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WO1997000281A1 - Composition de revetement pulverisable presentee dans deux emballages - Google Patents

Composition de revetement pulverisable presentee dans deux emballages Download PDF

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Publication number
WO1997000281A1
WO1997000281A1 PCT/US1996/010330 US9610330W WO9700281A1 WO 1997000281 A1 WO1997000281 A1 WO 1997000281A1 US 9610330 W US9610330 W US 9610330W WO 9700281 A1 WO9700281 A1 WO 9700281A1
Authority
WO
WIPO (PCT)
Prior art keywords
anhydride
composition according
chemical compound
hydroxyl
molecular weight
Prior art date
Application number
PCT/US1996/010330
Other languages
English (en)
Inventor
Robert John Barsotti
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
Priority to AU62795/96A priority Critical patent/AU6279596A/en
Publication of WO1997000281A1 publication Critical patent/WO1997000281A1/fr

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
    • C08G59/18—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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules

Definitions

  • This invention concerns a two-package (known as a 2K) coating composition having a low volatile organic content (VOC).
  • a 2K coating composition having a low volatile organic content (VOC).
  • the exterior panels of many automobiles and other outdoor articles are coated with a multilayer finish that contains a colorcoat or basecoat layer and a clearcoat layer.
  • Basecoat- clearcoat systems have found wide acceptance in the past decade as automotive finishes. Continuing effort has been directed to such coating systems to improve the overall appearance, the clarity of the topcoat, and the resistance to deterioration, particularly environmental etching. Further effort has been directed to the development of coating compositions having low volatile organic content (VOC) for purposes of improved environmental safety.
  • VOC volatile organic content
  • a common coating composition contains epoxy resins and polymers which include cyclic anhydrides such as maleic anhydride and itaconic anhydride polymers and copolymers reacted with epoxy functional compounds.
  • Other efforts to improve coating properties have suggested use of hydroxyl resins in combination with isocyanates to form urethane coatings.
  • U.S. 4,755,581 concerns coating compositions having epoxy and hydroxyl functionality on separate molecules. The patent does not suggest the differential cure rate necessary to maximize solids content. Applicants effect solids maximization by use of a binder component that is normally expected to be volatile at the cure temperature, a very active catalyst, and epoxy and hydroxyl functionality in the same molecule.
  • This invention concerns a heat-curable, two-package sprayable coating composition with a volatile organic content of no more than about 2.5 pounds per gallon and a binder that comprises: i) an organic chemical compound having a weight average molecular weight less than about 2,000, a polydispersity not exceeding about 1.5, and functionality "A”; ii) an organic chemical compound having a weight average molecular weight less than about 2,000, a polydispersity not exceeding about 1.5, and functionalities "B” and “C”; and iii) an optional catalyst to promote a differential reaction rate of "A” with "B” and "C”; wherein: one of components i and ii is normally volatile at the cure temperature; functionality "A” and “B” react very rapidly with each other upon mixing to build molecular weight without crosslinking, while retaining the volatile component; functionality "C” reacts with the reaction product of "A” and
  • Preferred functionality "A” is selected from one or more of anhydride, hydroxyl, amine, isocyanate, carboxylic acid, aziridine, carbodiimide, acrylate, methacrylate, and the like.
  • Preferred functionality "B” is selected from one or more of anhydride, hydroxyl, amine, isocyanate, carboxylic acid, aziridine, carbodiimide, acrylate, methacrylate, and the like.
  • polydispersity is meant weight average molecular weight divided by number average molecular weight, both measured by gel permeation chromotography.
  • Preferred functionality “C” is selected from one or more of hydroxyl, isocyanate, melamine, epoxy, carboxylic acid, anhydride, ketamine, aldimine, carbonate, oxazoline, silane, and the like. It is common to use low molecular weight volatile compounds, such as solvents, to lower the viscosity of a coating for spray application. These compounds, because of their volatility, lower the measured weight solids of the coating and thus increase VOC. This invention concerns a method of reacting these types of volatile compounds into the film to preclude evaporation, thus reducing VOC.
  • Typical representative "A” plus “B” reactions (very rapid): anhydride + hydroxyl anhydride + amine isocyanate + primary amine isocyanate + secondary amine acid + aziridine acid + carbodiimide amine + pendant acrylate/methacrylate.
  • Typical "C” plus reaction product of "A+B” and/or "A” (slower reaction rate than above): hydroxyl + isocyanate hydroxyl + melamine hydroxyl + epoxy acid + epoxy anhydride + epoxy amine + epoxy isocyanate + ketamine isocyanate + aldimine isocyanate + epoxy isocyanate + acid acid + melamine carbonate + amine acid + oxazoline silane + silane silane + hydroxyl.
  • the product of "A" plus “B” should be soluble or compatible in the final coating or be able to melt at the cure temperature to form a uniform coating film.
  • CM is a central moiety
  • R 1 is an organic moiety
  • n is a number of pendant anhydride groups that averages greater than one.
  • the central moiety can be aliphatic, cycloaliphatic or aromatic, with a plurality of anhydride groups bonded to it.
  • Suitable non-polymeric central moieties are those derived from multifunctional alcohols such as pentaerythritol, trimethylolpropane and neopentyl glycol.
  • the multifunctional alcohols are reacted with cyclic, monomeric anhydride such as methyl hexahydrophthalic anhydride to give a multifunctional acid- containing moiety.
  • the resulting product is then reacted with ketene to form the pendant anhydride.
  • the central moiety is linked to more than one noncyclic anhydride moiety, on average. It is preferably linked to at least 2 noncyclic anhydride groups on average and more preferably to at least 3 noncyclic anhydride groups on average.
  • the anhydride equivalent weight (formula weight per anhydride group) is preferably about 200 to 1000.
  • the molecular weight (weight average) of the anhydride resin is preferably 400 to 1,000, and the anhydride resin preferably has 3 to 4 pendant, noncyclic anhydride moieties bonded to each central moiety.
  • Each anhydride moiety is typically terminated by an organic group (R 1 ). This group is preferably aliphatic and more preferably alkyl.
  • the oligomeric anhydride can optionally contain a polyvalent organic moiety (PVO) that is linked to a plurality of anhydride groups by a plurality of pendant linking groups (LG), as illustrated in the following formula:
  • the linking group (LG) can contain, for example, ester linkages, alkylene groups, ether linkages, urethane linkages and combinations of them.
  • the polyvalent organic group can contain, for example, a polyvalent alkyl or aromatic group.
  • the combination of the polyvalent organic moiety (PVO) and the linking groups (LG) forms the central moiety (CM) as previously described.
  • the central moiety can optionally contain other functional groups in addition to the pendant noncyclic anhydride groups, including pendant acid groups.
  • the molar ratio of pendant noncyclic anhydride groups to pendant acid groups in the oligomeric anhydride is preferably at least about 25:75, more preferably about 50:50, and more highly preferably about 75:25. Most preferably, the anhydride contains substantially no pendant acid groups.
  • the central moiety can also contain minor quantities of cyclic anhydride moieties.
  • an “A” compound is an isocyanate, such as the isocyanurate trimer of hexamethylene diisocyanate which can be reacted with compounds (ii) such as volatile amine/alcohols or anime/aldimines.
  • compounds (ii) such as volatile amine/alcohols or anime/aldimines.
  • Typical specific compounds that meet the recited requirements include compounds that contain both epoxy and hydroxyl functionality such as: sorbitol polyglycidyl ether (DCE- 358 from Dixie Chemical), mannitol polyglycidyl ether, pentaerythritrol polyglycidyl ether, glycerol polyglycidyl ether, low molecular weight epoxy resins such as epoxy resins of epichlorohydrin and bisphenol-A and low molecular weight resins containing glycidyl methaciylate or glycidyl acrylate and a hydroxyl functional monomer such as hydroxy ethyl acrylate.
  • DCE- 358 from Dixie Chemical
  • mannitol polyglycidyl ether pentaerythritrol polyglycidyl ether
  • glycerol polyglycidyl ether low molecular weight epoxy resins such as epoxy resins of epichlorohydrin and bisphenol-A
  • compound (ii) are volatile amine/alcohols or amine/aldimines which can be reacted and retained in the film through rapid reaction with isocyanate functional crosslinkers such as the isocyanurate trimer of hexamethylene diisocyanate.
  • isocyanate functional crosslinkers such as the isocyanurate trimer of hexamethylene diisocyanate.
  • compound (ii) is a volatile epoxy/hydroxyl-containing compound such as glycidol which can react with the anhydrides described with respect to component (i).
  • Optional Catalyst fiiil Compositions of this invention can contain a functional amount of active catalyst to increase the reaction rate between "A" and "B” at temperatures below the bake temperature, preferably at room temperature. This accentuates the difference in rate between the volatile incorporation reaction and the crosslinking reaction.
  • Particularly beneficial catalysts in the anhydride/hydroxyl/epoxy reaction are tertiary amine catalysts such as triethylene diamine, bis(2-dimethyl aminoethyljether and N,N,N 1 ,N l-tetxamethylethylenediamine.
  • compositions of the present invention can contain a surface tension reducing agent in an amount sufficient to wet the surface onto which it is applied.
  • a surface tension reducing agent can be used, depending on the particular coating formulation and the surface onto which it is applied. However, conventional silicone and fluorocarbon surfactants have been found to be satisfactory.
  • the coating compositions of the present invention are formulated into high solids coating systems and can be dissolved in at least one solvent.
  • Preferred solvents include aromatic hydrocarbons such as petroleum naphtha or xylenes; ketones such as methyl amyl ketone, methyl isobutyl ketone, methyl ethyl ketone or acetone; esters such as butyl acetate or hexyl acetate; and glycol ether esters such as propylene glycol monomethyl ether acetate.
  • the coating compositions of the present invention can also contain conventional additives such as pigments, stabilizers, rheology control agents, flow agents, toughening agents and fillers. Such additional additives will, of course, depend on the intended use of the coating composition. Fillers, pigments, and other additives that would adversely affect the clarity of the cured coating will not be included if the composition is intended as a clear coating.
  • epoxy functional oligomers such as di- and polyglycidyl esters of carboxylic acids, such as Araldite CY-184® from Ciba-Geigy, or XU-71950 from Dow Chemical and cycloaliphatic epoxies, such as ERL-4221 from Union Carbide; and monomeric or polymeric alkylated melamine formaldehyde resins or silane-containing oligomers or resins. Small amounts of high molecular weight acrylic or polyester resins common in the art can also be added.
  • compositions of the present invention are typically applied to a substrate by conventional techniques such as spraying, electrostatic spraying, roller coating, dipping or brushing.
  • a surprising aspect of this invention is the ability to spray these very low VOC coatings with excellent appearance using conventional two component equipment.
  • the substrate is generally prepared with a primer and/ or a colorcoat or other surface preparation prior to coating with the present compositions. Clearcoats of the present coating compositions are preferably applied using conventional techniques such as application over dried waterborne basecoats.
  • the present compositions are cured by heating to a temperature of about 125° to 140°C for a period of about 15 to 90 minutes.
  • the performance characteristics of the final cured coating composition are excellent, providing a combination of excellent gloss and durability to abrasion, sunlight and acid rain.
  • Milldride® MHHPA from Milliken (70/30 weight ratio 44.62 of methyl hexahydrophthalic anhydride and hexahydrophthalic anhydride)
  • BYK-301 silicone flow additive from BYK-Chemie
  • 0.26 bis(2 dimethylaminoethyl) ether Naax A-99 from 1.49
  • Tinuvin 384 UV screener from Ciba Giegy
  • Tinuvin 292 hindered amine light stabilizer from 1.39
  • This composition was sprayed using a 2-component gun over a waterborne basecoat which had received a warm air prebake to remove water. The final coating was baked for 30 minutes at 285°F. The weight solids of this clearcoat at spray was over 96% when measured at 60 min at 110°C. The film had excellent appearance, cure, hardness, and chemical resistance.
  • the system was cured for 30 minutes at 265°F.
  • the spray solids of this clearcoat was over 84% by weight.
  • the film had excellent appearance, cure, hardness and mar resistance.
  • a crosslinking agent was prepared by mixing together 5 moles of adipic acid, 5 moles of azeleic acid, 2 moles of isononanoic acid, and 24 moles of acetic anhydride, reacting the monomers at 140°C while removing acetic acid as a by-product, heating the mixture to 160°C when acetic acid ceased flowing out, and removing an excess of acetic anhydride to terminate the reaction.
  • the resulting linear anhydride was dissolved in propylene glycol monomethyl ether acetate at a concentration of 80% by weight.
  • the linear anhydride has the formula:
  • R is the isononanoic group
  • R' is a blend of adipic and azeleic groups
  • n is about 10.
  • the anhydride resin was prepared from a tetra ⁇ functional half-acid ester.
  • the following constituents were charged to a reaction vessel equipped with a heating mantle, reflux condenser, thermometer, nitrogen inlet, and stirrer:
  • Portion 1 was charged into the reaction vessel, heated to 180°C under a nitrogen blanket and held for 30 minutes. After the hold period, the reaction mixture was cooled and Portion 2 added.
  • the solution prepared above was used to make a linear pendant anhydride.
  • the solution was charged into a 5L flask equipped with a stirrer and a gas inlet tube. The gas inlet tube was attached to a ketene generator and ketene was bubbled through the solution until all of the acid groups were converted to anhydride groups. Reaction progress was monitored via infrared analysis. Solvent was then removed under vacuum to give a linear pendant anhydride having 78% weight of solids and anhydride eq. wt. of 329 ⁇ 4 (on solution basis).
  • Resimene BM-9539 (melamine resin from Monsanto) 11.2
  • Example 2 can be modified by adding a low molecular weight acrylic resin containing glycidyl methacrylate and gamma- methacryloxypropyl trimethoxy silane to Part 2 to improve chemical resistance and marring.
  • a typical resin which can be added at a 10% level on binder solids contains styrene/butyl methacrylate/butyl acrylate/glycidyl methacrylate/gamma- methacryloxypropyl trimethoxy silane (15/25/20/15/25 by weight %).
  • the weight average molecular weight of this resin would be approximately 4,000.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)

Abstract

Une composition de revêtement pulvérisable présentée dans deux emballages comporte un liant qui comprend, dans un emballage, un composé chimique ayant une valence fonctionnelle 'A', dans un autre emballage, un composé chimique ayant des valences fonctionnelles 'B' et 'C'. Les valences fonctionnelles 'A' et 'B' réagissent rapidement de façon à établir un poids moléculaire sans réticulation alors que la valence fonctionnelle 'C' réagit avec le produit de réaction de 'A' et 'B' ou avec 'A' ou avec les deux, cette réaction se faisant plus lentement que la réaction de 'A' avec 'B', et forme un film réticulé lors du durcissement.
PCT/US1996/010330 1995-06-19 1996-06-13 Composition de revetement pulverisable presentee dans deux emballages WO1997000281A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU62795/96A AU6279596A (en) 1995-06-19 1996-06-13 Two-package sprayable coating composition

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US49217995A 1995-06-19 1995-06-19
US08/492,179 1995-06-19

Publications (1)

Publication Number Publication Date
WO1997000281A1 true WO1997000281A1 (fr) 1997-01-03

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PCT/US1996/010330 WO1997000281A1 (fr) 1995-06-19 1996-06-13 Composition de revetement pulverisable presentee dans deux emballages

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AU (1) AU6279596A (fr)
WO (1) WO1997000281A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6037014A (en) * 1997-11-06 2000-03-14 The Edgington Co. Coating composition
WO2001025356A1 (fr) * 1999-10-02 2001-04-12 Basf Aktiengesellschaft Melange de substances solides contenant des liaisons activables par radiation actinique
GB2472474B (en) * 2009-12-14 2012-04-11 Pro Teq Surfacing Uk Ltd Method for applying a coating to a surface
WO2019110808A1 (fr) * 2017-12-07 2019-06-13 Basf Coatings Gmbh Revêtements pour automobiles résistants aux rayures et à l'ongle

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0257512A2 (fr) * 1986-08-21 1988-03-02 Ppg Industries, Inc. Composition de revêtement thermodurcissable à haute teneur en matière sèche à base d'époxydes contenant des groupes hydroxyliques et d'anhydrides
US5214104A (en) * 1990-09-01 1993-05-25 Bayer Aktiengesellschaft Compositions suitable as binders and their use in coating and sealing compositions
US5418297A (en) * 1991-11-26 1995-05-23 Kansai Paint Company, Limited Crosslinking agent and curable composition
WO1996001864A1 (fr) * 1994-07-08 1996-01-25 E.I. Du Pont De Nemours And Company Composition servant de revêtement de finition a faible teneur en composes organiques volatils

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0257512A2 (fr) * 1986-08-21 1988-03-02 Ppg Industries, Inc. Composition de revêtement thermodurcissable à haute teneur en matière sèche à base d'époxydes contenant des groupes hydroxyliques et d'anhydrides
US5214104A (en) * 1990-09-01 1993-05-25 Bayer Aktiengesellschaft Compositions suitable as binders and their use in coating and sealing compositions
US5418297A (en) * 1991-11-26 1995-05-23 Kansai Paint Company, Limited Crosslinking agent and curable composition
WO1996001864A1 (fr) * 1994-07-08 1996-01-25 E.I. Du Pont De Nemours And Company Composition servant de revêtement de finition a faible teneur en composes organiques volatils

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6037014A (en) * 1997-11-06 2000-03-14 The Edgington Co. Coating composition
WO2001025356A1 (fr) * 1999-10-02 2001-04-12 Basf Aktiengesellschaft Melange de substances solides contenant des liaisons activables par radiation actinique
US6780897B1 (en) 1999-10-02 2004-08-24 Basf Coating Ag Solid substance mixture containing bonds that can be activated by actinic radiation and the use thereof
GB2472474B (en) * 2009-12-14 2012-04-11 Pro Teq Surfacing Uk Ltd Method for applying a coating to a surface
US9017769B2 (en) 2009-12-14 2015-04-28 Pro-Teq Surfacing (Uk) Ltd Method and apparatus for applying a coating to a surface
WO2019110808A1 (fr) * 2017-12-07 2019-06-13 Basf Coatings Gmbh Revêtements pour automobiles résistants aux rayures et à l'ongle
CN111433300A (zh) * 2017-12-07 2020-07-17 巴斯夫涂料有限公司 耐划痕和抗划伤的汽车涂料
US11884837B2 (en) 2017-12-07 2024-01-30 Basf Coatings Gmbh Scratch and mar resistant automotive coatings

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Publication number Publication date
AU6279596A (en) 1997-01-15

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