EP0986597A1 - Compositions de revetements en poudre a base de polyester epoxyde - Google Patents

Compositions de revetements en poudre a base de polyester epoxyde

Info

Publication number
EP0986597A1
EP0986597A1 EP97922931A EP97922931A EP0986597A1 EP 0986597 A1 EP0986597 A1 EP 0986597A1 EP 97922931 A EP97922931 A EP 97922931A EP 97922931 A EP97922931 A EP 97922931A EP 0986597 A1 EP0986597 A1 EP 0986597A1
Authority
EP
European Patent Office
Prior art keywords
acid
polyester
iii
anhydride
solid
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP97922931A
Other languages
German (de)
English (en)
Inventor
Charles John Stark
Edward John Marx
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Resolution Research Nederland BV
Original Assignee
Shell Internationale Research Maatschappij BV
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 Shell Internationale Research Maatschappij BV filed Critical Shell Internationale Research Maatschappij BV
Publication of EP0986597A1 publication Critical patent/EP0986597A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/027—Polycondensates containing more than one epoxy group per molecule obtained by epoxidation of unsaturated precursor, e.g. polymer or monomer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • 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
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
    • C08G63/54—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/553—Acids or hydroxy compounds containing cycloaliphatic rings, e.g. Diels-Alder adducts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91—Polymers modified by chemical after-treatment
    • C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/918—Polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation

Definitions

  • Thermosetting powder coatings with some degree of exterior durability can be prepared from polyester and acrylic-based resins combined with suitable co-reactants .
  • exterior grade epoxy group- containing materials are exemplified by triglycidyl isocyanurate (TGIC) and glycidyl methacrylate (GMA) containing acrylic resins.
  • TGIC-based powder coatings do not have sufficient weatherability, as evidenced by loss of gloss and discoloration.
  • acrylic materials generally have superior weatherability, they are known to have poor physical properties!
  • a curable coating powder composition comprising:
  • the epoxidized polyester must be friable and non- sintering to be useful for powder coatings applications.
  • the polyester sinters if it agglomerates (sticks together) at room temperature within one week and cannot be readily redispersed.
  • the solid epoxidized polyester preferably has a melting point of at least 100 °C to obtain good performance . It has been found that solid epoxidized polyesters useful for powder coatings applications can be prepared by epoxidizing a polyester having a Tg of preferably greater than 50 °C, a melting point of at least 90 °C and a viscosity (ICI Cone & Plate viscosity) of at most 50 Poise at 200 °C.
  • Such polyesters can be prepared by reacting the hereinbefore specified components (i)-(iv) in the hereinbefore specified molar ratio.
  • the total acid to hydroxyl equivalent ratio is from 0.85 to 1 to about 0.95 to 1, the equivalent ratio of (i) to (iii) from 4:1 to 1:4, and more preferably from about 2:1 to 1:2; and an equivalent ratio of (ii) to (iv) of 100:0 to 12.5:1.
  • the reaction is typically carried out by heating the mixture at a temperature within the range of from 150 °C, preferably from 170 °C, to 240 °C, preferably to 230 °C until the acid value of the reaction mixture reaches 5 or less, preferably less than 2.
  • the reaction mixture can also contain inert organic solvents, for example, ketones such as 2-butanone, 4-methyl-2-pentanone and hydrocarbons such as xylene and toluene .
  • a catalyst can be added to facilitate the completion of the reaction.
  • Such catalysts include for example, those prepared from titanium, zirconium, tin and antimony, as well as other conventional catalysts used in polyesterification reactions.
  • the solid polyester resins produced can be recovered by conventional methods.
  • the alcohol is preferably a polyhydric alcohol having 5-50 carbon atoms and two to four hydroxyl groups per molecule. Small amounts, at most 15 equivalent percent, preferably less than 10 equivalent percent, if any, of the total hydroxyl content, of polyhydric alcohols having 4 carbon atoms or less or monohydric alcohols may also be present in the reaction mixture.
  • Examples of the tetrahydrophthalic acids or anhydrides useful for preparing the solid polyester include, cyclohex-4-ene-l, 2-dicarboxylic anhydride, 3 -methylcyclohex-4 -ene- 1 , 2 -dicarboxylic anhydride , 4 -methylcyclohex-4 -ene- 1 , 2 -dicarboxylic anhydride , cyclohex-4-ene-l, 2 -dicarboxylic acid, 3-methylcyclohex- 4 -ene- 1, 2 -dicarboxylic acid, 4-methylcyclohex-4-ene- 1, 2 -dicarboxylic acid, and mixtures thereof.
  • Examples of the cycloaliphatic polyols useful for preparing the solid polyester include cyclohexanedimethanol and hydrogenated bisphenol A, and mixtures thereof.
  • Examples of the saturated polycarboxylic acids useful for preparing the solid polyester include hexahydrophthalic anhydride, hexahydrophthalic acid, 1 , 4-cyclohexanedicarboxylic acid, the dimethylester of cyclohexanedicarboxylic acid, and mixtures thereof.
  • Examples of the polyhydric alcohols, component (iv) include trimethylolpropane, neopentyl glycol, trimethylolethane, pentaerythritol, and mixtures thereof.
  • Examples of the polyhydric alcohol having 4 carbon atoms or less include ethylene glycol, 1 , 3-propanediol , 1, 4-butanediol .
  • Examples of the monohydric alcohols include butanol, 2-ethyl-l-hexanol and cyclohexanol .
  • the solid polyesters can be epoxidized by any conventional epoxidation method such as disclosed in U.S. Patent Nos . 5,244,985, 3,493,631 and 2,928,805.
  • the solid polyesters can be epoxidized by treatment with acid solutions such as peracetic acid, performic acid, generated separately or in-situ from formic acid and hydrogen peroxide in the presence of a strong acid or an acidic resin, or mixtures of molybdic acid and hydrogen peroxide, in the presence of a sufficient quantity of a base such as sodium carbonate, sodium bicarbonate or disodium hydrogen phosphate to neutralize the contained strong acid, at a temperature within the range of from 0 °C, preferably from 20 °C, to 70 °C, preferably to 40 °C.
  • the resulting epoxidized solid polyesters preferably have WPE (weight per equivalent of epoxy functionality) values within the range of 350 to 1500.
  • the solid, friable epoxidized polyesters are recovered by conventional methods.
  • the carboxylic acid curing agent must also be solid and friable to be useful for powder coatings applications. It has been found that such a carboxylic acid component useful as a curing agent for powder coatings application must have an acid equivalent weight within the range of from 100 to 1500 and preferably from 110 to 900. Such a carboxylic acid preferably has 10 to 100 carbon atoms and two to four carboxyl groups, more preferably two carboxyl groups per molecule on average, provided it has an acid equivalent weight within the range of from 100 to 1500.
  • the polycarboxylic acids include, straight or branched chain solid, preferably crystalline, alkanoic acids such as dodecanedioic acid and sebacic acid.
  • Another preferable polycarboxylic acid can be prepared by reacting a mixture, including at least one cycloaliphaticdicarboxylic acid or anhydride and at least one polyhydric alcohol having 5-50 carbon atoms in an acid to hydroxyl equivalent ratio of less than 2:1, preferably 1.2:1, to 2:1, preferably to 1.4:1.
  • a mixture of more than one polyhydric alcohol is preferred to obtain optimum performance and ease of handling.
  • a curable coating powder composition comprises (a) the solid epoxidized polyester and (b) the acid functional component.
  • the amount of (a) to (b) will generally be within plus or minus 35 percent of the stoichiometric amount.
  • the ratio may be adjusted to compensate for the type of catalyst, cure conditions, and desired coating properties. Ratios outside the range can lead to low molecular weight, poorly cross-linked products with less than optimum properties.
  • Conventional powder coating additives such as flow control agents, anti-popping agents, powder flow materials, fillers and pigments may also be included.
  • the curable coating powder composition may further include a small percentage of catalysts such as phosphonium salts (e.g., ethyltriphenylphosphonium iodide) , imidazoles and tin salts (e.g., dibutyltin oxide) in order to increase the crosslinking rate of the coating composition depending on the desired application.
  • catalysts such as phosphonium salts (e.g., ethyltriphenylphosphonium iodide) , imidazoles and tin salts (e.g., dibutyltin oxide) in order to increase the crosslinking rate of the coating composition depending on the desired application.
  • thermosetting coating powder compositions can be prepared by the various methods known to the powder coating industry: dry blending, melt compounding by two roll mill or extruder and spray drying. Typically the process used is the melt compounding process: dry blending the ingredients in a planetary mixer and then melt blending the admixture in an extruder at a temperature within the range of 80 °C to 130 °C . The extrudate is then cooled and pulverized into a particulate blend.
  • thermosetting coating powder composition can then be applied directly to a substrate of, e.g., a metal such as steel or aluminium.
  • a substrate e.g., a metal such as steel or aluminium.
  • Non-metallic substrates such as plastics and composites can also be used.
  • Application can be by electrostatic spraying or by use of a fluidized bed. Electrostatic spraying is the preferred method.
  • the coating powder can be applied in a single sweep or in several passes to provide a film thickness after cure of 2.0 to 15.0 mils.
  • the substrate can optionally be preheated prior to application of a coating powder composition to promote uniform and thicker powder deposition.
  • the powder-coated substrate is baked, typically at 120 °C, preferably from 150 °C, to 205 °C for a time sufficient to cure the powder coating composition, typically from 1 minute to 60 minutes, preferably from 10 minutes to 30 minutes.
  • the coating powder compositions can be applied directly upon bare metal or plastics or composites (e.g., upon untreated, unprimed steel) or upon pretreated surfaces (e.g., phosphatized, unprimed steel).
  • the powder coating compositions can also be applied upon phosphatized steel having a thin (0.8 mils to 2 mils) layer of an electrodeposited primer, cured or uncured before the application of the coating powder composition or over a chip-resistant coating layer as a top coating layer. Examples of a chip-resistant layer is described, for example in U.S. Patent Nos . 5,115,029 and 5,264,503.
  • the electrodeposited primer coating upon the metal substrate can be, for example, a cathodic electrodeposition primer composition.
  • the coating powder composition can be applied directly upon an uncured electrodeposited primer coating and the coating powder can be co-cured by heating at temperatures between 150 °C to 180 °C from 10 minutes to 30 minutes.
  • the powder coating compositions of this invention exhibit good UV resistance, which can be seen by good retention of gloss at 60°, good chemical resistance and have good flow under cure conditions useful for exterior durable powder coatings for automobiles, for general metal surfaces such as wheel covers and architectural components such as window frames.
  • the powder coating compositions of the invention are desirable over conventional liquid systems because they have essentially no volatile organic content .
  • Tetrahydrophthalic anhydride was obtained from Janssen Chemical. Hexahydrophthalic anhydride and hydrogenated bisphenol A were obtained from Milliken Chemical. 1 , 4 -Cyclohexanedimethanol was obtained from either Aldrich Chemical Co. or from Eastman Chemical Co.. 1,4-Cyclohexane dicarboxylic acid was provided by Eastman Chemical Co.. Trimethylolpropane mentioned in the examples below was obtained from Aldrich Chemical Co.. Tin catalyst (Fascat 4100) was obtained from Elf Atochem. Equilibrium peracetic acid (35%) was purchased from Aldrich Chemical Co.. Examples 1-8
  • the acid-functional reactants, HBPA and toluene were placed in a 5.0 litre flask, equipped with a Dean-Stark trap and condenser, thermocouple and overhead stirrer assembly.
  • the flask and its contents were briefly purged with nitrogen; then, a positive pressure of nitrogen was maintained until initiation of sparge.
  • the components were heated to reflux and held for one hour.
  • a solution of 2-butanone (800 grams) and the remaining hydroxyl components were added, allowing for continuous removal of solvent.
  • cyclohexanedimethanol was added along with the other reactants prior to heating.
  • the reaction mixture was warmed slowly to 200 °C, removing solvent and by-product water as required.
  • the reaction mixture was maintained at reflux to facilitate removal of water until the evolution rate of water diminished. Fascat 4100 (a butylated tin oxide) was added all at once, either at the beginning of the reaction or after the initial evolution of water of condensation slowed. After maintaining a temperature of 200 °C for 1-2 hours, the reaction mixture was further warmed to 220 °C and was sparged with nitrogen. This was maintained until the acid number of the resin was less than 1. Acid number was measured by titration of a 50:50 (w/w) toluene/isopropanol solution of resin with 0. IN ethanolic potassium hydroxide. The polyester resin produced was isolated by transferring the contents of the flask to aluminum pans.
  • Fascat 4100 a butylated tin oxide
  • Mn is the theoretical number average molecular weight
  • the polyesters of Examples 1-2 and 5-8 have melting points of above 90 °C and viscosity measurements of less than 50 Poise at 200 °C .
  • Example 4 is provided as a comparative example with the melting point too low.
  • Example 3 is provided as a comparative example with the viscosity too high.
  • the acid to OH ratio of Example 7 is such as to obtain a low viscosity value suitable for processing in powder coating applications.
  • Examples 9-13 Preparation of solid epoxidized polyester
  • polyesters obtained above were dissolved in toluene or methylene chloride (25/75-40/60 w/w) and reacted with equilibrium 35% peracetic acid at 25 to
  • reaction mixture was treated with sufficient sodium carbonate to neutralize the sulfuric acid contained in the peracetic acid.
  • epoxidized polyester was isolated in one of two ways .
  • method A the reaction mixture was condensed under reduced pressure to remove water, unreacted hydrogen peroxide, peracetic acid and acetic acid as well as some solvent. The residue was diluted to 25% solids with toluene or methylene chloride and either filtered or washed
  • reaction mixture after completion of the epoxidation reaction was diluted to 25% solids as above then filtered; afterwards, the mixture was washed 4-5 times with water and condensed by distillation and sparging as described above.
  • the WPE weight per equivalent of epoxy functionality
  • Mettler melting point M.P. in degree centigrade
  • ICI Cone & Plate viscosity at 200 °C are listed below in Table 3.
  • the WPE was determined by titration of a dichloromethane/acetic acid solution of resin and tetraethylammonium bromide with standardized 0.1 N perchloric acid in acetic acid to a crystal violet endpoint .
  • CHDA cyclohexane dicarboxylic acid
  • HHPA hexahydrophthalic anhydride
  • CHDM 1, 4 -cyclohexanedimethanol
  • TMP trimethylolpropane
  • a Acid functional polyester resin from DSM A Acid functional polyester resin from DSM. Acid
  • compositions were processed using a typical coating powder manufacturing process: Intensive premix, high shear melt compounding (extrusion) , grinding and sieving through a 200 mesh screen. Powder Coating Performance
  • Coatings were electrostatically sprayed to about two mils cured film thickness on "type S" Q-Pane. _s and cured as listed
  • EMMAQUA 60° gloss retention 65-85%, 5 Yr. 50%, 3 Yr.
  • PCI Powder Coating Institute Test Procedure #6.
  • the powder coating of the invention has superior weatherability and other performance properties at least equivalent to a typical TGIC-polyester powder, Example 19. 60° gloss retention was 97% after 1000 hours for the invention versus 30% after 200 hours for the TGIC- polyester powder.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Paints Or Removers (AREA)

Abstract

Cette invention se rapporte à une composition durcissable à base de polyester époxydé, conçue pour des applications de revêtements en poudre. On fabrique cette composition en époxydant un polyester ayant un point de fusion supérieur ou égal à 90 °C et une viscosité inférieure ou égale à 50 Poise à 200 °C, ledit polyester étant un polyester que l'on prépare en faisant réagir (i) un acide ou anhydride tétrahydrophthalique, (ii) au moins un polyol cycloaliphatique, (iii) au moins un acide polycarboxylique saturé et (iv) éventuellement au moins un autre alcool dans des conditions permettant d'obtenir un polyester solide doté d'un point de fusion d'au moins 90 °C. On obtient ainsi ladite poudre pour revêtement durcissable contenant le polyester époxydé et un agent de traitement solide à base d'acide carboxylique ayant un poids en équivalent acide compris entre 100 et 1500.
EP97922931A 1997-04-25 1997-04-25 Compositions de revetements en poudre a base de polyester epoxyde Withdrawn EP0986597A1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/EP1997/002234 WO1998049215A1 (fr) 1997-04-25 1997-04-25 Compositions de revetements en poudre a base de polyester epoxyde

Publications (1)

Publication Number Publication Date
EP0986597A1 true EP0986597A1 (fr) 2000-03-22

Family

ID=8166612

Family Applications (1)

Application Number Title Priority Date Filing Date
EP97922931A Withdrawn EP0986597A1 (fr) 1997-04-25 1997-04-25 Compositions de revetements en poudre a base de polyester epoxyde

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EP (1) EP0986597A1 (fr)
CA (1) CA2288086A1 (fr)
WO (1) WO1998049215A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ITVI20130240A1 (it) * 2013-09-30 2015-03-31 Rekord S R L Sistema di protezione e finitura per serramenti e relativi serramenti

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2928805A (en) * 1957-04-08 1960-03-15 Armstrong Cork Co Epoxidized resinous polyester containing tetrahydrophthalic anhydride and compositions containing same
US3493631A (en) * 1967-11-16 1970-02-03 Ppg Industries Inc Epoxidized polyesters prepared from hydrogenated bisphenols and tetrahydrophthalic acid in equimolar amounts
US3836606A (en) * 1970-03-20 1974-09-17 Koppers Co Inc Unsaturated polyester resins
SE7414789L (fr) * 1973-11-26 1975-05-27 Sumitomo Chemical Co
JPS6011051B2 (ja) * 1980-06-30 1985-03-22 大日本インキ化学工業株式会社 光硬化性組成物
EP0319203A3 (fr) * 1987-11-30 1990-08-29 MITSUI TOATSU CHEMICALS, Inc. Matériaux pour la production de matières à mouler thermodurcissables renforcées par des fibres
US5244985A (en) * 1991-03-29 1993-09-14 New Japan Chemical Co., Ltd. Epoxidized polyesters and method of production thereof
JPH0632872A (ja) * 1992-07-17 1994-02-08 New Japan Chem Co Ltd エポキシ樹脂組成物
JPH0762064A (ja) * 1993-08-26 1995-03-07 New Japan Chem Co Ltd 熱硬化性エポキシ樹脂組成物

Non-Patent Citations (1)

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Title
See references of WO9849215A1 *

Also Published As

Publication number Publication date
WO1998049215A1 (fr) 1998-11-05
CA2288086A1 (fr) 1998-11-05

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