WO1998050444A1 - Compositions de revetement contenant des composants epoxy et aldimine - Google Patents

Compositions de revetement contenant des composants epoxy et aldimine Download PDF

Info

Publication number
WO1998050444A1
WO1998050444A1 PCT/US1997/007464 US9707464W WO9850444A1 WO 1998050444 A1 WO1998050444 A1 WO 1998050444A1 US 9707464 W US9707464 W US 9707464W WO 9850444 A1 WO9850444 A1 WO 9850444A1
Authority
WO
WIPO (PCT)
Prior art keywords
aldimine
epoxy
composition according
isocyanate
group
Prior art date
Application number
PCT/US1997/007464
Other languages
English (en)
Inventor
Lee R. Harper
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 PCT/US1997/007464 priority Critical patent/WO1998050444A1/fr
Publication of WO1998050444A1 publication Critical patent/WO1998050444A1/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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • C08G18/3253—Polyamines being in latent form
    • C08G18/3256—Reaction products of polyamines with aldehydes or ketones
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
    • C08G18/6237—Polymers of esters containing glycidyl groups of alpha-beta ethylenically unsaturated carboxylic acids; reaction products 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
    • 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
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4014—Nitrogen containing compounds
    • C08G59/4042—Imines; Imides
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes

Definitions

  • This invention relates to two-package nonaqueous coating compositions comprising (i) an admixture of an epoxy and an aldimine (precursor) and (ii) an isocyanate that reacts with (i).
  • the coating compositions described herein are characterized by good storage stability and by improved overall appearance, clarity and resistance to deterioration, particularly that caused by environmental etching.
  • R is the residue from a compound having at least two amino functionalities selected from the group isophorone-diamine, methyl substituted or nonsubstituted bis-4-amino-cyclohexylmethane, 1,6-diamino hexane, l,5-diamino-3-methylpentane and other polyamines;
  • R' is the residue of a monofunctional aldehyde selected from the group isobutyraldehyde, n-butyraldehyde, pivaldehyde, and cyclohexane aldehyde;
  • n is at least 2; and the ratio of epoxy-containing material to aldimine is from 6 to 1 to 1 to 6 by weight.
  • This invention also concerns the precursor described above, designated as (i), in combination with an isocyanate, designated (ii), having an average isocyanato functionality above about 2.0, said isocyanate being selected from the group aliphatic and cycloaliphatic diisocyanate trimers, dimers and other oligomers and mixtures thereof. Examples are the poly- isocyanurate of hexamethylene diisocyanate and analogs, the trimer of isophorone diisocyanate, and other polyfunctional derivatives and oligomers of diisocyanates.
  • This invention also concerns a coating composition comprising (i),
  • the epoxy material is selected from the group known as polyglycidyl ethers or polyglycidyl esters, as well as poly cyclohexane epoxides.
  • polyglycidyl ethers are the sorbitol or mannitol polyethers and epoxy resins such as epoxy resins of epichlorohydrin and bis-phenol A or hydrogenated bis-phenol A.
  • polyglycidyl esters are diglycidyl esters of cyclohexane- 1,2-dicarboxylic acid, triglycidyl esters of tricarboxylic acids such as trimellitic acid, and the like.
  • Examples of useful cyclohexane epoxide compounds are bis 2,3-epoxy cyclohexane esters known as ERL-4221 (Union Carbide) [(3',4'-epoxycyclohexylmethyl) 3,4-epoxycyclohexanecarboxylate] and similar cycloaliphatic di- or poly- epoxide compounds.
  • ERL-4221 Union Carbide
  • epoxy-containing materials useful in admixture with aldimines to form precursors (i) of this invention are bis(3,4-epoxy-6- methylcyclohexylmethyl) adipate; diglycidyl azelate, sebacate, adipate, or the like; and copolymers of glycidyl methacrylate and butyl methacrylate, and the like.
  • Aldimines bis(3,4-epoxy-6- methylcyclohexylmethyl) adipate; diglycidyl azelate, sebacate, adipate, or the like; and copolymers of glycidyl methacrylate and butyl methacrylate, and the like.
  • Useful aldimines include the bis-aldimine of isobutyraldehyde and bis(4-amino-cyclohexylmethane) and the bis-aldimine of isobutyraldehyde and isophorone-diamine and the bis- dimine of isobutyraldehyde and methylpentane diamine and the bis-aldimine of isobutyraldehyde and hexamethyldiamine, and the like.
  • the ratio of epoxy material to aldimine will be in the weight ratios of 6: 1 to 1:6, preferably 2: 1 to 1:2.
  • the precursor adds hardness, flexibility, and appropriate crosslink density and Tg to the coating compositions of the invention.
  • the choice of epoxy and ratios is made in order to conform to end use requirements of durability, VOC, hardness, chemical resistance, solvent resistance and appearance.
  • polyisocyanates can be employed to form coating compositions of this invention in combination with (i) and (iii).
  • Preferred isocyanates include the trimer (isocyanurate) of hexamethylene diisocyanate, isophorone diisocyanate, diisocyanate/triol adducts, and mixtures of these.
  • the weight ratio of (i) to (ii) is from 8:1 to 1:1, preferably, 4:1 to 2:1.
  • Catalysts are those which contain active hydrogen(s) to facilitate reaction of (i) and (ii) and include water, secondary and/or tertiary alcohol(s), carboxylic acids and anhydrides. Enolic and/or phenolic alcohols can be used. Acetic acid is representative of the acids that are useful. Use of amines and ammonia is also contemplated.
  • the catalytic component will be less than about 2% by weight of the total composition of (i), (ii) and (iii).
  • the catalyst can be added as a vapor, liquid or dissolved solid, or solutions of any of the above., preferrably as a component of (i).
  • catalysts are the metal salts such as Sn, Zn and Fe salts, tertiary amines and the like.
  • metal salts such as Sn, Zn and Fe salts, tertiary amines and the like.
  • tin esters such as dibutyl tin dilaurate.
  • the precursors of this invention and the coating composition comprising (i), (ii) and (iii), can also contain coating adjuvants typically employed to improve stability, handling, sprayability, UV stability, endurance, flow, leveling, anti-cratering, and the like.
  • 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 in an amount sufficient to wet the surface onto which it is applied.
  • surfactants 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 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 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
  • 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 at room temperature or by heating to a temperature of up to about 125° to 150°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.
  • the coating clearcoats derived from the disclosed compositions cure rapidly at ambient temperatures and have long activated pot life. They form coatings also useful as primers and single stage enamels for refinish, maintenance and OEM automotive applications.
  • the compositions provide low viscosity without diminishing the cured film properties nor the curing schedule. The prolonged pot-life is beneficial for spraying uniformly over an entire vehicle. Optimization of the cure rate and pot life is readily accomplished by choice of type and amount of catalyst(s).
  • This coating formulation is characterized by use of low molecular weight epoxy-containing oligomers or polymeric epoxy materials in combination with catalysts and coreactants to optimize the balance of cure at various humidity conditions.
  • Preferred embodiments of this invention provide an overall balance of properties in a composition with the appearance and coating performance normally associated with isocyanate-based coatings but at extremely low VOC levels.
  • Epoxy equivalent weight (on solids) 236.67 EXAMPLES Description of materials employed in the Examples are set out in the "Key" following Example 4.
  • Multi-component clear coating compositions were prepared by mixing the following materials just prior to spraying over a basecoat which provided the color required for an automotive refinish coating.
  • the aldimine for Examples 1 and 2 was the bis-aldimine of isobutyraldehyde and bis(4-amino-cyclohexylmethane).
  • the aldimine for Example 3 was the bis-aldimine of isobutyraldehyde and isophorone-diamine.
  • the epoxy ester is diglycidyl- 1,2-cyclohexane dicarboxylate.
  • Multi-component clear coating compositions were prepared by mixing the following materials just prior to spraying over a waterbome basecoat which provides the color required for an automotive refinish coating.
  • the aldimine is that of Example 3 and the epoxy ester is the polymer of Procedure A.
  • Cast film was clear and solvent resistant after drying at ambient conditions for several days.

Landscapes

  • 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)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne une composition de revêtement comprenant (i) un mélange physique d'au moins un composant contenant de l'époxy et d'une aldimine (formant ensemble un précurseur de revêtement) avec (ii) un isocyanate et (iii) un catalyseur permettant de faire réagir le précurseur avec l'isocyanate; le(s) précurseur(s); les revêtements obtenus à partir desdites compositions; et des substrats revêtus avec ces derniers.
PCT/US1997/007464 1997-05-02 1997-05-02 Compositions de revetement contenant des composants epoxy et aldimine WO1998050444A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/US1997/007464 WO1998050444A1 (fr) 1997-05-02 1997-05-02 Compositions de revetement contenant des composants epoxy et aldimine

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1997/007464 WO1998050444A1 (fr) 1997-05-02 1997-05-02 Compositions de revetement contenant des composants epoxy et aldimine

Publications (1)

Publication Number Publication Date
WO1998050444A1 true WO1998050444A1 (fr) 1998-11-12

Family

ID=22260834

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1997/007464 WO1998050444A1 (fr) 1997-05-02 1997-05-02 Compositions de revetement contenant des composants epoxy et aldimine

Country Status (1)

Country Link
WO (1) WO1998050444A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002062908A2 (fr) * 2001-02-02 2002-08-15 Battelle Memorial Institute Revetements epoxydiques a composant unique a faible teneur en compose organique volatil, durcissable a temperature ambiante ,

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3397178A (en) * 1966-10-13 1968-08-13 Gen Mills Inc Hardenable epoxy resin compositions
EP0686654A1 (fr) * 1994-06-06 1995-12-13 Basf Corporation Compositions de revêtement comprenant de l'aldimine et de l'isocyanate et procédé de leur préparation
US5523376A (en) * 1994-12-21 1996-06-04 Bayer Corporation Coating compositions based on aldimines and polyisocyanates containing uretdione groups
US5545705A (en) * 1994-12-14 1996-08-13 Bayer Corporation Aldimines based on 2-methyl-1,5-pentane diamine and their use for the production of polyurea coatings

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3397178A (en) * 1966-10-13 1968-08-13 Gen Mills Inc Hardenable epoxy resin compositions
EP0686654A1 (fr) * 1994-06-06 1995-12-13 Basf Corporation Compositions de revêtement comprenant de l'aldimine et de l'isocyanate et procédé de leur préparation
US5545705A (en) * 1994-12-14 1996-08-13 Bayer Corporation Aldimines based on 2-methyl-1,5-pentane diamine and their use for the production of polyurea coatings
US5523376A (en) * 1994-12-21 1996-06-04 Bayer Corporation Coating compositions based on aldimines and polyisocyanates containing uretdione groups

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002062908A2 (fr) * 2001-02-02 2002-08-15 Battelle Memorial Institute Revetements epoxydiques a composant unique a faible teneur en compose organique volatil, durcissable a temperature ambiante ,
WO2002062908A3 (fr) * 2001-02-02 2002-09-26 Battelle Memorial Institute Revetements epoxydiques a composant unique a faible teneur en compose organique volatil, durcissable a temperature ambiante ,
US6649673B2 (en) 2001-02-02 2003-11-18 Battelle Memorial Institute Single component room temperature curable low VOC epoxy coatings

Similar Documents

Publication Publication Date Title
EP1226199B1 (fr) Composes a base d'isocyanate sequence et compositions contenant ceux-ci
US5578675A (en) Non-isocyanate basecoat/clearcoat coating compositions which may be ambient cured
US7427647B2 (en) Durable coating compositions containing aspartic amine compounds with improved potlife
US6545117B1 (en) Sprayable coating compositions comprising an oxazolidine functional compound, an isocyanate functional compound, and a compound selected from a mercapto and a sulfonic acid functional compound
EP1581575B1 (fr) Preparations de revetement durables contenant des composes aspartiques
US5492961A (en) Physically drying water-based coating agents and use thereof
US7763354B2 (en) Waterborne 2k coating composition having good pot life
EP0770103B1 (fr) Composition servant de revetement de finition a faible teneur en composes organiques volatils
CA2088130A1 (fr) Polyurethanne carboxy-fonctionnel, et composition de revetement durcissable
CA2196741C (fr) Revetements mats de polyurethane en poudre et leur emploi pour l'enrobage de substrats thermoresistants
EP1237974B1 (fr) Compositions de revetement stables pulverulentes
WO1998050444A1 (fr) Compositions de revetement contenant des composants epoxy et aldimine
CZ289758B6 (cs) (Poly)anhydridy dikarboxylových kyselin, modifikované polyisokyanáty a jejich pouľití
US5837353A (en) Low VOC refinish coating composition
EP1237976B1 (fr) Compositions de revetement en poudre stables formant des finis durables
WO2009024556A1 (fr) Utilisation de polyisocyanates modifiés apolaires
US20210292465A1 (en) Non-aqueous crosslinkable composition with improved appearance
AU741972B2 (en) Oligomeric epoxy/isocyanate systems
WO2013113642A1 (fr) Procédé de réparation et composition d'apprêt
US6426148B1 (en) Oligomeric epoxy/isocyanate systems
JP2983039B2 (ja) 二液型ウレタン塗料用樹脂組成物
WO1997000281A1 (fr) Composition de revetement pulverisable presentee dans deux emballages
MXPA00000757A (es) Sistemas de epoxi/iosocianato oligomericos

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): CA MX

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE

121 Ep: the epo has been informed by wipo that ep was designated in this application
NENP Non-entry into the national phase

Ref country code: CA

NENP Non-entry into the national phase

Ref country code: CA

122 Ep: pct application non-entry in european phase