WO2012139520A1 - Revêtement en poudre doux au toucher à l'aspect anodisé - Google Patents

Revêtement en poudre doux au toucher à l'aspect anodisé Download PDF

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Publication number
WO2012139520A1
WO2012139520A1 PCT/CN2012/073991 CN2012073991W WO2012139520A1 WO 2012139520 A1 WO2012139520 A1 WO 2012139520A1 CN 2012073991 W CN2012073991 W CN 2012073991W WO 2012139520 A1 WO2012139520 A1 WO 2012139520A1
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Prior art keywords
powder coating
coating composition
polymer
dye
substrate
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PCT/CN2012/073991
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English (en)
Inventor
Xiaodong Wang
Pu ZENG
Original Assignee
Akzo Nobel Powder Coatings (Ningbo) Co., Ltd.
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Application filed by Akzo Nobel Powder Coatings (Ningbo) Co., Ltd. filed Critical Akzo Nobel Powder Coatings (Ningbo) Co., Ltd.
Priority to CN201280014701.XA priority Critical patent/CN103443212B/zh
Priority to KR1020137027393A priority patent/KR102030507B1/ko
Publication of WO2012139520A1 publication Critical patent/WO2012139520A1/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
    • 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
    • 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
    • C09D5/032—Powdery paints characterised by a special effect of the produced film, e.g. wrinkle, pearlescence, matt finish
    • 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
    • C09D7/42—Gloss-reducing agents
    • 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
    • C09D7/65—Additives macromolecular
    • 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
    • C09D7/66—Additives characterised by particle size
    • C09D7/69—Particle size larger than 1000 nm
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/53—Core-shell polymer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers

Definitions

  • the present invention relates to a powder coating composition that will result, when cured, in a special effect coating, viz. a soft feel coating with an anodised look.
  • Powder coating compositions are solid compositions that generally comprise a solid film-forming resin, usually with one or more pigments and, optionally, one or more performance additives such as plasticizers, stabilizers, flow aids and extenders.
  • the resins are usually thermosetting, incorporating, for example, a binder resin and a corresponding crosslinking agent (which may itself be another binder resin).
  • the resins have a T g , softening point or melting point above 30°C.
  • the manufacture of a powder coating comprises melt-mixing the components of the composition.
  • Melt-mixing involves the high speed, high intensity mixing of dry ingredients and then the heating of the mixture to an elevated temperature - above the softening temperature of the resin but below the curing temperature - in a continuous compounder to form a molten mixture.
  • the compounder preferably comprises a single or twin screw extruder as these serve to improve the dispersion of the other ingredients in the resin as the resin melts.
  • the molten mixture is extruded, typically rolled in the form of a sheet, cooled to solidify the mixture and subsequently crushed (pulverized).
  • Such processing is then generally followed by a sequence of particle sizing and separation operations - such as grinding, classifying, sifting, screening, cyclone separation, sieving and filtering - that precede the application of the powder to a substrate and the heating of that powder to melt and fuse the particles and to cure the coating.
  • the main methods by which powder coatings are applied include fluidized-bed and electrostatic fluidized- bed processes and electrostatic spray processes in which the powder coating particles are electrostatically charged by a spray gun and directed onto an earthed substrate.
  • Anodising is an electrochemical process wherein a protective layer of aluminium oxide is formed on the surface of an aluminium sheet. This layer can be coloured by dyeing the electrochemical bath. Anodising gives aluminium a deeper, richer metallic appearance than possible with organic coatings. An anodised surface is translucent, so the base metal underneath stays visible, even after the treatment.
  • An anodised look can be measured in an objective way by determining the reflection along and across the observed texture. For each measurement the L, a and b values can be recorded and the colour differences along and across the texture can be calculated using the standard colour difference equation.
  • a AE(along - across texture) is larger than 3 is found.
  • a AE(along - across texture) smaller than 2 is found.
  • a surface having an anodised look is a surface having a ADE-index larger than 3, where the ADE-index is defined as AE(along - across texture) measured in accordance with the method described above.
  • ADE-index is defined as AE(along - across texture) measured in accordance with the method described above.
  • JP 63243176 various powder coating compositions are disclosed. These powder coating compositions when applied to a substrate and cured will not give an anodised look.
  • a polymer A composed of particles having an average particle size of 0.1 -60 ⁇ and having a T g of from -60°C to 75°C, and e. less than 10 wt.% of a pigment or dye that is not-soluble in a solvent, the wt.% based on the total weight of the powder coating composition.
  • T g of a compound is measured in accordance with ASTM D3418.
  • the solvent soluble dye is a metal complex dye.
  • the powder coating composition comprises an agent that enhances the solubility of the dye in the binder resin.
  • the agent that enhances the solubility of the dye in the binder resin comprises isocyanates groups.
  • the agent that enhances the solubility of the dye in the binder resin comprises caprolactam blocking groups.
  • a polymer A composed of particles having an average particle size of 0.1 -60 ⁇ and having a T g of from -60°C to 75°C, and e. less than 10 wt.% of a pigment or dye that is not-soluble in a solvent, the wt.% based on the total weight of the powder coating composition
  • suitable resins for inclusion within the powder coating premix include both thermoplastic and thermosetting base resins. When used in powder coatings, thermoplastic resins must melt and flow out to a thin film within a few minutes at stoving temperatures from 120°C to 300°C without significant degradation.
  • suitable thermoplastic resins for use in the practice of the present invention include polyamides, polyesters, cellulose esters, polyethylene, polypropylene, polyvinyl chloride) [PVC], poly(vinylidene fluoride) [PVF2], polyphenylsulfones and poly(tetrafluoroethylene) [PTFE] of which polyphenylsulfones and PTFE are particularly preferred. All of the suitable thermoplastic resins are readily available from commercial sources.
  • the thermosettable resins which are suitable for this invention include epoxy resins, polyurethanes, silicones, crystalline resins, polyesters (including unsaturated polyesters), acrylics, and hybrids such as epoxy-acrylic, polyester- acrylic, and epoxy-polyester.
  • the glass transition temperature (T g ) of these resins must be high enough that the particles do not fuse together or sinter at temperatures likely to be encountered during transportation and storage.
  • the T g is in the range from 45° to 120°C, within which range a T g greater than 55° is more preferred.
  • a powder coating according to the present invention is obtainable by processing a mixture of the various ingredients. This processing can be any process known to the skilled person to prepare a powder coating composition.
  • a process for the preparation of a powder coating composition known to the skilled person is for example the process described in Chapter 5 (Technology of Production of Powder Coatings) of "Powder Coatings Chemistry and Technology” by P.G. de Lange, Hannover, Vincentz Network, 2004. This process includes the following steps: Weighing of raw materials - premixing - hot melt compounding - cooling - granulation - fine gridning - classifying - packing.
  • VAMP VEDOC Advanced Manufacturing Process
  • CPCSP Continuous Powder Coating Spray Process
  • Suitable epoxy resins are those containing aliphatic or aromatic backbones with oxirane functionality and are exemplified by: the diglycidyl ether condensation polymers resulting from the reaction of epichlorohydrin with a bisphenol e.g. bisphenol A and bisphenol F in the presence of an alkaline catalyst; and, glycidyl ethers of phenolic novolac resins synthesised by reacting phenolic novolac resin with epichlorohydrin in presence of sodium hydroxide as a catalyst.
  • the epoxy resins should have: an epoxide equivalent weight (EEW) between 600 and 2000; a hydroxyl equivalent weight between 300 and 400; and, a melt viscosity in the range from 200 to 2000 centipoise (cps) at 150°C, preferably from 300 to 1000 cps.
  • EW epoxide equivalent weight
  • cps centipoise
  • the low melt viscosities of such resins may allow them to be extruded at temperatures less than 200°C.
  • Commercially available epoxy resins which are preferred for the purposes of this invention are the bisphenol A epoxies sold under the trademarks ARALDITE® GT-7004, GT-7071 , GT-7072, GT-6259 (Huntsman LLC) EPON® 1001 and 2042 (Shell Chemicals, Inc.).
  • a wide variety of curing agent for epoxy resins is available depending on the process and properties required.
  • Dicyandiamide, modified and substituted dicyandiamides, solid dicarboxylic acids and their anhydrides are examples of those agents that may be used for the curing of epoxy resins.
  • a curing agent in solid form is preferred for convenience in the formulation of epoxy resin-based powders as well as in the formulation of other resin-based powders in this invention.
  • Silicone resins for use in this invention should be: solid at room temperature; have a T g of greater than 55° C, preferably greater than 60°C; and a viscosity of between about 500 and about 10,000 cps at 150° C, preferably 2000 to 5000 cps.
  • Suitable silicone resins for use in this invention are described inter alia in U.S. Patents Nos. 3,170,890; 4,879,344; 3,585,065; and, 4,107,148 the disclosures of which are herein incorporated by reference.
  • suitable, commercially available silicone resins are phenylsilicone SY-430 and methylsilicone MK (both products of Wacker Silicone, USA) and methylphenylsilicone 6-2230 (Dow Corning).
  • Suitable hydroxy functional polyesters for use in the process of this invention are predominantly hydroxyl in functionality and should preferably be characterized by having: i) a hydroxyl number in the range from about 25 to about 50; ii) an acid number less than or equal to 15 but preferably in the range from about 1 to 2; and, iii) a T g higher than 50°C.
  • polyesters meeting these requirements are commercially available as RUCOTE ® 107, CARGILL ® 3000 / 3016, and CRYLCOAT ® 3109. Equally, however such polyesters may be formed as the condensation products of polybasic carboxylic acids and polyhydric alcohols.
  • carboxylic acids useful for the preparation of such polyester resins include one or more of phthalic acid, tetra- and hexahydrophthalic acids and their anhydrides, succinic acid, adipic acid, sebacic acid, terephthalic and isophthalic acids, 1 ,3- and 1 ,4-cyclohexane-dicarboxylic acids, and trimellitic anhydride, esters of such acids.
  • suitable difunctional alcohols include ethylene-, diethylene-, propylene-, isomers of 1 ,2 and 1 ,3 propylene glycol and trimethylene glycol and suitable dihydric alcohols include hexanediol, 1 ,3-, 1 ,2-, and 1 ,4-butanediols, neopentyl glycol, 2-butyl-2-ethyl-1 ,3-propanediol, 2-methyl- 1 ,3-propanediol, 1 ,4-cyclohexanediol, thmethylolpropane, and mixtures thereof.
  • suitable difunctional alcohols include ethylene-, diethylene-, propylene-, isomers of 1 ,2 and 1 ,3 propylene glycol and trimethylene glycol and suitable dihydric alcohols include hexanediol, 1 ,3-, 1 ,2-, and 1 ,4-butanediols,
  • the hydroxyl-functional polyesters are curable through the hydroxyl groups with aliphatic and aromatic isocyanates and with aminoplasts.
  • Isocyanate curing forms resins which technically are polyesters but when cured are described as polyurethanes.
  • Aminoplasts are oligomers that are the reaction products of aldehydes, particularly formaldehyde, with amino- or amino-group-carrying substances exemplified by melamine, urea, dicyandiamide, and benzoguanamine.
  • aminoplasts such as hexamethylol melamine, dimethylol urea, and their etherified forms, i.e., modified with alkanols having from one to four carbon atoms.
  • Hexamethoxymethyl melamine and tetramethoxy glycoluril exemplify said etherified forms.
  • Particularly preferred are the amino cross-linking agents CYMEL ® available from American Cyanamid.
  • Aminoplast curing agents are typically provided in an amount sufficient to react with at least one-half the hydroxyl groups of the polyester, i.e., an amount at least one-half the stoichiometric equivalent of the hydroxyl functionality.
  • the amount of cross- linking agent is sufficient to substantially completely react with all of the hydroxyl functionality of the polyester, and cross-linking agents having nitrogen cross- linking functionality are provided in amounts of from about 2 to about 12 equivalents of nitrogen cross-linking functionality per equivalent of hydroxyl functionality of the polyester.
  • Acidic catalysts may be used to modify the curing of the polyester with an aminoplast resin by lowering the required temperature or raising the reaction rate or both.
  • the acidic catalyst may be blocked with an amine. Volatile amines which may escape from the curing film when the catalyst is unblocked by heat are suitable for this purpose. It is particularly desirable for the purposes of this invention to delay full curing of the composition.
  • NACURE ® 1557 an amine- blocked dinonylnaphthalenesulfonic acid available King Industries, is an example of the blocked acid catalyst suitable for use in the aminoplast curing of the powder coating composition of this invention.
  • Diisocyanates cure hydroxy-functional polyester resins by forming urethane linkages between the polymer chains at the hydroxyl group sites.
  • Common aliphatic diisocyanates are exemplified by hexamethylene diisocyanate (HDI), diisocyanato di-cyclohexylmethane (sold as DESMODUR W® by Miles Chemical) and isophorone diisocyanate (IPDI).
  • HDI hexamethylene diisocyanate
  • IPDI isophorone diisocyanate
  • TKI is an example of a suitable aromatic diisocyanate.
  • the low-temperature reactivity of free diisocyanates may be reduced by adducting them with blocking agents selected from phenol, cresols, isononylphenol, amides such as epsilon - caprolactam, oximes such as methyl-ethyl ketoxime and butanoneoxime, active methylene group-containing compounds such as diethylmalonate, and isopropylidene malonate and the acetoacetates, and sodium bisulfite.
  • the blocked diisocyanates include caprolactam blocked isophorone diisocyanate and caprolactam blocked hexamethylene diisocyanate.
  • Examples of commercially available curing agents of this type are the 24-2400, 24-2430, and 24-2450 products sold under the CARGILL trademark.
  • Another group of blocked curing agents are the uretdiones which can be described as internally blocked.
  • Carboxyl-functional polyesters are also suitable for the purposes of this invention. These may be made from the same polyfunctional acids and glycols as the hydroxyl-functional polyesters but with an excess of the acids. The acid number is from about 10 to about 100. Suitable commercial products are: CRYLCOAT ® 430, 3010 and 7617 (available from UCB); URALAC ® 3400 and 3900; EL6500 or EL6700 or EL8800 available from Chan Sieh Enterprises Fast cure of these carboxy functional polyesters may be achieved with polyepoxide curing agents such as triglycidyl isocyanurate (TGIC).
  • TGIC triglycidyl isocyanurate
  • curing agents to TGIC include: Primids, such as Primid XL552 and QM1260 which are hydroxyalkylamides available from EMS-Primid; Araldite PT910 gylcidyl ester available from Ciba Geigy; and Uranox available from DSM.
  • Unsaturated polyesters suitable for use in the practice of the invention include ethylenically unsaturated reaction products of an organic di- or polyfunctional acid and a di- or polyfunctional alcohol. Typically the acid is unsaturated.
  • Such polyester resins typically work best in combination with a copolymerizable second resin such as diallyl phthalate. Initiators may also need to be incorporated.
  • the preferred acrylic resins for powder coatings are copolymers of alkyl acrylates and/or methacrylates with glycidyl-methacrylates and/or acrylates and olefinic monomers such as styrene.
  • Glycidyl-functional acrylic resins are sold by Mitsui Toatsu Chemicals, Inc. as ALMATEX ® for which a carboxy-terminated polymer may be used as a cross-linking agent. Hydroxyalkyl acrylate and methacrylate copolymers are also suitable for this invention.
  • Hybrid resin systems such as the epoxy-acrylic and polyester-acrylic mixtures, are also suitable for this invention. However, where such a system is employed, it is preferably a polyester-epoxy hybrid.
  • polyester-epoxy hybrids comprise both epoxy resins and carboxyl terminated polyester resins and may also comprise a catalyst to drive the curing reaction.
  • the acidic polyester has an equivalent weight between 600 and 4000 and the epoxy resin has an equivalent weight between 400 and 1 100.
  • Catalysts for the epoxy- acid reaction include quaternary ammonium salts, quaternary phosphonium salts, phosphines, amines, imidazoles and metal salts.
  • Amphoteric catalysts such as, zinc oxide (ZnO 2 ) is effective at 1 -5 parts per hundred parts by weight of the resins to improve the cure rate and physical properties of the product.
  • the powder coating composition according to the present invention also comprises a solvent soluble dye.
  • a solvent soluble dye normally show good solubility in solvents like alcohol, ketones, and glycol ether and ester solvents.
  • the solvent soluble dye is a metal complex dye.
  • Metal-complex dyes are also known as pre-metallized dyes. Metal complex dyes find application for dyeing fibres, both natural and synthetic fibres such as polyamide fibres and wool. Chemically speaking, Metal complex Dyes can be broadly classified into two classes. 1 :1 metal-complexes, where, one dye molecule gets co-ordinated with a single metal atom. In 1 :2 metal complexes, one metal atom is co-ordinated with double dye molecules.
  • the dye molecules are typically a monoazo structure which can contain additional groups like hydroxyl, carboxyl or amino groups. They can form strong co-ordination complexes with transition metal ions, like Nickel, Chromium, Cobalt and Copper.
  • the solvent soluble dye is 1 :2 metal complex dye.
  • solvent soluble dyes examples include metal complex dyes, fluorescent dyes, polymer soluble dyes, and polysynthren dyes.
  • An example of a dyes that can be used in the coating compositions of the present invention are Savinyl ® - type dyes supplied by Clariant
  • solubility can be enhanced by using a compound that has isocyanates groups.
  • solubility can be enhanced by using a compound with caprolactam groups.
  • a compound that has both isocyanates functionality and caprolactam functionality for example a compound having isocyanates groups blocked with ⁇ -caprolactam.
  • Examples of a compounds that can be used to improve the solubility of the dye in the binder resin include Vestagon® B1530 (an ⁇ -caprolactam blocked polyisocyanate ex. Degussa) and Vestagon ® B1540 (a blocked uretdione compound, ex Degussa_.
  • the coating composition according to the present invention also comprising a matting effect compound.
  • a matting effect compound is an essential ingredient to get a cured powder coating with an anodised look.
  • a matting effect compound is a compound that is added to the composition to get a matting effect.
  • various types of matting effect compounds can be used, such as:
  • Suitable waxes can be selected from the group consisting of polyamide wax and polyethylene wax.
  • the waxes can have modifications, such as being micronised or PTFE-modified.
  • the waxes have a melting temperature in the range of 100 to 160 °C.
  • compositions comprising two different types of polyester resins, one type of polyester resin with a relatively short gel time, the other type of polyester resin with a relatively long gel time.
  • An example of a gloss reducing agent that reacts with the binder resin is Synthacryl 700, when used in combination with a polyester binder resin.
  • Another example of such compound is T-325, a resin based delustering agent, when used in a polyester/epoxy hybrid binder system.
  • Barium sulphate and calcium carbonate with coarse particles can be used in relatively high amounts to obtain a cured powder coating with a matt appearance.
  • the composition according to the present invention comprises a polymer A giving a soft feel or soft touch effect, the soft feel polymer A composed of particles having an average particle size of 0.1 -60 ⁇ and having a T g of from - 60°C to 75°C.
  • the optimum soft feel properties are observed when the (co)polymer has a T g below 10°C, for example a T g in the range from -10 to - 50°C
  • the polymer A is a copolymer of carbon monoxide, ethylene and unsaturated ester monomers which can be vinyl esters of saturated carboxylic acids having 1 -18 carbon atoms and alkyl acrylates and methacrylates having 1 to 10 carbon atoms in the alkyl group.
  • Typical vinyl ester softening monomers that can be used in accordance with the present invention include vinyl acetate, vinyl propionate, vinyl 2-ethylhexoate and vinyl neodecanoate.
  • Typical alkyl acrylate and methacrylate softening monomers include methyl acrylate, isobutyl acrylate, n- butyl acrylate, 2-ethylhexyl acrylate, ethyl methacrylate, isobutyl methacrylate, and isononyl methacrylate. Mixtures of softening monomers can be used.
  • the copolymer contains 40-80 mol% ethylene, 10-60 mol% vinyl acetate, and 3-30 mol% carbon monoxide.
  • unsaturated ester softening monomers such as vinyl esters of saturated carboxylic acids having 1 -18 carbon atoms and alkyl acrylates and methacrylates having 1 to 10 carbon atoms in the alkyl group, can be substituted for vinyl acetate in these copolymers.
  • the copolymers can be prepared by passing a compressed mixture of ethylene, unsaturated ester monomers and carbon monoxide along with a free radical generating catalyst into an autoclave held at elevated temperature and pressure, for example, 155 -225 °C. and 140-250 MPa, while removing product polymer and unreacted monomers at the same rate. Under these conditions about 10% by weight of the monomers fed are converted to polymer.
  • the preparative procedure is more fully described in U.S. Pat. No.3,780,140 to Hammer and U.S. Pat. No. 2,495,286 to Brubaker.
  • the polymer A is made from (meth)acrylate monomers, vinyl monomers or reactive resins may be chosen from the group consisting of t-butyl acrylate (t-BA) (co)polymer, 2-ethylhexyl (meth)acrylate (co)polymer, ethyl (meth)acrylate copolymer, sec-butyl (meth)acrylate (co)polymer, methyl acrylate (co)polymer, hexyl (meth)acrylate (co)polymer, isobutyl (meth)acrylate (co)polymer, benzyl (meth)acrylate (co)polymer, isopropyl (meth)acrylate (co)polymer, decyl (meth)acrylate (co)polymer, dodecyl (meth)acrylate (co)polymer, n-butyl (meth)acrylate (co)polymer, C21 to C30 al
  • the (co)polymer particles may comprise multi-stage (co)polymers with, for example, a core-shell or layered structure, such as a multilobal structure.
  • Multistage (co)polymers may comprise a polymeric core phase and one or more polymeric shell phase and may comprise a graded refractive index composition.
  • the core may be prepared from a variety of vinyl monomers, and may be a rubbery or glassy polymer.
  • the core may be prepared from polymerization or copolymerization of such monomers as diolefins, for example, butadiene or isoprene; vinyl aromatic monomers, for example, styrene or chlorostyrene; vinyl esters, for example, vinyl acetate or vinyl benzoate; methacrylonitrile; (meth)acrylate esters, for example, methyl methacrylate, butyl methacrylate, phenyl meth-acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and benzyl acrylate; vinyl chloride; and other monomer polymerizable by free-radical initiation.
  • monomers as diolefins, for example, butadiene or isoprene
  • vinyl aromatic monomers for example, styrene or chlorostyrene
  • vinyl esters for example, vinyl acetate or vinyl benzoate
  • methacrylonitrile (me
  • the (co)polymer particles may also comprise multi-stage polymers having rubbery cores, i.e. having a Tg of 20°C or less, or 10°C or less.
  • the rubbery cores may comprise synthetic or natural rubbers, or, preferably, acrylic rubbers.
  • the acrylic rubber cores comprise alkyi acrylate copolymers, the alkyi group having from 2 to 8 carbon atoms, preferably, t-BA or BA, copolymerized with from 0 to 10 wt%, preferably up to about 5 wt%, or up to 1 wt%, or 0.05 wt% or more, of one or more crosslinker, based on the total weight of core monomers, from 0 to 10 wt%, preferably up to 5 wt%, or up to 2.5 wt%, and, preferably, 0.1 wt% or more, or 0.5 wt% or more, of one or more graftlinker, based on the total weight of core monomers, and from 0 to 50 wt% of one or more copolymerizable vinyl monomer, based on the total weight of core monomers.
  • the shell(s) may comprise from 0 to 40 wt% of the multistage particles.
  • the copolymerizable vinyl monomer or monomers may be monovinyl monomers, such as alkyi methacrylates and monovinyl arenes, for example, styrene, alkylstyrenes such as methylstyrene and ethylstyrene, other substituted vinylbenzenes wherein the substitutents do not interfere with polymerization, and vinyl polycyclic aromatic monomers.
  • a preferred two-stage 5 ⁇ average particle size copolymer comprises rubbery poly(BA) crosslinked with allyl methacrylate and has a hard shell of poly methyl methacrylate (pMMA), the shell comprising 20 wt% of the particle.
  • the above (co)polymer may be made by any known aqueous polymerization process which results in particles having average particle size of 0.1 -60 ⁇ , preferably 0.5-20 ⁇ , more preferably 0.5-10 ⁇ .
  • the particles preferably have a narrow particle size distribution (PSD).
  • the (co)polymer with particles at the upper end of the desired size range may be made by suspension polymerization techniques but this requires post polymerization particle classification.
  • the (co)polymer particles may also be prepared by aqueous emulsion polymerization of at least one monomer to form emulsion (co)polymer or oligomer seed particles, followed by swelling the seed particles with one or more monomer components, and polymerizing the one or more monomer within the emulsion seed particles to yield the particles of a desired average diameter. The swelling and polymerizing steps may be repeated until the particles have grown to the desired core or single stage (co)polymer size.
  • particles of varying size and composition suitable for use can be produced by using appropriately sized swellable (co)polymer or oligomer seeds. Suitable emulsion polymerization processes of making the (co)polymer particles have been stated in US20070218291 .
  • the above (co)polymer particles are spray dried or freeze dried into powders with an average particle size of 0.1 to ⁇ , preferably of 0.5-20 ⁇ , and more preferably of 0.8-5 ⁇ .
  • the (co)polymer particles having such particle size are suitable for this invention.
  • the average particle size of the soft feel (co)polymer is less than 0.1 ⁇ , it will become difficult to achieve a good mixing and dispersion of the (co)polymer in the coating powder composition during extrusion, which will result in an inconsistent matting appearance of the powder coatings after cure. If the average particle size of the (co)polymer is greater than 60 ⁇ , a seed problem will result on the powder coating surface or one will not be able to make a smooth powder coatings during application, especially when the applied coating thickness is less than 70-80 ⁇ .
  • the amount of the soft feel polymer A in the powder composition of the present invention varies from 0.1 to 40 weight percentage, based on the total weight of the composition.
  • the content of the (co)polymer is less than 0.1 wt%, the coating fails to decrease in gloss or obtain a soft touch sensation.
  • a low content of the (co)polymer within 0.5 to 19 wt%, preferably 0.5 to 10 wt% of the coating powder composition is enough to bring about a smooth, low gloss and soft touch surface to the coating formed, with improved mechanical properties, such as good flexibility and less coating cracking in the Mandrel Bend test and 180° Bend test.
  • the coating surface obtained achieves a textured and soft touch sensation.
  • the content of the soft feel (co)polymer should not exceed 40 wt% of the coating powder composition.
  • a high content of the soft feel (co)polymer causes the coating surface obtained to be textured with poor mechanical properties, as insufficient wetting of the (co)polymer by the resins and poor film formation.
  • Suitable compounds that can be used a soft feel (co)-polymer include Eosares Flex 7002 (ex. Kimya Chemicals), Elvaloy 741 and Elvaloy 742 (ex DuPont de Nemours), and various crosslinked and non-crosslinked core- shell polymers produced by Dow Chemical having 80wt% a rubbery core of poly(BA) (crosslinked with allyl methacrylate) and 20wt% a hard shell of poly methyl methacrylate (pMMA), with a particle size in the range from 0,8 to 5 ⁇ .
  • Eosares Flex 7002 ex. Kimya Chemicals
  • Elvaloy 741 and Elvaloy 742 ex DuPont de Nemours
  • various crosslinked and non-crosslinked core- shell polymers produced by Dow Chemical having 80wt% a rubbery core of poly(BA) (crosslinked with allyl methacrylate) and 20wt% a hard shell of poly methyl methacrylate (pMMA), with a particle
  • the powder coating compositions may comprise other components that are conventionally known in the art. These may include: fillers, flow control agents, degassing agents, and antiblocking agents.
  • the powder coating composition according to the present invention contains less than 10 wt.% of a pigment or dye that is not-soluble in a solvent, the wt.% based on the total weight of the powder coating composition.
  • the powder coating composition according to the present invention is substantially free of any non-transparent pigments, but it can contain small amounts of transparent pigments. High amounts of pigments may destroy the anodised/translucent look of the coating.
  • substantially free means that the composition contains less than 0,5 wt.% of any non-transparent pigment, more in particular less than 0,1 wt.% of any non-transparent pigment.
  • the composition does not contain any non-transparent pigments, but it can contain small amounts of transparent pigments.
  • non-transparent pigments include inorganic pigments such as titanium dioxide, red and yellow iron oxides, chrome pigments and carbon black.
  • Further suitable additives for the powder coating composition may include: adhesion promoters; light stabilizers and UV absorbers; flow and leveling additives; gloss-modifying additives; cratering agents; cure agents; texturizers; surfactants; wetting agents; antioxidants (in particular phosphites, hindered phenols and propionates); biocides; and, organic plasticizers.
  • Fillers may be employed to reduce cost and/or reinforce or modify the performance and appearance of the coatings.
  • Fillers comprising glass particles, glass fibres, metal fibers, metal flakes and particles of micas or calcium metasilicate could be included in the powder coating compositions of this invention.
  • Inorganic sulphates such as barites, carbonates such as chalk, and silicates such as talc are commonly used.
  • Metallics including zinc rich anticorrosive particulates may be added to powder coating compositions to impart corrosion resistance to the underlying substrate.
  • Flow control agents may be present in the powder coating compositions in an amount up to 3 wt. % based on the weight of the composition.
  • Such flow control agents which enhance the compositions melt-flow properties and assist in eliminating surface defects, typically include acrylics and fluorine based polymers.
  • Examples of commercially available flow control agents include: Resiflow® P-67, Resiflow® P-200 and Clearflow® (all available from Estron Chemical Inc., Calvert City, KY); BYK® 361 and BYK® 300 from BYK Chemie (Wallingford, CONN); Mondaflow® 2000 from Monsanto (St. Louis, MO); and, Acranal 4F from BASF.
  • Degassing agents can also be used in the powder coating compositions of the present invention in an amount between 0.1 and 5 wt. %, based on the weight of the composition. Such degassing agents facilitate the release of gases during the curing process. Examples of commercially available degassing agents include: Benzoin available from Well Worth Medicines; and, Uraflow® B available from GCA Chemical Corporation (Brandenton, FLA).
  • the powder coating compositions may also comprise an antiblocking agent (dry-flow additive) in an amount from 0.05 to 1 .0 wt. %, based on the total weight of the composition.
  • dry-flow additive dry-flow additive
  • examples of such additives include fumed silica, precipitated silica, fumed alumina, clay, talc and mixtures thereof.
  • a typical powder coating compositions according to the present invention can have the following ingredients:
  • the above wt.% being calculated on basis of the total weight of the powder coating composition and the sum of all ingredients in the powder coating composition adding up to 100 wt.%.
  • a typical powder coating compositions according to the present invention based on a polyester binder resin can have the following ingredients:
  • the above wt.% being calculated on basis of the total weight of the powder coating composition and the sum of all ingredients in the powder coating composition adding up to 100 wt.%.
  • a typical powder coating compositions according to the present invention based on a hybrid binder resin can have the following ingredients:
  • the above wt.% being calculated on basis of the total weight of the powder coating composition and the sum of all ingredients in the powder coating composition adding up to 100 wt.%.
  • the powder coating according to the present invention can be applied over a wide range of applied film thicknesses, typically from thin films of, for example, 30 microns or less up to films of 50, 100, 150 or 200 microns.
  • a typical minimum film thickness is 5 microns.
  • the powder coating according to the present invention can be applied by electrostatic spray equipment. Normally, the powder is sprayed under 60 - 80 KV at a film thickness between 40 - 60 micron. Unused powder can be collected and recycled through the application system.
  • the powder coating composition according to the present invention can be applied to a wide range of substrates, such a metal, wood, and plastic. The best results on substrates having an anodised look were found when the powder coating compositions are applied to an aluminium substrate.
  • the ADE-index is an objective way to quantitatively describe a genuine anodised surface or a surface with an anodised look.
  • the ADE-index can be measured using apparatus that are able to do colour measuring at discrete angles in a plane.
  • an X-rite MA68II portable multi angle spectrophotometer can be used.
  • the ADE-index can be measured by determining the reflection along and across the observed texture. For each measurement the L, a and b values are recorded and the colour differences along and across the texture are calculated using the standard colour difference equation. The reflection is measured at the flop angle (1 10° from the specular reflection) of the surface to be measured.
  • the ADE-index is AE(along - across texture). For a surface having of a genuine anodised object or of an object with an anodised look an ADE-index of larger than 3 is found. For non-anodised surfaces or surfaces not having an anodised look at low or high gloss an ADE-index smaller than 2 is found.
  • the invention relates to a substrate coated with a powder coating having an anodised look, which means that the coated surface has an ADE-index of larger than 3.
  • the powder coatings according to the present invention show a number of advantageous properties when subjected to various mechanical or chemical tests known to the skilled person. The properties have been listed in the table below:
  • the T g of a material can be measured using differential scanning calorimetry (DSC). In this measurement the energy released when heating a sample is measured. The results of this measurement can be used to determine the T g . This procedure is well known to the skilled person. The T g values mentioned in this document were measured using a heating rate of 20 K/min. Before each measurement, a sample is heated for a short period of time to a temperature just above the (expected) T g
  • the particle size of a material e.g a polymer of a powder coating composition
  • Polyester-prim id powder coating compositions were prepared by making a premix of the components in Table 1 . This premix was then melt processed in a twin screw. After melt processing, the material was cooled and grinded to a particle size for use in a powder coating composition (usually a particle size in the range of 1 - 100 ⁇ ). The powder coating composition was then sprayed on a aluminum substrate and cured at 200°C for 15 minutes. All coated substrates showed an anodized look (all had an ACE-index of above 3 and a soft feel).
  • solvent soluble dye 9 14 2 0.04 solvent soluble dye 10 15 3 solvent soluble dye 1 1 16 1
  • Polyurethane powder coating compositions were prepared by making a premix of the components in Table 2. This premix was then melt processed in a twin screw. After melt processing, the material was cooled and grinded to a particle size for use in a powder coating composition (usually a particle size in the range of 1 - 100 pm). The powder coating composition was then sprayed on a aluminum substrate and cured at 200°C for 15 minutes. All coated substrates showed an anodized look (all had an ACE-index of above 3 and a soft feel).

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Paints Or Removers (AREA)

Abstract

La présente invention concerne une composition de revêtement en poudre ayant un aspect anodisé après durcissement. Cette composition de revêtement en poudre comprend les ingrédients suivants : a. une résine liante, b. un colorant soluble dans un solvant, c. un composé à effet matifiant, d. un polymère A composé de particules ayant une granulométrie moyenne de 0,1-60 μm et ayant une Tg entre -60°C et 75°C, et e. moins de 10 % en poids d'un pigment ou d'un colorant insoluble dans un solvant, le pourcentage en poids étant basé sur le poids total de la composition de revêtement en poudre. L'invention concerne aussi un substrat ayant un aspect anodisé avec un indice ADE supérieur à 3.
PCT/CN2012/073991 2011-04-13 2012-04-13 Revêtement en poudre doux au toucher à l'aspect anodisé WO2012139520A1 (fr)

Priority Applications (2)

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CN201280014701.XA CN103443212B (zh) 2011-04-13 2012-04-13 具有阳极化外观的柔感粉末涂料
KR1020137027393A KR102030507B1 (ko) 2011-04-13 2012-04-13 애노다이징된 외양을 가진 소프트 필 분말 코팅

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103525250A (zh) * 2013-10-12 2014-01-22 成都桑瑞斯粉末涂料有限公司 一种密度板专用粉末涂料及其制备方法
WO2016069410A1 (fr) * 2014-10-27 2016-05-06 Valspar Sourcing, Inc. Revêtement tgic extrêmement résistant aux intempéries, hautement flexible
WO2019157412A1 (fr) * 2018-02-12 2019-08-15 Omnova Solutions Inc. Tissu résistant à la décoloration

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1308658A (zh) * 1998-07-03 2001-08-15 国际涂料有限公司 粉末涂料组合物
CN1445313A (zh) * 2002-03-20 2003-10-01 斯普雷赖特股份有限公司 粉末涂料组合物和方法
WO2011110089A1 (fr) * 2010-03-10 2011-09-15 Akzo Nobel Powder Coatings (Ningbo) Co. Ltd. Revêtement en poudre ayant une apparence anodisée

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1308658A (zh) * 1998-07-03 2001-08-15 国际涂料有限公司 粉末涂料组合物
CN1445313A (zh) * 2002-03-20 2003-10-01 斯普雷赖特股份有限公司 粉末涂料组合物和方法
WO2011110089A1 (fr) * 2010-03-10 2011-09-15 Akzo Nobel Powder Coatings (Ningbo) Co. Ltd. Revêtement en poudre ayant une apparence anodisée

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103525250A (zh) * 2013-10-12 2014-01-22 成都桑瑞斯粉末涂料有限公司 一种密度板专用粉末涂料及其制备方法
WO2016069410A1 (fr) * 2014-10-27 2016-05-06 Valspar Sourcing, Inc. Revêtement tgic extrêmement résistant aux intempéries, hautement flexible
WO2019157412A1 (fr) * 2018-02-12 2019-08-15 Omnova Solutions Inc. Tissu résistant à la décoloration

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