WO2022129201A1 - Agent de matité lamellaire pour peinture en poudre et peintures en poudre - Google Patents

Agent de matité lamellaire pour peinture en poudre et peintures en poudre Download PDF

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Publication number
WO2022129201A1
WO2022129201A1 PCT/EP2021/085944 EP2021085944W WO2022129201A1 WO 2022129201 A1 WO2022129201 A1 WO 2022129201A1 EP 2021085944 W EP2021085944 W EP 2021085944W WO 2022129201 A1 WO2022129201 A1 WO 2022129201A1
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Prior art keywords
additive
substrate
formula
atoms
butyl
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PCT/EP2021/085944
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English (en)
Inventor
Michael GRÜNER
Roland Albert
Günter KAUPP
Christian Rummer
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Eckart Gmbh
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Publication of WO2022129201A1 publication Critical patent/WO2022129201A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/06—Treatment with inorganic compounds
    • C09C3/063—Coating
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/40—Compounds of aluminium
    • C09C1/405—Compounds of aluminium containing combined silica, e.g. mica
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/40—Compounds of aluminium
    • C09C1/407—Aluminium oxides or hydroxides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/40—Compounds of aluminium
    • C09C1/42—Clays
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/12—Treatment with organosilicon compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/03—Powdery paints
    • C09D5/033—Powdery paints characterised by the additives
    • C09D5/035—Coloring agents, e.g. 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent

Definitions

  • the present invention relates to a matting agent which can be used in powder coatings. Especially the matting agent can be used as a so-called post-adding additive in powder coatings. The invention relates also to powder coatings containing this matting agent.
  • Powder coating is a fast growing segment in the coatings industry due to the fact that no emission of organic solvents are involved during application and preparation of the coating compositions. Further advantages are the easy manageability of the systems and their ready-to-use properties. They exhibit a high efficiency in the sense that overspray can usually be recycled.
  • Additives for powder coatings are usually added to the pre-mix and then mixed with other components. Thereafter the composition is melt-extruded and then milled to a certain grain size.
  • JP 2004 010735 A discloses fillers based on CaCCh for powder coatings.
  • CN 111378298 A discloses a filler for powder coatings based on rod-like fillers. These fillers enable an increase of the gloss of the powder coatings.
  • WO 2014/202495 A1 discloses a powder coating composition with two different silicon resins and mica as a filler for high-temperature resistant compositions.
  • DE 102009023158 A1 discloses transparent platelet-like substrates which are coated with a SiO2 layer or with SiO2 particles embedded in a matrix for use in powder coatings. These fillers or effect pigments enable better electrostatic application in powder coatings.
  • WO 2015/057895 A1 discloses expanded volcanic glass functional fillers for use as reinforcing and functional additives in polyolefins, engineering alloys and blends and also in epoxy powder coating systems. These fillers can also be surface modificated by e.g. organofunctional silanes.
  • Polysiloxane coated fillers were disclosed in EP 1690884 A1 for use in plastics.
  • Matting additives are used to lower and control the gloss of the powder coating film.
  • waxes can be used either in pure form or in combination with other fillers.
  • the use of waxes limits the matting effect to a gloss > 40 (60° geometry).
  • the waxes may be given off depending on their incompatibility with the binder components of the powder coating leading to greasy surfaces.
  • Matted powder coating surfaces can be made, for example, by:
  • curing agents which can react with different functional groups of the binder (e.g. a mixture of hydroxyl- or carboxyl polyester) or itself have different functional groups.
  • Examples 1) to 3) are used for epoxy-, polyester-epoxy-, or polyurethane powder coating systems, whereas examples 4) and 5) are solely used for polyurethane systems. These methods have the disadvantage that the degree of glossiness is obtained during the preparation of the powder coating composition by steps of pre-mixing, extruding, grinding and optionally mixing and therefore cannot be corrected afterwards.
  • WO 99/36481 discloses matting agents based on fumed metal oxides.
  • CN 106675152 A discloses a matting agent for powder coating based of silane modified inorganic fillers.
  • the inorganic filler is typically a glass-like non-platelet material.
  • silanes a mixture of a first silane and a second silane is used, wherein the first silane is selected from methacryloxy silane or vinyl silane and the second silane is selected from the group consisting of fluoro silane, alkyl silane and sulfur- containing silane or a mixture thereof.
  • a new additive was recently introduced in the market based on trimellite acid derivates which is capable to be used as post-adding additive and matting agent.
  • This additive is used in amounts of about 5 to 20 % per weight and more preferably even 10 to 20 % per weight which is a remarkable high value for an additive.
  • Such high amounts of an additive may have detrimental effects to the powder coatings.
  • EP 2698403 B1 discloses surface modified pearlescent pigments and EP 2318463 B1 discloses surface modified metal effect pigments which can be both used in powder coatings by extrusion.
  • the additive should be usable in small amounts in the order of only a few weight-% of the powder coating and it should not significantly alter other optical properties of the powder coatings film like Hue, Chroma or Lightness.
  • the additive can be used as matting agent in a wide variety of powder coatings.
  • the matting agent should easily be manufactured. Powder coatings should be easily manageable with such additive.
  • the object is solved by providing an additive comprising a transparent platelet substrate which is at least partially coated on the surface of the substrate with a surface modification agent of formula (I):
  • the object of the invention is also solved by providing a method of producing the additive, wherein the surface of the transparent platelet substrate is coated with a polysiloxane of formula (II):
  • the object of the invention is also solved by the use of the matting agent of claims 1 to 12 in powder coatings as a post-adding additive.
  • the object of the invention is also solved by providing a powder coating composition containing the additive of claims 1 to 12.
  • the additive of the present invention is particularly suitable as matting agent for powder coating. Most preferred is the use of this additive as a post-adding matting additive for powder coatings.
  • the transparent substrate has to have a platelet-like shape.
  • the aspect ratio is defined as the ratio of the longest dimension (D50) and the average thickness of a particle and is preferably at least 5:1 , more preferably more than 10:1 and further preferably more than 50:1.
  • the size of the additive (matting agent) according to this invention is a crucial parameter.
  • the size distribution is preferably determined by laser granulometry and can be expressed as volume weighted frequency distribution function.
  • the median value D50 is defined as the size where 50% of the volume weighted particles have this size or below.
  • the D50 can be used as a measure of the average particle size and is preferably in a range of 2 to 25 pm, more preferably in a range of 3 to 24 pm and most preferably in a range of 5 to 23 pm.
  • the platelet substrate coated with the surface modification agent has not too large particles in its particle size distribution.
  • a measure for the coarse particle sizes is the Dgo-value, which is defined as the size where 90% of the volume weighted particles have this size or below.
  • the Dgo-value of the volume averaged particle size distribution of the matting agent is ⁇ 60 pm, more preferably is Dgo ⁇ 55 pm and most preferably is Dgo ⁇ 45 pm.
  • the Dw-value is a common expression.
  • the Dw-value of the additive is in a range of 1.5 to 13.0 pm and more preferably in a range of 3.0 to 12 pm.
  • the width of a particle size distribution can be commonly described by the span D- value which is defined as
  • AD (Dgo-D )/D5o ("la)
  • the span for the additive is in a range of 0.9 to 3.3, and more preferably in a range of 1.0 to 3.0 and most preferable in a range of 1.0 to 2.0.
  • the span does not necessarily be very low as a brought particle size distribution is also possible in order to achieve the desired matting effect.
  • the size distribution of the additive is determined with laser granulometry using a Mastersizer 2000 (Malvern Panalytical) using Fraunhofer approximation and volume weighted size values referring to equivalent spheres.
  • the transparent platelet substrate is preferably synthetic mica, natural mica, glass flakes, AhOs-flakes, SiC>2-flakes, kaolin, octasilicates or mixtures thereof.
  • An example of an octasilicate is ilerite.
  • the transparent substrate is synthetic mica, glass flakes, AhOs-flakes or SiC>2-flakes or mixtures thereof and even more preferably it is synthetic mica or glass flakes.
  • the substrate is synthetic mica.
  • this material has the advantage that it is colourless, whereas natural mica always has a certain own colour which can lead to stronger deviation in the optical impression compared to a powder coating without the matting agent.
  • the surface of synthetic mica is less flat and uniform which potentially leads to higher scattering phenomena which can help in the reduction of gloss.
  • the additive suitable as matting agent is not a pearlescent pigment and is not or does not comprise an effect pigment at all as it is not coated with high- refractive index coatings such as TiC>2 or Fe20s typically used for pearlescent pigments.
  • the substrate is transparent and is essentially colourless and therefore does also not include any further dopants like e.g. dye's as described, for example in WO 1993/008237 A1 , which would impart absorption colours to the additive.
  • the additive is intended to reduce the gloss of coatings, but not to alter other properties like the Hue or Chroma of the coating.
  • the substrate is not coated with any other layer than the surface modification agent.
  • the substrate may be precoated with colourless transparent layers of metal oxides with a refractive index of ⁇ 1.8, preferably ⁇ 1.6 at optical wavelengths.
  • Typical examples may be SiC>2, AI2O3, AI(OH)s or mixtures thereof.
  • the purpose of such pre-coatings is primarily to enhance the bonding of the surface modification agent on the substrate surface in cases that the surface modification agent does not properly on the pure substrate surface.
  • the average thicknesses of the transparent substrates is preferably in a range of 0.05 to 3.0 pm, more preferably in a range of 0.08 to 2.0 pm and most preferably in a range of 0.1 to about 1 .0 pm.
  • the particles are too thick to show the matting effect. Below 0.05 pm the particles may be too thin and tend to agglomeration because of their high specific surface which is detrimental to the intended use.
  • the surface modification agent is of utmost importance for the matting effect.
  • the surface modification agent is a polysiloxane based on formula (I):
  • R 1 is a saturated or unsaturated linear or branched alkyl moiety with 1 to 30 C- atoms and/or an aryl-, alkylaryl- or arylalkyl moiety with 6 to 30 C-atoms.
  • R 2 , R 3 , R 4 und R 5 are independently saturated or unsaturated linear or branched alkyl moieties with 1 to 6 C-atoms and/or aryl-, alkylaryl- or arylalkyl moiety with 6 to 12 C-atoms.
  • p is from 0.3 to 2.0 and denotes to the fact that a mixture of different species of the polysiloxane regarding the termination groups can be involved.
  • p is from 0.5 to 1.9, more preferably from 0.8 to 1.8 and most preferably from 0.9 to 1.1.
  • p 1.0 and denotes to a monofunctional polysiloxane.
  • the rational number p is at least 0.3 as otherwise there is not enough polysiloxane which can be effectively bound to the substrate via the X (or R 7 or R 8 ) moieties.
  • the rational number m can be a rational as it denotes to an average value of a polymerisation length of the ethoxy moiety.
  • the entity [-CH2] y -A-B is at least two methylene moieties and that no peroxo bonds in this entity is formed.
  • R 7 and R 8 are independently O, OH or a saturated or unsaturated linear or branched alkyl moieties with 1 to 6 C-atoms and/or and/or aryl-, alkylaryl- or arylalkyl moiety with 6 to 9 C-atoms, and X is O or OH. At least one of R 7 , R 8 and/or X are bound to the surface of the substrate.
  • the polysiloxane of formula (I) contains no basic groups and hence no amino groups.
  • R 2 , R 3 , R 4 and R 5 in the polysiloxane of formula (I) are independently of one another saturated alkyl radicals such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or tert-butyl and/or an aromatic radical such as phenyl.
  • R 2 , R 3 , R 4 and R 5 are preferably the same.
  • R 2 , R 3 , R 4 and R 5 are all each methyl.
  • R 1 is alkyl, cycloalkyl or aryl having 1 to 12 C atoms. It has been found very suitable for R 1 to be methyl, ethyl, sec-butyl, n-propyl, isopropyl, n-butyl, secbutyl, tert-butyl, n-pentyl, neopentyl, cyclopentyl, n-hexyl, cyclohexyl, n-octyl, 2- ethylhexyl, phenyl, methylphenyl or ethylphenyl.
  • R 1 is an unbranched alkyl having 1 to 6 carbon atoms.
  • R 1 is methyl, ethyl, n-butyl, n-hexyl or phenyl.
  • R 1 is n- butyl or n-hexyl.
  • R 1 is n-butyl or n-hexyl and R 2 , R 3 , R 4 and R 5 are all each methyl.
  • the polysiloxane of formula (I) represents the polysiloxane bonded to the surface of the transparent, platelet substrate. It can be derived by hydrolysis and possibly condensation of the precursor polysiloxane of formula (II):
  • OR 9 stands for alkoxy radicals, more particularly methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy or isobutoxy. Methoxy and ethoxy are most preferred for Z.
  • the above-stated alkoxy radicals, fatty acid radicals or the halogen group can be hydrolyzed easily, the group(s) Z and also optionally R 7 and/or R 8 in formula (II) being replaced, as a result, by hydroxyl, which are then able to bond to the surface of the transparent, platelet substrate with condensation, as described above, preferably with formation of at least one metal — O — Si covalent bond, where the metal is a metal belonging of the transparent platelet substrate such as Al or Si.
  • the substrate will have metal-OH surface bonds like Si-OH or AI-OH which are capable to undergo a hydrolysis reaction with a Si-OH silanol group from the polysiloxane. In other cases also hydrogen bonds may be formed between the surface of the substrate and the Si-OH silanol or AI-OH bonds.
  • R 1 is different from R 2 , R 3 , R 4 and R 5 .
  • R 1 and also R 2 , R 3 , R 4 and R 5 are each alkyl radicals, with alkyl radical R 1 preferably having at least one carbon atom, more preferably at least 2 carbon atoms, even more preferably at least 3 carbon atoms, more than the alkyl radicals R 2 , R 3 , R 4 and R 5 .
  • R 1 is n-butyl or n-hexyl and R 2 , R 3 , R 4 and R 5 are each methyl.
  • the coated transparent substrate with the surface modification agent of formula (II) can be easily manufactured.
  • a polysiloxane of formula (II) is dissolved in a commercially customary solvent, if desired also under hydrolytic conditions, as for example in water or ethanol in the presence of acidic or basic catalyst, and is subsequently applied to the platelet-shaped substrate and dried.
  • a mixer of kneader optionally without adding water or catalysts.
  • a suitable solvent preferably an alcohol like ethanol or isopropanol
  • the polysiloxanes can be synthesized according to an equilibrium reaction described in Noll (Chemie und Technologie der Silikone, Wiley/VCH, Weinheim, 1984) which is well known to the skilled person.
  • alkyl lithium in step (1) it is possible to use alkyl lithium or aryl lithium R 1 Li, where R 1 is as defined in claim 1.
  • R 1 is as defined in claim 1.
  • use may be made of, for example, methyllithium, ethyllithium, sec-butyllithium, n-propyllithium, isopropyllithium, n- butyllithium, sec-butyllithium, tert-butyllithium, n-pentyllithium, neopentyllithium, cyclopentyllithium, n-hexyllithium, cyclohexyllithium, n-octyllithium, 2-ethyllithium, n-phenyllithium, methylphenyllithium or ethylphenyl-lithium, etc..
  • dialkylsilanol in step (1) and step (2) it is possible to use, for example, symmetrically or asymmetrically substituted dialkylsilanols R 2 R 3 Si(OH)2, where R 2 and R 3 are as defined in claim 1.
  • R 2 and R 3 are as defined in claim 1.
  • symmetrically substituted dialkylsilanols of dimethylsilanol, diethylsilanol, di-n- propylsilanol, di-isopropylsilanol, di-n-butylsilanol, di-sec-butylsilanol, di-tert- butylsilanol, etc.
  • dialkylsilanols it is possible to make use, for example, of ethylmethylsilanol, methyl-n-propylsilanol, n- butylmethylsilanol, isobutylmethylsilanol, tert-butylmethylsilanol, ethyl-n- propylsilanol, n-butyl-n-propylsilanol, n-butylethylsilanol, isobutyl-n-propylsilanol, tert-butyl-n-propylsilanol, etc. Preference is given to using symmetrically substituted dialkylsilanols.
  • step (3) it is possible to use symmetrically or asymmetrically substituted dialkylhalosilane, preferably dialkylchlorosilane HSiR 4 R 5 CI, where R 4 and R 5 are as defined in claim 1.
  • dialkylchlorosilane it is possible to make use, for example, of dimethylchlorosilane, diethylchlorosilane, di-n- propylchlorosilane, di-isopropylchlorosilane, di-n-butylchlorosilane, di-sec- butylchlorosilane, di-tert-butylchlorosilane, di-n-pentylchlorosilane, di-neo- pentylchlorosilane, di-cyclopentylchlorosilane, di-n-hexylchlorosilane, dicylcohexylchlorosilane, di-
  • dialkylchlorosilane As asymmetrically substituted dialkylchlorosilane it is possible to make use, for example, of ethylmethyl-chlorosilane, methyl-n-propylchlorosilane, n-butyl- methylchlorosilane, sec-butylmethylchlorosilane, tert-butyl-methylchlorosilane, n- butyl-ethylchlorosilane, sec-butyl-ethylchlorosilane, tert-butyl-ethylchlorosilane, etc.
  • a and B and also x and y in each case are as defined in claim 1.
  • the compounds used preferably as alkoxyalkylsilane or alkylchlorosilane in step (4) have a terminal ethylenic group, as for example a terminal alkenyl group such as a vinyl group or allyl group, or a 5-hexenyl radical, 7-octenyl radical or a 10- undecenyl radical.
  • alkoxy-alkylsilane or alkylchlorosilane it is possible, for example, to use vinyltrichlorosilane, vinyltri-tert-butoxysilane, vinyltriacetoxysilane, vinylphenylmethyl-methoxysilane, vinylphenylmethylchlorosilane, vinyl- phenyldiethoxysilane, vinyldiphenylchlorosilane, vinyl-dimethylethoxysilane, vinyldimethylchlorosilane, 1-vinyl-3-(chloromethyl)-1 ,1 ,3,3-tetramethyldisiloxane, vinyl(chloromethyl)dimethylsilane, vinyldimethylethoxy-silane, vinyltris(methoxypropoxy)silane, vinyltris-(2-methoxyethoxy)silane, vinyltrimethoxysilane, vinyl-triisopropoxysilane, vinyltriethoxysilane, vinylphenyl
  • the hydrosilylation reaction in step (4) is carried out in a usual way, preferably in the presence of a catalyst, as for example hexachloroplatinic(IV) acid at elevated temperature, as for example in the range from 20 to 200° C, preferably from 70 to 150° C.
  • a catalyst as for example hexachloroplatinic(IV) acid at elevated temperature, as for example in the range from 20 to 200° C, preferably from 70 to 150° C.
  • a preferred embodiment of the polysiloxane for use in producing the matting agent of the invention is represented in formula (IX), where the substituent C ⁇ g is preferably n-butyl.
  • the polysiloxane preferably contains an average of 2 to 200, more preferably of 2.5 to 150, more preferably still of 3 to 100, and even more preferably of 3.5 to 50, dimethylsiloxy units.
  • the compound (IX) thus hydrolyzed is attached, preferably covalently, to the transparent platelet substrate by way of the oxygen atoms.
  • the amount of the polysiloxane of formula (I) is preferably in a range of 0.1 to 5.0 wt.-%, referred to the total additive usable as matting agent. More preferably the amount is in a range of 0.2 to 4.0 wt.-%, furthermore preferably in a range of 0.3 to 3.0 wt.-% and most preferably in a range 0.35 to 2.0 wt.-%, each referred to the total amount of the additive usable as matting agent.
  • the particular amount used will depend on the specific surface of the transparent platelet substrate. Surprisingly already small amounts of this surface modification agent have a great positive impact to the matting agent properties of the transparent platelet substrate.
  • the surface modification agent is not effective enough and more than 5.0 wt.-% are hardly achievable as only a limited amount of the surface of the transparent platelet substrate can coated with the surface modification agent.
  • the surface modification agent will essentially not form more than a monolayer on the substrates surface as per molecule there is only one bond possible as derived from formula (II).
  • the surface of the transparent platelet substrate is further coated with organofunctional silanes different from formula (I).
  • the platelet structure of the transparent substrate modified with the polysiloxane of formula (I) act in a synergetic way to provide a matting effect of a powder coating.
  • a matting effect in powder coatings is connected with a controlled disturbance of the surface structure of the coated film.
  • the hydrophobic surface modification agent imparts “leafing” properties to the platelet-like substrate.
  • a leafing effect means that not essentially all platelet-like particles, but only a certain fraction of them is located on the top of the coating film due to incompatibility of the hydrophobic additive surface and the binder system of the powder coating. These “leafing” particles seem to be responsible for the matting effect.
  • a non-platelet morphology of the substrates would also not lead to this effect in such high effectivity as it is observed for the present additives.
  • Another object of the present invention is to provide a power coating composition containing the matting agent.
  • They can be used in a concentration range of 0.2 to 6.0 wt.-%, more preferably in a range of 0.5 to 5.0 wt.-%, even more preferably in a range of 0.6 to 4.0 wt.-% and most preferably in a range of 0.7 to 3.0 wt.-%, each based on the total amount of powder coating.
  • Other embodiments with ranges of 0.5 to 6.0 wt.-% or 0.8 to 4.5 wt.-% may be possible. The exact amount will depend on the desired level of gloss reduction of the powder coating.
  • the additive can be used in rather small amounts which will ensure that other properties like for example mechanical stability of the powder coating films are not adversely affected.
  • the powder coatings can be, for example, radiation-curing or chemically curing.
  • a large number of binders based on e.g. polyacrylates, polymethacrylates, polyesters, polyurethanes, polyepoxides, polyamide, polyvinyl butyrate, phenolic resins, polythetraflouroethylene, polyvinylidene fluorides, polyvinyl chloride or mixtures thereof are suitable.
  • Preferred binders are based on polyacrylates, polyesters, polyurethanes, polyepoxides and mixtures thereof.
  • the powder coatings do not contain any effect pigment, although they may contain inorganic or organic pigments or dyes.
  • the powder coatings may contain effect pigments such as platelet metal effect pigments or pearlescent pigments.
  • the powder coating may contain further fillers which are not modified by the surface modification agent of formula (I).
  • further fillers natural or synthetic mica, talc, glasses, kaolin, oxides of hydroxides of magnesium, calcium, zinc, barium sulfate, calcium sulfate calcium carbonate magnesium carbonate as well as mixtures thereof may be used.
  • matting agent of this invention it is possible to use the matting agent of this invention together with other matting agents.
  • waxes useable as matting agents such as Ceraflour® 970 or Ceraflour® 950 from Byk Additives GmbH.
  • the powder coatings can be applied on all kinds of substrates such as metals, glass, wood (particularly mdf), ceramics or plastics.
  • the powder coatings can be used as interior or exterior applications such as facade systems.
  • the powder coatings according to this invention are simple and easy to handle.
  • the matting agent is simply mixed with the powder coating in a dry blend step by using appropriate mixing equipment such as e.g. a paddle or tumbler mixer.
  • another embodiment of the present invention is directed to a process of producing a powder coating composition comprising the steps: a) preparing a powder coating composition and b) adding the matting agent by dry blend to the powder coating composition of a).
  • the degree of reaction was determined by NMR, until the hexa-methylcyclotrisiloxane fraction was ⁇ 1% by weight.
  • the reaction was then terminated by addition of 1.16 mol of dimethylchlorosilane for 0.5 h at 25° C, the reaction temperature being maintained at not more than 30° C with cooling. During the addition, lithium chloride was precipitated as a white solid.
  • the reaction product (macromeric alpha-n-butyl- omega-H-polydimethylsiloxane) was neutralized by addition of 150 ml of 10% strength aqueous sodium bicarbonate solution. The aqueous phase was subsequently removed by phase separation and the solvents by means of vacuum distillation at 130° C and 50 mbar. The product was subsequently filtered through a pressure filter.
  • the degree of reaction was determined by NMR, until the hexamethyl cyclotrisiloxane fraction was ⁇ 1% by weight.
  • the reaction was then terminated by addition of 1.16 mol of dimethylchlorosilane for 0.5 h at 25° C, the reaction temperature being maintained at not more than 30° C with cooling. During the addition, lithium chloride was precipitated as a white solid.
  • the reaction product (macromeric alpha-n-hexyl- omega-H-polydimethyl-siloxane) was neutralized by addition of 150 ml of 10 wt.-% aqueous sodium bicarbonate solution. The aqueous phase was subsequently removed by phase separation and the solvents by means of vacuum distillation at 130° C and 50 mbar. The product was subsequently filtered through a pressure filter
  • the so dried pigment has been used as additive for adjacent powder coating applications.
  • Example 3 In this example the same procedure as described under example 2 was used. However, an artificial mica fraction (sizes 10-50 pm) of Youjia has been used as a substrate.
  • Example 9 In this example the same procedure as described under example 3 was used. As coating compound 0.5 g surface modification agent of pre-example 1c has been used.
  • Comparative Example 1a Particles with fairly spherical appearance but with high inner porosity, typically used as matting agent in liquid coatings, Syloid AC1 (Grace Materials Technologies) were used without further surface modification.
  • Comparative Example 2a Glass spheres Spheriglass 5000 CP00 (Velox) were used without further surface modification.
  • Comparative Example 4a AEROXIDE Alu C, a non-lamellar filler for powder coating based on AI2O3 from Evonik was used without further surface modification.
  • Comparative Example 4b Comparative Example 4a was coated according to example 1 , but using as surface modification agent 2.0 g of pre-example 1a.
  • Comparative Example 5 to 7 Synafil S 115, Synafil S 525 and Synafil S 1050, all fillers based on synthetic mica used in cosmetic applications from Eckart GmbH. These fillers are not modified by any additive.
  • Comparative Example 10 A pearlescent pigment in accordance to EP 2 698403 B1 was used as additive.
  • Example 2 Like Example 2, but as a transparent substrate LAG glass flakes (Glassflake Ltd.
  • a commercially available polyester powder coating RAL9005 glossy for architectural applications (Drylac® 68/80020 from Tiger Coatings GmbH & Co. KG) was applied without any further modification with a GEMA PG 1 B-cup gun on steal substrates using corona charging at a voltage of about 60 kV as a reference sample. The coated substrate was then cured at 200 °C for 10 min.
  • the powder coating applications were evaluated qualitatively with respect to their sprayability and optical appearance such as spot occurrence and levelling.
  • the gloss was measured at 60° according to ISO 2813, using a BYK micro-TRI-gloss apparatus. The results are depicted in table 1.
  • the absolute gloss is depicted there as well as the percentage compared to the reference powder coatings without any matting agent which had a gloss of 84.
  • the gloss should be below 85% and most preferably equal or below 80% compared to the reference at a concentration of about 1 wt.-% of the matting agent sample.
  • the AE*-value should be equal or less than 1.0 unit. This value is regarded to indicate essentially no visible change in the optical appearance with respect to chroma, Hue and lightness.
  • matting agent from example 2 was applied at different concentrations in two other powder coatings systems: a hybrid powder coatings clear high gloss coat (Drylack® 89/0060 from Tiger Coatings GmbH & Co. KG) with a gloss at 60° of 100 and a polyester powder coatings RAL9005 high gloss (Drylac® 59/82170 from Tiger Coatings GmbH & Co. KG) with a gloss at 60° of 97 were used.
  • Table 2 The results are depicted in table 2.
  • All inventive Examples show powder coating applications without any defects such as spots, levelling glitters etc.
  • the loss of gloss at a pigmentation of 1.0 % by weight was significant and was at 60° 83% or below of the gloss of the reference sample without post-adding additive.
  • All AE*-values were below 1.0 which means that essentially no change of the optical appearance such as changes of Lightness or Hue were visible to the human eye.
  • Comparative Example 3 a phenylmethyl polysiloxane was used as modification agent.
  • Comparative Example 9 a 1 :1 mixture of an alkyl silane and a functional 3-methacryloxy silane was used as modification agent as it was suggested in CN 106675152 A1.
  • the powder coating applications were fine with respect to the general optical appearance, but the gloss was only lowered to 89% of the reference value, respectively.
  • Comparative Examples using non-platelet substrates either without surface modification (Comparative Examples 1a, 2a, and 4a) or with surface modification by an additive of formula (I) (Comparative Examples 1b, 2b, and 4b) generally exhibited a lower gloss reduction compared to the inventive Examples.
  • the applications showed in many cases defects like spots, craters or a bad leveling.
  • Comparative Example 11 a glassflake of larger dimensions was used with a surface modification but glitters occurred in the application. Also the gloss was reduced only to 93%. Such substrates seem to be too large. It is assumed that due to higher thickness, size and particle weight of this sample the desired leafing or semi leafing effect could't be achieved.

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Abstract

La présente invention concerne un additif pouvant être utilisé en tant qu'agent de matité pour des peintures en poudre, comprenant un substrat lamellaire transparent qui est au moins partiellement appliqué sur la surface du substrat à l'aide d'un agent de modification de surface constitué d'une polysilicone spéciale. L'invention porte en outre sur des compositions de peinture en poudre contenant cet agent de matité.
PCT/EP2021/085944 2020-12-18 2021-12-15 Agent de matité lamellaire pour peinture en poudre et peintures en poudre WO2022129201A1 (fr)

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WO1999036481A1 (fr) 1998-01-16 1999-07-22 Cabot Corporation Composition de revetement en poudre
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WO2015057895A1 (fr) 2013-10-15 2015-04-23 S&B Industrial Minerals S.A. Verre d'aluminosilicate d'origine volcanique traité en surface, micronisé et expansé utilisable en tant que charge fonctionnelle lamellaire pour plastiques et revêtements spéciaux
CN106675152A (zh) 2016-12-22 2017-05-17 重庆市锦艺硅材料开发有限公司苏州分公司 粉末涂料用消光改性剂及其应用、以及含有其的消光粉末涂料
CN111378298A (zh) 2018-12-27 2020-07-07 苏州锦艺新材料科技有限公司 一种粉体材料、其制备方法及粉末涂料

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