WO2012088394A1 - Composition de revêtement pulvérulente - Google Patents

Composition de revêtement pulvérulente Download PDF

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Publication number
WO2012088394A1
WO2012088394A1 PCT/US2011/066784 US2011066784W WO2012088394A1 WO 2012088394 A1 WO2012088394 A1 WO 2012088394A1 US 2011066784 W US2011066784 W US 2011066784W WO 2012088394 A1 WO2012088394 A1 WO 2012088394A1
Authority
WO
WIPO (PCT)
Prior art keywords
powder coating
meth
coating composition
functionalised
glycidyl
Prior art date
Application number
PCT/US2011/066784
Other languages
English (en)
Inventor
Mike Schneider
Peter Frese
Phu Qui Nguyen
Karina Fuhrmann
Franziska Isele
Original Assignee
E. I. Du Pont De Nemours And Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by E. I. Du Pont De Nemours And Company filed Critical E. I. Du Pont De Nemours And Company
Publication of WO2012088394A1 publication Critical patent/WO2012088394A1/fr

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Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/062—Copolymers with monomers not covered by C09J133/06
    • C09J133/068—Copolymers with monomers not covered by C09J133/06 containing glycidyl groups

Definitions

  • the present invention is directed to a powder coating composition curable at low temperature, for industrial applications.
  • Curing powder coatings with elevated temperatures does not allow for the use of temperature-sensitive substrates, such as, wood or plastics. Therefore, powder coatings can be cured by high energy radiation to cure such compositions in a short time under moderate temperatures and to provide quality and productivity with low operating and equipment costs.
  • powder coating compositions for the use as clear coats, also for metal substrates should be able to be cured at lower temperature, and, at the same time, suitable to be over-coated at a temperature regime higher than the low curing temperature, without any damages of the resulted coatings.
  • EP-A 1963443 refers to powder coating compositions based on specific acrylic binders and polyurethane hardeners useful also as clear coat and providing low gloss coatings on the substrate surfaces.
  • the present invention provides a powder coating composition
  • a powder coating composition comprising
  • wt% are based on the total weight of the powder coating composition.
  • the powder coating composition of this invention may provide coatings with high appearance and, surprisingly, providing coatings with improved scratch resistance, and at the same time coatings suitable, in specific applications, for overcoating at higher temperature, without loosing the high-performed clear coating properties such as high smoothness and durability of the coatings as well as very good adhesion on metallic substrates.
  • the powder coating composition of this invention comprises at least one glycidyl-functionaiised (meth)acrylic resin A), in a range of 1 to 99 wt%, preferably 20 to 90 wt%, the wt% based on the total weight of the powder coating composition, wherein the glycidyl-functionaiised (meth)acrylic resin has modified polarity.
  • modified polarity refers to a polarity of the glycidyl-functionaiised (meth)acrylic resin A) given by a hydroxyl value of the glycidyl-functionaiised (meth)acrylic resin A) in a range of 1 to 20 mg KOH/g resin, preferably 1 to 10 mg KOH/g resin, more preferably 2 to 5 mg KOH/g resin.
  • hydroxyl value in this document is defined as the number of mg of potassium hydroxide (KOH) which is equal to the number of mg acetic acid for acetalizing of 1 g of the resin, determined according to DIN 53240.
  • (Meth)acrylic is intended to mean acrylic and/or methacrylic.
  • the giycidyl-functionalised (meth)acrylic resin A) may be produced from monomers selected from the group consisting of glycidyl monomers and co- monomers such as (meth)acrylic acid esters, hydroxyl functionalised (meth)acrylic acid esters together with styrene derivatives and/or vinyltoluene.
  • glycidyl monomers are glycidyl (meth)acrylate, epoxycyclopentyl (meth)acrylate, (meth)allylglycidyl ether, epoxyvinylcyclohexane.
  • co-monomers are methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, isobutyl
  • (meth)acrylate lauryl (meth)acrylate, hydroxyethyl and hydroxypropyl (meth)acrylic acid esters, styrene, methyl styrene, butyl styrene, Veova 10 (vinylester of versatic acid), isobornyl acrylate (IBOA), isobornyl methacrylate (IBOMA).
  • IBOA isobornyl acrylate
  • IBOMA isobornyl methacrylate
  • Preferred is the use of glycidyl (meth)acrylate, (meth)acrylic acid esters and styrene derivatives.
  • Monomers such as hexandioldi(meth)acrylate (HDDMA) and/or
  • allyl(meth)acrylate can be used to slightly crosslink the giycidyl-functionalised (meth)acrylic resin A), as known in the art.
  • the giycidyl-functionalised (meth)acrylic resin A) may be produced in a conventional manner from glycidyl (meth)acrylic monomers, as is, for example, described in D.A. Bates, The Science of Powder Coatings, volumes 1 & 2, Gardiner House, London, 1990, pages 62-70, and as known by the person skilled in the art.
  • the giycidyl-functionalised (meth)acrylic resin A) have an epoxide equivalent weight (EEW) in a range of 300 to 2000, epoxy equivalent weight determined by means of ADSAM142 , a method cojS ⁇ of the EEW test using auto-tritator (Brinkman Metrohm 751 GPD Titrino) and known by a person skilled in the art, and a glass transition temperature Tg in a range of, e.g. 30 to 80°C, preferably 40 to 70, Tg determined by means of differential scanning calorimetry (DSC).
  • EW epoxide equivalent weight
  • Tg glass transition temperature
  • the giycidyl-functionalised (meth)acrylic resin A) have a hydroxyl value of the glycidyl-functionalised (meth)acrylic resin A) in a range of 1 to 20 mg KOH/g resin, preferably 1 to 10 mg KOH/g resin, more preferably 2 to 5 mg KOH/g resin.
  • the person skilled in the art selects the nature and proportion of the monomers selected from the group consisting of glycidyl monomers and co- monomers such as (meth)acrylic acid esters, hydroxyl functionalised (meth)acrylic acid esters together with styrene derivatives and/or vinyltoluene for the production of the glycidyl-functionalised (meth)acrylic resin A) in such a manner that the glycidyl- functionalised (meth)acrylic resin A) according to the invention is obtained having the hydroxyl value as described above.
  • glycidyl monomers and co- monomers such as (meth)acrylic acid esters, hydroxyl functionalised (meth)acrylic acid esters together with styrene derivatives and/or vinyltoluene
  • the glycidyl-functionalised (meth)acrylic resin A) may be partially replaced by further resins such as, for example, diglycidyl ethers of bisphenol, epoxy novolak and other resins containing epoxy groups, in quantities in the range of lower than 10 wt%, based on the total weight of the powder coating composition.
  • one or more di- and/or poly-carboxylic acids or the anhydrides thereof are used with quantities in the range of 1 to 99 wt%, preferably 20 to 90 wt%, the wt% based on the total weight of the powder coating composition.
  • the di- and/or poly-carboxylic acids or the anhydrides thereof have an acid value in the range of higher 30 mg KOH/g resin, preferably, in the range of 50 to 600 mg KOH/g resin, more preferably 100 to 400 mg KOH/g resin.
  • Examples are di- carboxylic acids with a number of carbon atoms C in the range of 4 to 20, preferably, 10 to 18, for example, C12-dodecanedioic acid.
  • acid value in this document is defined as the number of mg of potassium hydroxide (KOH) required to neutralise the carboxylic groups of 1 g of the resin, determined according to DIN EN ISO 21 14.
  • the carboxyl functionalised hardener B) may be partially replaced by further hardeners, such as, for example, hardeners containing carboxyl groups such as carboxyl group containing polyesters, carboxyl group containing (meth)acrylates and/or carboxyl group containing polyurethane resins, and/or hardeners containing amid or amino groups, for example, dicyandiamide and the derivatives thereof, in quantities in the range of lower than 10 wt%, wt% based on the total weight of the powder coating composition of the invention.
  • the carboxyl group containing polyurethane resihs can have an acid value, for example, in the range of 50 to 300, preferably of 80 to 200.
  • the carboxyl group containing polyurethane resins may be produced as known in the art, by, for example, reacting hydroxyl functionalised polyurethanes with acid anhydrides, furthermore, by reacting diisocyanates or polyisocynates or isocyanate functionalised pre-polymers with hydroxyl carboxyl acids.
  • the hydroxyl functionalised polyurethanes may be prepared in a conventional manner as known to the person skilled in the art, e.g. they may be produced by reacting polyisocyanates with polyols in excess.
  • the person skilled in the art selects the nature and proportion of the polyisocyanates and polyols in such a manner that the polyurethane resins are obtained which are solid at room temperature.
  • the powder coating composition according to the invention may contain as further components the constituents conventional in powder coating technology, such as, additives, pigments and/or fillers as known by a person skilled in the art, in amounts in a range of 0.05 to 50 wt%, preferably 0.1 to 40 wt%, based on the total weight of the powder coating composition.
  • the constituents conventional in powder coating technology such as, additives, pigments and/or fillers as known by a person skilled in the art, in amounts in a range of 0.05 to 50 wt%, preferably 0.1 to 40 wt%, based on the total weight of the powder coating composition.
  • a person skilled in the art selects the nature and proportion of such constituents for the production of the powder coating composition of the invention.
  • Additives are, for example, degassing auxiliaries, flow-control agents, flatting agents, texturing agents, fillers (extenders), photo-initiators, catalysts, dyes.
  • Examples are flow-control agents incorporated in the composition according to the invention via an inorganic carrier or by master-batch techniques known by a person skilled in the art. Compounds having anti-microbial activity may also be added to the powder coating compositions.
  • the cross-linking (hardening) reaction may be additionally accelerated by the presence in the powder coating composition according to the invention of catalysts known from thermal cross-linking such as, for example, tin salts, phosphides, amines and amides. They may be used, for example, in quantities of 0 to 5 wt%, based on the total weight of the powder coating composition. Preferably, no such catalysts are used for the cross-linking reaction, and, surprisingly, a high cross-linking density can be achieved at lower temperature, based on the powder coating composition according to this invention.
  • the powder coating composition of this invention may contain transparent, color-imparting and/or special effect-imparting pigments and/or fillers (extenders), as such known in the art.
  • Suitable transparent and color-imparting pigments are any conventional coating pigments of an organic or inorganic nature.
  • inorganic or organic color-imparting pigments are titanium dioxide, micronized titanium dioxide, carbon black, azopigments, and phthalocyanine pigments.
  • Examples of special effect-imparting pigments are metal pigments, for example, made from aluminum, copper or other metals, interference pigments, such as, metal oxide coated metal pigments and coated mica.
  • Examples of usable extenders are silicon dioxide, aluminum silicate, barium sulfate, and calcium carbonate. Preferred is the use of transparent pigments.
  • the constituents are used in conventional amounts known to the person skilled in the art, for example, 0.05 to 30 wt. %, based on the total weight of each powder coating base, preferably 0.1 to 20 wt. %.
  • the powder coating composition according to the invention consists of
  • wt% are based on the total weight of the powder coating composition.
  • the powder coating composition according to this invention may be prepared by conventional manufacturing techniques used in the powder coating industry, such as, extrusion and/or grinding processes, known by a person skilled in the art.
  • the ingredients can be blended together by dry-blending ' methods and can be heated to a temperature to melt the mixture, and then the mixture is extruded.
  • the extruded material is then cooled on chill roles, broken up and ground to a fine powder, which can be classified to the desired grain size, for example, to an average particle size of 20 to 200 ⁇ .
  • composition according to the invention may also be prepared by spraying from supercritical solutions, NAD "non-aqueous dispersion” processes or ultrasonic standing wave atomization process.
  • specific components of the powder coating composition according to the invention may be processed with the finished powder coating particles after extrusion and grinding by a "bonding" process using an impact fusion.
  • the specific components may be mixed with the powder coating particles.
  • the individual powder coating particles are treated to softening their surface so that the components adhere to them and are homogeneously bonded with the surface of the powder coating particles.
  • the softening of the powder particles' surface may be done by heat treating the particles to a temperature, e.g., the glass transition temperature Tg of the composition, in a range, of e.g., 50 to 60°C. After cooling the mixture the desired particle size of the resulted particles may be proceed by a sieving process.
  • the powder coating composition of this invention may be applied by, e.g., electrostatic spraying, thermal or flame spraying, or fluidized bed coating methods, also coil coating techniques, all of which are known to those skilled in the art.
  • the coating composition may be applied to, e.g., metallic substrates, non- metallic substrates, such as, paper, wood, plastics, glass and ceramics, as a one- coating system or as coating layer in a multi-layer film build, in a dry-film thickness in a range of, for example, 40 to 100 Mm.
  • the substrate to be coated may be pre-heated before the application of the powder composition, and then either heated after the application of the powder or not.
  • gas is commonly used for various heating steps, but other methods, e.g., microwaves, IR or NIR are also known.
  • the powder coating compositions according to the invention can be applied directly on the substrate surface or on a layer of a primer which can be a liquid or a powder based primer.
  • the powder coating compositions according to the invention can also be applied as a coating layer of a multilayer coating system based on liquid or powder coats, for example, as powder clear coat layer applied onto a color- imparting and/or special effect-imparting base coat layer or a pigmented one-layer powder or liquid top coat applied onto a prior coating.
  • the applied and melted powder coating layer can be cured by thermal energy.
  • the coating layer may, for example, be exposed by thermal energy such as convective, gas and/or radiant heating, e.g., infra red (IR) and/or near infra red (NIR) irradiation, as known in the art, to temperatures of, e.g., 100°C to 300°C, preferably of 140°C to 250°C, more preferably at low temperature in a range of 140°C to 170°C, most preferably 140°C to 160°C (object temperature).
  • thermal energy such as convective, gas and/or radiant heating, e.g., infra red (IR) and/or near infra red (NIR) irradiation, as known in the art, to temperatures of, e.g., 100°C to 300°C, preferably of 140°C to 250°C, more preferably at low temperature in a range of 140°C to 170°C, most
  • the coating composition of the invention is suitable to be applied to metallic substrates and to be cured at low temperature, in a range of preferably 140°C to 160°C (object temperature) and then to be over-coated with additional layer(s) of the coating composition of the invention and curing the over-coated layer(s) at a temperature higher then 170°C, for example, at temperature in a range of 180°C to 200°C (object temperature), without any damages of the previous coating cured at low temperature.
  • the powder coating composition can also be cured by high energy radiation known by a skilled person.
  • UV (ultraviolet) radiation or electron beam radiation may be used as high-energy radiation. UV-radiation is preferred. Irradiation may proceed continuously or discontinuously.
  • Dual curing may also be used. Dual curing means a curing method of the powder coating composition according to the invention where the applied
  • composition can be cured, e.g., both by UV irradiation and by thermal curing methods known by a skilled person.

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

Abstract

La présente invention concerne une composition de revêtement pulvérulente comprenant A) de 1 à 99 % en poids d'au moins une résine (méth)acrylique fonctionnalisée par glycidyle ayant une polarité modifiée, B) de 1 à 99 % en poids d'au moins une résine de réticulation fonctionnalisée par carboxyle (durcisseur) et C) de 0,05 à 50 % en poids d'au moins un additif de revêtement, et facultativement, un pigment et/ou une charge, les % en poids étant basés sur le poids total de la composition de revêtement pulvérulente, produisant des revêtements ayant une résistance améliorée aux rayures et des revêtements appropriés pour une couche de finition à température élevée.
PCT/US2011/066784 2010-12-22 2011-12-22 Composition de revêtement pulvérulente WO2012088394A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US201061426129P 2010-12-22 2010-12-22
US201061426136P 2010-12-22 2010-12-22
US61/426,136 2010-12-22
US61/426,129 2010-12-22

Publications (1)

Publication Number Publication Date
WO2012088394A1 true WO2012088394A1 (fr) 2012-06-28

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WO (1) WO2012088394A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000056821A1 (fr) * 1999-03-19 2000-09-28 Vantico Ag Agents de matite pour systemes thermodurcissables
EP1134264A1 (fr) * 2000-03-17 2001-09-19 Toyo Aluminium Kabushiki Kaisha Compositions de revêtement en poudre, leur procédé de préparation et procédé de formation des revêtements
EP1491567A2 (fr) * 2003-06-26 2004-12-29 Bayer MaterialScience AG Réticulant carboxyfonctionnel pour liant de revêtement en poudre époxyfonctionnel
WO2007075776A2 (fr) * 2005-12-20 2007-07-05 E. I. Du Pont De Nemours And Company Composition de revetement en poudre appropriee pour des substrats thermosensibles
WO2007075777A2 (fr) * 2005-12-20 2007-07-05 E. I. Du Pont De Nemours And Company Composition de revetement en poudre conferant peu de brillant

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000056821A1 (fr) * 1999-03-19 2000-09-28 Vantico Ag Agents de matite pour systemes thermodurcissables
EP1134264A1 (fr) * 2000-03-17 2001-09-19 Toyo Aluminium Kabushiki Kaisha Compositions de revêtement en poudre, leur procédé de préparation et procédé de formation des revêtements
EP1491567A2 (fr) * 2003-06-26 2004-12-29 Bayer MaterialScience AG Réticulant carboxyfonctionnel pour liant de revêtement en poudre époxyfonctionnel
WO2007075776A2 (fr) * 2005-12-20 2007-07-05 E. I. Du Pont De Nemours And Company Composition de revetement en poudre appropriee pour des substrats thermosensibles
WO2007075777A2 (fr) * 2005-12-20 2007-07-05 E. I. Du Pont De Nemours And Company Composition de revetement en poudre conferant peu de brillant
EP1963443A2 (fr) 2005-12-20 2008-09-03 E.I. Du Pont De Nemours And Company Composition de revetement en poudre conferant peu de brillant

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
D.A. BATES: "The Science of Powder Coatings", vol. 1, 2, 1990, GARDINER HOUSE, pages: 62 - 70

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