups in the polymer to be crosslinked.
  • reactive groups such as e.g. B. epoxy and isocyanate groups complementary reactive groups in the polymer to be crosslinked.
  • isocyanates react with alcohols to form urethanes, with amines to form urea derivatives, while epoxides react with these complementary groups to form hydroxyethers or hydroxyamines.
  • Post-crosslinking is also understood to mean photochemical curing, an oxidative or an air or moisture-induced curing of the systems.
  • the monomers and crosslinking agents mentioned above can be combined with one another and (co-) polymerized in a targeted manner in such a way that an optionally crosslinked (co-) polymer is obtained with the desired refractive index and the required stability criteria and mechanical properties.
  • the coating of organic polymers is carried out by grafting, preferably by emulsion polymerization or ATR polymerization. there the methods and monomers described above can be used accordingly.
  • the core is one before the shell is polymerized on
  • the effect colorants contain at least one contrast material.
  • the contrast materials cause an increase in the brilliance, contrast and depth of the color effects observed in the effect colorants according to the invention.
  • Contrast materials are understood according to the invention to mean all materials which bring about such an enhancement of the optical effect. These contrast materials are usually pigments.
  • pigments mean any solid
  • a pigment is an inorganic or organic, colored or achromatic colorant that is practically insoluble in the application medium. Both inorganic and organic pigments can be used according to the invention.
  • pigments can be divided into absorption pigments and gloss pigments.
  • Absorption pigments are pigments that absorb at least part of the visible light and therefore produce a color impression and, in extreme cases, appear black.
  • luster pigments are pigments in which luster effects are created by specular reflection on predominantly flat and aligned metallic or highly refractive pigment particles.
  • interference pigments are glossy pigments whose coloring effect is wholly or predominantly based on the phenomenon of interference.
  • Pigments or fire-colored metal bronzes are of particular importance among the interference pigments.
  • the pearlescent pigments consist of colorless, transparent and highly refractive platelets. After orientation in a matrix, they produced a soft gloss effect, which is referred to as pearlescent.
  • Peilglanz pigments are guanine-containing fish silver, pigments based on lead carbonates, bismuth oxychloride or titanium dioxide mica.
  • the titanium dioxide mica which is characterized by mechanical, chemical and thermal stability, is often used for decorative purposes.
  • absorption and gloss pigments can be used, and interference pigments in particular can also be used. It has been shown that the use of absorption pigments is preferred in particular to increase the intensity of the optical effects. Both white and
  • Coloring or black pigments are used, the term color pigments meaning all pigments which give a different color impression than white or black, such as, for example, Heliogen TM Blue K 6850 (from BASF, Cu-phthalocyanine pigment), Heliogen TM Green K 8730 ( BASF, Cu phthalocyanine pigment), Bayferrox TM 105 M (Bayer, iron oxide-based red pigment) or chrome oxide green GN-M (Bayer, chrome oxide-based green pigment).
  • the black pigments are preferred among the absorption pigments because of the color effects achieved.
  • pigmentary carbon black e.g. the carbon black product line from Degussa (in particular
  • Black mica qualities can also be used advantageously as black pigment (eg Iriodin TM 600, Merck; iron oxide-coated mica).
  • the particle size of the at least one contrast material is at least twice as large as the particle size of the core material. If the particles of the contrast material are smaller, only insufficient optical effects are achieved. It is believed that smaller particles interfere with the arrangement of the nuclei in the matrix and cause a change in the lattices that form.
  • the particles of at least twice the size of the cores which are preferably used according to the invention interact only locally with the lattice formed from the core.
  • the particle size of the contrast materials which are often also platelet-shaped as pigments, means the greatest extent of the particles in each case. If platelet-shaped pigments have a thickness in the region of the particle size of the cores and or even below it, this disturbs the
  • the shape of the embedded contrast material particles has little or no influence on the optical effect.
  • both spherical and platelet-shaped and needle-shaped contrast materials can be incorporated. Only the absolute particle size in relation to the particle size of the nuclei seems to be of importance. It is therefore preferred according to the invention if the particle size of the at least one contrast material is at least twice as large as the particle size of the core material, the particle size of the at least one contrast material preferably being at least four times as large as the particle size of the core material, since then the observable interactions are even smaller are.
  • a reasonable upper limit for the particle size of the contrast materials results from the limit at which the individual particles themselves become visible or, owing to their particle size, impair the mechanical properties of the effect colorant.
  • the person skilled in the art has no difficulty in determining this upper limit.
  • the amount of contrast material that is used is also important for the effect desired according to the invention. It has been shown that effects are usually observed when at least 0.05% by weight of contrast material, based on the weight of the effect colorant, is used. It is particularly preferred if the effect colorant is at least 0.2% by weight and particularly preferably at least 1% by weight. % Contains contrast material, since these increased contents of contrast material generally also lead to more intensive effects according to the invention.
  • contrast material may impair the processing properties of the core / shell particles and thus make it more difficult to produce the effect colorants according to the invention.
  • the effect colorant contains a maximum of 20% by weight of contrast material, based on the weight of the effect colorant, it being particularly preferred if the effect colorant contains a maximum of 12% by weight and particularly preferably a maximum of 5% by weight. Contains contrast material.
  • the effect colorants contain as large amounts of contrast material as possible. This is particularly the case if the contrast material is to increase the mechanical strength of the effect colorant at the same time.
  • the effect colorant according to the invention is preferably platelet-shaped particles whose thickness is preferably in the range from 0.5 to 20 ⁇ m, particularly preferably in the range from 1 to 10 ⁇ m, with at least 5, preferably at least 8 and in particular in the platelet in each spatial direction preferably at least 10 core layers follow one another.
  • the effect colorants according to the invention can be obtained by grinding or breaking from films of core-shell particles, the production of which in
  • the present invention further provides a process for the production of effect colorants, in which core-shell particles, the core of which is essentially solid and have an essentially monodisperse size distribution, with a difference between the refractive indices of the core material and the shell material , a film is produced, the matrix of which is brittle, and the film is subsequently comminuted into particles, preferably ground.
  • core-shell particles are used, the shell of which is made of polymers
  • Polystyrene derivatives such as. B. poly (iodostyrene) and poly (bromostyrene),
  • core-shell particles are used, the shell of which consists of polymers that are crosslinkable
  • the core-shell particles are preferably additized with postcrosslinking additives before the film is produced and the actual crosslinking takes place after the film has been produced.
  • the post-crosslinker or crosslinkable functionality can in particular be those described above
  • Networking can are started according to the methods described, thermal activation for postcrosslinking being particularly preferred.
  • a mixture of core-shell particles and possibly other additives is first produced.
  • the mixture is then preferably subjected to a mechanical force at a temperature at which the jacket is flowable.
  • the temperature at which the mixture is exposed to the mechanical force is at least 40 ° C., preferably at least 60 ° C. above the glass point of the shell of the core-shell particles. It has been shown empirically that the flowability of the jacket in this temperature range particularly meets the requirements for economical production of the films.
  • the flowable mixtures are cooled under the action of the mechanical force to a temperature at which the jacket is no longer flowable.
  • the mechanical action of force can, according to the invention, be such a force action that occurs in the usual processing steps of polymers.
  • the mechanical force is applied either: - by uniaxial pressing or - during a transfer pressing process, - during a (co-) extrusion or - during a calendering process or - during a blowing process.
  • the films according to the invention are preferably films. Films according to the invention can preferably also be produced by calendering, film blowing or flat film extrusion.
  • the films according to the invention can contain auxiliaries and additives. They can be used to optimally set the application data or properties desired or required for application and processing.
  • auxiliaries and / or additives are plasticizers, film-forming aids, leveling agents, fillers, melting aids,
  • n is a number from 2 to 4, preferably 2 or 3, and m is a number from 0 to 500.
  • the number n can vary within the chain and the various chain links can be built in in a statistical or block-wise distribution.
  • auxiliaries are ethylene glycol, propylene glycol, di-, tri- and
  • organic or inorganic solvents, dispersants or diluents which, for example, extend the open time of the formulation, ie the time available for its application to substrates, are also possible, waxes or hot-melt adhesives as additives. If desired, stabilizers against UV radiation and weather influences can also be added to the films.
  • z. B derivatives of 2,4-dihydroxybenzophenone, derivatives of 2-cyano-3,3'-dephenyl acrylate, derivatives of 2,2 ', 4,4'-tetrahydroxybenzophenone,
  • the total amount of auxiliaries and / or additives is up to 40% by weight.
  • the films consist of at least 60% by weight, preferably at least 80% by weight and particularly preferably at least 95% by weight of core-shell particles.
  • the effect colorants according to the invention are produced from these films by cutting, breaking and / or grinding the films to give pigments of a suitable size. This process can take place, for example, in a continuous belt process. A rolling mill or a grinder can be used. If particularly uniform particle sizes are desired for the effect colorants, one or more sieving steps can follow the comminution step.
  • the resulting pigments are particularly suitable for use in paints, varnishes, printing inks, plastics, ceramic materials, glasses and cosmetic formulations.
  • pigments for example inorganic and organic absorption pigments, metallic effect pigments and LCP
  • Pigments mixed.
  • the particles according to the invention are also suitable for the production of pigment preparations and for the production of dry preparations, such as, for example, granules.
  • Such pigment particles preferably have a platelet-shaped structure with an average particle size of 5 ⁇ m - 5 mm.
  • the pigment of the invention can then be used to pigment paints, powder coatings, paints, printing inks, plastics and cosmetic formulations, such as e.g. lipsticks, nail polishes, cosmetic sticks, press powder, make-ups, shampoos and loose powders and gels.
  • cosmetic formulations such as e.g. lipsticks, nail polishes, cosmetic sticks, press powder, make-ups, shampoos and loose powders and gels.
  • the concentration of the effect colorant in the application system to be pigmented, i.e. the dispersion is generally between 0.1 and 70% by weight, preferably between 0.1 and 50% by weight and in particular between 1.0 and 20% by weight, based on the total solids content of the system. It is usually dependent on the specific
  • Plastics usually contain the pigment according to the invention in amounts of from 0.01 to 50% by weight, preferably from 0.01 to 25% by weight, in particular from 0.1 to 7% by weight, based on the plastic composition.
  • the pigment mixture is used in amounts of 0.1 to 30% by weight, preferably 1 to 10% by weight, based on the
  • Lacquer dispersion used.
  • alkyd resins have proven to be particularly advantageous for incorporating the effect colorants according to the invention.
  • Alkyd resins are physically curing paints made from polyester resins, oils and fatty acids with a solvent content of usually less than 15%.
  • Pigmentation of binder systems e.g. for paints and printing inks for gravure printing, offset printing or screen printing, or as a preliminary product for printing inks, e.g. in the form of highly pigmented pastes, granules, pellets, etc., have become especially pigment mixtures with spherical colorants, such as Ti0 2 , carbon black , Chromium oxide, iron oxide and organic
  • Color pigments have proven to be particularly suitable.
  • the pigment is generally added to the printing ink in amounts of 2-35% by weight, preferably 5- 25 wt .-%, and in particular 8-20 wt .-% incorporated.
  • Offset printing inks can contain the pigment up to 40% by weight or more.
  • the invention therefore also includes dispersions which contain the effect colorant according to the invention and contain a suitable film former and / or carrier.
  • Example 1 Production of particles with a core made of polystyrene.
  • Intermediate layer made of p (MMA-co-ALMA) and sheath made of polv (cvclohexyl methacrylate)
  • Example 2 Production of particles with a core made of polv (methyl methacrylate) and a jacket made of polystyrene
  • a receiver In a 1-liter stirred tank reactor preheated to 75 ° C. with a propeller stirrer, argon protective gas inlet and reflux condenser, a receiver is heated to 4 ° C., consisting of 217 g water, 0.4 g ALMA (Fa.
  • Example 3 Production of particles by isostatic pressing and subsequent grinding
  • Example 4 Preparation of a paint dispersion
  • Formulations each consisting of 5% by weight of effect colorant from Example 3 in alkyd resin clearcoat (Swing Color Clearcoat glossy from Bauhaus) are prepared by stirring the pigment particles into the paint.
  • the resulting dispersion is spread on a paint card.
  • a color effect coating results from brightly reflecting pigments which, depending on the viewing direction, have an intensely green or intensely blue color.
  • Example 5 Production of particles by extrusion of films and subsequent grinding
  • 3 kg of the core-shell particles from example 1 or 2 are comminuted in a cutting mill (Rapid, type: 1528) with ice cooling and then in a single-screw extruder (Plasti-Corder; Brabender; screw diameter 19 mm with 1- Hole nozzle (3mm)) compounded. After a cooling section, a granulator A 90-5 (Fa.
  • the granules are made on a flat film line consisting of a single-screw extruder (from Göttfert; type: extrusiometer; screw diameter 20 mm; L / D 25), a thickness-adjustable film tool (width 135 mm) and a temperature-controlled smoothing unit (from Leistritz; roll diameter 15 mm;
  • Roller width 350 mm processed.
  • a film strip 125 mm wide and 1 mm thick is obtained.
  • the film is crushed into pigment particles in a rolling mill.
  • Example 6 Production of core-shell particles with a crosslinkable shell
  • a stirred tank reactor preheated to 75 ° C. with a propeller stirrer, argon protective gas inlet and a reflux condenser, a template tempered to 4 ° C., consisting of 217 g water, 0.4 g butanediol diacrylate (Merck, destabilized), 3.6 g styrene ( BASF, destabilized) and 80 mg of sodium dodecyl sulfate (SDS; Merck) and under strong
  • Example 6a Core-shell particles, the shell of which consists of 80% by weight Cvclohexyl methacrylate, 18% by weight ethyl acrylate and 2% by weight hydroxyethyl methacrylate
  • the reaction is started by directly adding 50 mg sodium bisulfite (Merck), 350 mg sodium peroxodisulfate (Merck) and again 50 mg sodium bisulfite, each dissolved in 5 g water. After 20 minutes, a monomer emulsion of 8.1 g BDDA, 72.9 g styrene (Merck, destabilized), 0.375 g SDS, 0.1 g KOH and 110 g water is metered in continuously over a period of 120 minutes. The reactor contents are stirred for 30 minutes without further addition.
  • a second monomer emulsion comprising 1.5 g of ALMA (from Merck, destabilized), 13.5 g of MMA (methyl methacrylate, from Merck, desatbilized), 0.075 g of SDS and 20 g of water is then metered in continuously over a period of 25 minutes , The reactor contents are then stirred for 30 minutes without further addition.
  • a monomer emulsion consisting of 100 g CHMA (cyclohexyl methacrylate) (Degussa, destabilized), 20 g ethyl acrylate (Merck, destabilized), 5 g hydroxyethyl methacrylate (Merck, destabilized), 136 g water and 0.375 g SDS ( Na dodecyl sulfate) was metered in continuously over a period of 150 min. For almost complete reaction of the monomers, the mixture is then stirred for a further 60 min. The core-shell particles are then precipitated in 1 liter of methanol, the precipitation is completed by adding 25 g of concentrated aqueous sodium chloride solution, the suspension is mixed with 1 liter of demineralized water, suction filtered and dried.
  • CHMA cyclohexyl methacrylate
  • 20 g ethyl acrylate Merck, destabilized
  • 5 g hydroxyethyl methacrylate Merck, destabilized
  • the film is removed hot from the press and then cooled without pressure.
  • the film is then heated at 220 ° C. for 10 min without pressure for crosslinking.
  • the thin film is then ground into small particles in an agate mortar.
  • Example 7 Production of particles by extrusion of films and subsequent grinding
  • % By weight isocyanate hardener (CRELAN TM; Bayer) compounded. After a cooling section, granulation is carried out in an A 90-5 granulator (from Automatic). The granules are placed on a flat film line consisting of a single-screw extruder (from Göttfert; type: extrusiometer;
  • Foil tool width 135 mm
  • a temperable smoothing unit Fa.
  • the film is then heated to 190 ° C. After crosslinking, the brittle film is crushed into pigment particles in a rolling mill.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une matière colorante à effet sensiblement constituée de particules composées d'un noyau et d'une enveloppe, l'enveloppe formant une matrice et le noyau étant sensiblement solide et ayant une distribution dimensionnelle sensiblement monodispersée. La matière noyau et de la matière enveloppe ont des indices de réfraction différents. L'invention est caractérisée en ce que la matrice est friable. L'invention concerne également le procédé de production de cette matière colorante à effet et son utilisation.
PCT/EP2004/013005 2003-12-10 2004-11-17 Matiere colorante a effet contenant des particules composees d'un noyau et d'une enveloppe WO2005056621A1 (fr)

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DE2003157679 DE10357679A1 (de) 2003-12-10 2003-12-10 Effektfarbmittel enthaltend Kern-Mantel-Partikel
DE10357679.7 2003-12-10

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WO2007102910A2 (fr) * 2005-12-21 2007-09-13 Basf Corporation Procede d'incorporation d'un pigment dans une peinture par formation de billes de resine
WO2009023353A1 (fr) * 2007-05-23 2009-02-19 Carnegie Mellon University Structures composites de particule hybride avec une diffusion réduite
US7893173B2 (en) 2005-08-26 2011-02-22 Carnegie Mellon University Polymerization process with catalyst reactivation
WO2011023946A1 (fr) 2009-08-24 2011-03-03 Cambridge Enterprise Limited Matériaux optiques composites, utilisation de matériaux optiques composites et procédés pour la fabrication de matériaux optiques composites
US8252880B2 (en) 2007-05-23 2012-08-28 Carnegie Mellon University Atom transfer dispersion polymerization
US8273823B2 (en) 2005-08-23 2012-09-25 Carnegie Mellon University Atom transfer radical polymerization in microemulsion and true emulsion polymerization processes
US8367051B2 (en) 2006-10-09 2013-02-05 Carnegie Mellon University Preparation of functional gel particles with a dual crosslink network
US8962764B2 (en) 2009-03-27 2015-02-24 Carnegie Mellon University Preparation of functional star macromolecules
US9533297B2 (en) 2012-02-23 2017-01-03 Carnegie Mellon University Ligands designed to provide highly active catalyst complexes
US9561615B2 (en) 2011-01-12 2017-02-07 Cambridge Enterprise Limited Manufacture of composite optical materials
US9644042B2 (en) 2010-12-17 2017-05-09 Carnegie Mellon University Electrochemically mediated atom transfer radical polymerization
US9982070B2 (en) 2015-01-12 2018-05-29 Carnegie Mellon University Aqueous ATRP in the presence of an activator regenerator
US9993397B2 (en) 2010-11-23 2018-06-12 Conopco Inc. Composite particles and compositions with composite particles
US10072042B2 (en) 2011-08-22 2018-09-11 Carnegie Mellon University Atom transfer radical polymerization under biologically compatible conditions
WO2019180619A1 (fr) * 2018-03-22 2019-09-26 3M Innovative Properties Company Particules de nitrure d'aluminium modifiées et leurs procédés de production
US11174325B2 (en) 2017-01-12 2021-11-16 Carnegie Mellon University Surfactant assisted formation of a catalyst complex for emulsion atom transfer radical polymerization processes
US11820844B2 (en) 2018-03-22 2023-11-21 3M Innovative Properties Company Charge-modified particles and methods of making the same

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US8273823B2 (en) 2005-08-23 2012-09-25 Carnegie Mellon University Atom transfer radical polymerization in microemulsion and true emulsion polymerization processes
US7893173B2 (en) 2005-08-26 2011-02-22 Carnegie Mellon University Polymerization process with catalyst reactivation
WO2007102910A3 (fr) * 2005-12-21 2007-11-29 Basf Corp Procede d'incorporation d'un pigment dans une peinture par formation de billes de resine
WO2007102910A2 (fr) * 2005-12-21 2007-09-13 Basf Corporation Procede d'incorporation d'un pigment dans une peinture par formation de billes de resine
US8367051B2 (en) 2006-10-09 2013-02-05 Carnegie Mellon University Preparation of functional gel particles with a dual crosslink network
WO2009023353A1 (fr) * 2007-05-23 2009-02-19 Carnegie Mellon University Structures composites de particule hybride avec une diffusion réduite
GB2463198A (en) * 2007-05-23 2010-03-10 Univ Carnegie Mellon Hybrid particle composite structures with reduced scattering
US8252880B2 (en) 2007-05-23 2012-08-28 Carnegie Mellon University Atom transfer dispersion polymerization
GB2463198B (en) * 2007-05-23 2013-05-22 Univ Carnegie Mellon Hybrid particle composite structures with reduced scattering
US8865797B2 (en) 2007-05-23 2014-10-21 Carnegie Mellon University Hybrid particle composite structures with reduced scattering
US8962764B2 (en) 2009-03-27 2015-02-24 Carnegie Mellon University Preparation of functional star macromolecules
WO2011023946A1 (fr) 2009-08-24 2011-03-03 Cambridge Enterprise Limited Matériaux optiques composites, utilisation de matériaux optiques composites et procédés pour la fabrication de matériaux optiques composites
US9993397B2 (en) 2010-11-23 2018-06-12 Conopco Inc. Composite particles and compositions with composite particles
US9644042B2 (en) 2010-12-17 2017-05-09 Carnegie Mellon University Electrochemically mediated atom transfer radical polymerization
US9561615B2 (en) 2011-01-12 2017-02-07 Cambridge Enterprise Limited Manufacture of composite optical materials
US10072042B2 (en) 2011-08-22 2018-09-11 Carnegie Mellon University Atom transfer radical polymerization under biologically compatible conditions
US9533297B2 (en) 2012-02-23 2017-01-03 Carnegie Mellon University Ligands designed to provide highly active catalyst complexes
US9982070B2 (en) 2015-01-12 2018-05-29 Carnegie Mellon University Aqueous ATRP in the presence of an activator regenerator
US11174325B2 (en) 2017-01-12 2021-11-16 Carnegie Mellon University Surfactant assisted formation of a catalyst complex for emulsion atom transfer radical polymerization processes
WO2019180619A1 (fr) * 2018-03-22 2019-09-26 3M Innovative Properties Company Particules de nitrure d'aluminium modifiées et leurs procédés de production
CN111886216A (zh) * 2018-03-22 2020-11-03 3M创新有限公司 改性的氮化铝粒子及其制备方法
US11492495B2 (en) 2018-03-22 2022-11-08 3M Innovative Properties Company Modified aluminum nitride particles and methods of making the same
US11820844B2 (en) 2018-03-22 2023-11-21 3M Innovative Properties Company Charge-modified particles and methods of making the same

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